WO2006134846A1 - Curing accelerator, thermosetting resin composition, photosensitive composition, photosensitive film, permanent pattern and method for forming same - Google Patents

Curing accelerator, thermosetting resin composition, photosensitive composition, photosensitive film, permanent pattern and method for forming same Download PDF

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Publication number
WO2006134846A1
WO2006134846A1 PCT/JP2006/311654 JP2006311654W WO2006134846A1 WO 2006134846 A1 WO2006134846 A1 WO 2006134846A1 JP 2006311654 W JP2006311654 W JP 2006311654W WO 2006134846 A1 WO2006134846 A1 WO 2006134846A1
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Prior art keywords
group
photosensitive
permanent pattern
compound
curing accelerator
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PCT/JP2006/311654
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French (fr)
Japanese (ja)
Inventor
Takashi Tamura
Toshiaki Hayashi
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Fujifilm Corporation
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Publication of WO2006134846A1 publication Critical patent/WO2006134846A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • Curing accelerator thermosetting resin composition, photosensitive composition and photosensitive film, and permanent pattern and method for forming the same
  • the present invention does not cause a reaction at room temperature during storage, is excellent in storage stability, exhibits a curing acceleration effect and a thermal crosslinking effect by heating, initiates a reaction with a resin, cures, and cures
  • Highly sensitive and developable, photosensitive composition exhibiting excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, etc. after development, photosensitive film using the same, and high Fine permanent pattern (protective film, interlayer insulation film, solderale It is sampled patterns) and its efficient formation methods.
  • components such as semiconductors, capacitors and resistors are soldered on the printed wiring board.
  • a soldering process such as IR reflow
  • it corresponds to the unnecessary part of soldering as a protective film and an insulating film.
  • a method of forming a permanent pattern is adopted.
  • a solder resist is preferably used as the permanent pattern of the protective film.
  • solder resist a thermosetting material is often used, and a method in which this is applied by screen printing is generally used.
  • the screen printing method has a limit in terms of resolution, and a photo solder resist that forms an image by the photolithographic method has been actively used.
  • alkali development type photo solder resists that can be developed with a weak alkali solution such as sodium carbonate solution are mainly used in terms of working environment and global environment conservation.
  • a manufacturing method is used in which a liquid solder resist is applied to one side of a substrate on which wiring has been formed by screen printing, spray coating, dip coating, and the like, and then dried on the opposite side. .
  • the alkali development type photo solder resist as described above as a main component, a compound in which an acid group for imparting an ethylenically unsaturated double bond and alkali developability to an epoxy compound is introduced (epoxy acrylate). And an addition-polymerizable compound (monomer) having an ethylenically unsaturated double bond is generally used, and specifically disclosed in Patent Document 1.
  • the solder resist described in Patent Document 1 has a high surface hardness after post-baking and excellent chemical resistance, but the surface tack remains and dust tends to adhere to increase the defects, or the photo resist. There is a problem of deteriorating handling properties such as contamination of the mask.
  • the tack remains on the surface because the molecular weight of epoxy acrylate, which is a binder soluble in an alkaline aqueous solution, is as low as several hundreds, and the monomer is usually a liquid or semi-solid with a high boiling point. It is believed that there is.
  • the exposure sensitivity of such a solder resist is usually as low as 300 to 1,000 mj / cm 2, which is becoming a bottleneck in speeding up the production line, and further sensitivity improvement is required.
  • the ability to increase the blending amount of the monomer is effective for increasing the sensitivity. When a large amount of monomers are blended, the problem that the surface tack is further deteriorated occurs, and no solution has been found.
  • LDI laser direct imaging system
  • the solder resist used in the LDI is required to have an exposure sensitivity of 100 mj / cm 2 or more in order to cope with a UV laser of 365 nm or 405 nm. For this reason, a film-type solder resist that is easy to obtain high sensitivity is required.
  • the solder resist described in Patent Document 1 is made into a film, the tackiness of the surface is strong, the support or protective film is difficult to peel off from the photosensitive layer, and the handling property is poor. Even frozen storage can only be stored for a few months, and there is a problem of storage stability.
  • it has a drawback.
  • Patent Document 2 uses a binder soluble in a relatively high molecular weight alkaline aqueous solution having a molecular weight of 10,000 or more, has a small surface tackiness, excellent heat resistance, and relatively storage stability.
  • a good solder resist has a problem that the surface hardness is low and the laminate property is inferior. Therefore, it is necessary to apply a liquid monomer as an undercoat layer in advance to the outermost layer of a printed wiring board on which wiring has been formed without generating bubbles, which makes the process complicated and inferior in handleability. have.
  • the cured film is flexible as a result of the use of a copolymer component that forms a rigid polymer such as methyl methacrylate and styrene (Tg of each homopolymer is 105 ° C or higher and 100 ° C). It is considered that the surface hardness does not increase due to chipping, and that sufficient fluidity cannot be obtained in the heating and laminating process under vacuum conditions, causing bubble generation. Furthermore, there is a drawback that there is no sensitivity to laser light having a wavelength of 405 nm.
  • the film-type solder resist As a result of this film formation, a binder and a monomer and a thermal cross-linking agent are mixed in the photosensitive layer, so that a cross-linking reaction occurs and storage stability is poor.
  • a curing accelerator for a thermosetting resin composition such as an epoxy resin composition
  • a reaction does not occur during storage, but it has a property of reacting and curing by heating, so-called latent. Proposals have been made using photocuring accelerators.
  • Non-patent Document 1 and Patent Document 3 proposals have been made that contain a salt composed of zinc 2-ethylhexylate and triethanolamine, and a salt composed of triethylenediamine and an aliphatic carboxylic acid (Non-patent Document 1 and Patent Document 3). reference). These are intended to reduce solubility, suppress reaction activity, and improve storage stability by using a complex accelerator as a curing accelerator.
  • thermosetting agent a thermosetting agent
  • the amine compound since the amine compound has an action of suppressing radical polymerization, it has a sensitivity. The problem is that high improvement cannot be achieved.
  • a curing accelerator using a simple, inexpensive material with high storage stability and a curing accelerator that can be cured by heat and excellent in storage stability, and excellent in chemical resistance and hardness after curing.
  • Thermosetting resin composition that exhibits dielectric properties and electrical insulation, etc., and the above accelerator can be used to form an image by UV exposure.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 61-243869
  • Patent Document 2 Japanese Patent Laid-Open No. 02-097502
  • Patent Document 3 Japanese Patent Laid-Open No. 11-246651
  • Patent Document 4 Japanese Patent Laid-Open No. 56-155222
  • Patent Document 5 Japanese Unexamined Patent Publication No. 57-100127
  • Patent Document 6 Japanese Unexamined Patent Publication No. 59-053526
  • Patent Document 7 Japanese Unexamined Patent Publication No. 2000-001526
  • Non-Patent Document 1 Nippon Oil & Fats, Endooka IJ (Tokyo Tech) Network Polymer voll 9, No. 4, P2 28—235, 1998
  • An object of the present invention is to solve the conventional problems and achieve the following object. That is, the present invention does not cause a reaction at room temperature during storage, has excellent storage stability, exhibits a curing acceleration effect and a thermal crosslinking effect by heating, initiates a reaction with an epoxy resin compound, and cures.
  • a thermosetting resin composition that expresses the above, and the above-mentioned curing accelerator can be used to form an image by UV exposure, the surface tackiness is small, the laminate and handling properties are good, and the storage stability is excellent.
  • a curing accelerator made of a compound having a structure having a carboxylate group and an amide group in a ratio of 1: 1 in the molecule that generates an amine by external stimulation causes a reaction at low or normal temperature. It has been found that a cured product having excellent storage stability, curing at a rapid reaction at the heat treatment temperature and excellent in surface hardness, alkali resistance and the like can be obtained during heat treatment.
  • thermosetting resin composition having at least the curing accelerator and the epoxy resin compound can be cured by heat and has excellent storage stability, and excellent chemical resistance after curing. It has been found that it exhibits hardness, dielectric properties and electrical insulation.
  • the curing accelerator, a polymer having one or more carboxyl groups and ester groups in one molecule, a polymerizable compound, a photopolymerization initiator, A photosensitive composition having at least a thermal crosslinking agent has excellent storage stability, high sensitivity and excellent developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development. It was found that the storage stability of film-type solder resists can be improved.
  • the present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
  • a curing accelerator characterized by having a structure in which an amine is generated by an external stimulus and a carboxynole group and an amide group are in a ratio of 1: 1 in the molecule.
  • the curing accelerator which does not cause a reaction at a low temperature or a normal temperature and a compound using the curing accelerator can be excellent in storage stability, and can be subjected to heat treatment.
  • a cured product exhibiting a rapid reaction at the heat treatment temperature and excellent in surface hardness, alkali resistance and the like can be obtained.
  • ⁇ 3> According to any one of the above ⁇ 1> to ⁇ 2> represented by any one of the following general formulas (1), (2), (3), (4), (5) and (6) It is a curing accelerator.
  • R ⁇ R 18 represents either a hydrogen atom or a substituent
  • Ai A 6 represents a divalent substituent
  • 1 is a single bond, double bond, and represents one of the divalent substituent.
  • thermosetting resin composition comprising at least an epoxy resin compound and the curing accelerator according to any one of 1 to 3 above.
  • the thermosetting resin composition according to ⁇ 4> is curable by heat and has excellent storage stability. Excellent chemical resistance, hardness, heat resistance, dielectric properties, electrical insulation, etc. can be expressed.
  • thermosetting resin composition according to ⁇ 4> wherein the content of the curing accelerator is 0.01 to 50% by mass.
  • a photosensitive composition comprising at least the curing accelerator according to any one of ⁇ 1> to ⁇ 3>.
  • the photosensitive composition according to ⁇ 6> since it contains the curing accelerator according to any one of ⁇ 1> to ⁇ 3>, it has excellent storage stability and safety, and has a low dielectric constant.
  • the effect accelerator functions as a thermal crosslinking agent, the film strength of the cured region of the photosensitive layer can be increased without adding a thermal crosslinking agent separately.
  • the photosensitive composition according to ⁇ 6> further including (E) a thermal crosslinking agent.
  • the film strength in the cured region of the photosensitive layer can be further improved by the synergistic effect of the thermal crosslinking effect of the curing accelerator and the thermal crosslinking agent.
  • ⁇ 8> The photosensitive composition according to any one of ⁇ 6> Karaku 7>, wherein the content power of (D) the curing accelerator is 0.01 to 40% by mass.
  • the thermal crosslinking agent is at least selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative.
  • the photosensitive composition according to any one of ⁇ 6> to ⁇ 8>, which is one kind.
  • thermo crosslinking agent is a compound represented by any one of the following general formulas (7) to (9): is there.
  • P represents an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene group, or an arylene group
  • Q represents boron.
  • W represents naphthalene having a bond with two X 26 s
  • a 21 A 25 represents a single bond, an alkylene group, or an arylene group.
  • X 21 X 26 represents either OCONH— NHCOO NHCO—
  • R R Represents one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
  • thermo crosslinking agent is an epoxy compound having two or more oxosilane groups in the molecule.
  • thermo crosslinking agent is an oxetane compound having two or more oxetanyl groups in the molecule.
  • thermo crosslinking agent is represented by any one of the following structural formulas (I) and (II):
  • R represents either a hydrogen atom or an alkyl group having from 6 to 6 carbon atoms, and n represents an integer of 0 to 20.
  • ⁇ 16> The photosensitivity according to any one of ⁇ 6>, ⁇ 13>, wherein the polymer (A) contains at least one of a butyl copolymer having a (meth) ataryloyl group and an acidic group in the side chain. It is a composition.
  • X represents any of a hydrogen atom and a substituent containing at least an acidic group
  • ⁇ represents any of a methylene group, an isopropylidene group, and a sulfonyl group
  • n is Represents an integer of 1-20.
  • the polymer is (a) maleic anhydride, (b) an aromatic bull monomer, and (c) a vinyl monomer, which is a homopolymer of the bull monomer.
  • a copolymer obtained by reacting 0.1 to 1.0 equivalents of primary amine compound to the anhydride group of a copolymer comprising a vinyl monomer having a glass transition temperature (Tg) of less than 80 ° C
  • Tg glass transition temperature
  • the photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexarylbiimidazole, oxime derivative, organic peroxide, thio compound, keton compound, aromatic onium salt, or ketoxime.
  • a photosensitive film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to any one of ⁇ 6> to ⁇ 22> on the support. It is.
  • the minimum energy of light used for the exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 100 (mj / cm 2 )
  • the photosensitive film according to the above item 23> is 0.1 to 100 (mj / cm 2 )
  • ⁇ 27> The photosensitive film according to any one of ⁇ 23> to ⁇ 26>, which is long and wound in a roll.
  • the thickness of the photosensitive layer is 3 to 100/1111.
  • the photosensitive layer modulates the light from the light irradiating means by the light modulating means having n picture elements for receiving and emitting the light from the light irradiating means, the light is emitted from the light emitting means.
  • the photosensitive composition according to any one of ⁇ 6> to ⁇ 22> is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated.
  • This is a permanent pattern forming method characterized by this.
  • the photosensitive composition is applied to the surface of the substrate, and the applied photosensitive composition is dried to form the photosensitive layer.
  • the photosensitive layer is exposed, and the exposed photosensitive layer is developed and heated, whereby the film strength of the cured region of the photosensitive layer is increased.
  • an optimum permanent pattern is formed as a protective film having a high surface hardness, an interlayer insulating film, and a solder resist pattern.
  • the photosensitive film according to any one of the above items ⁇ 23> to ⁇ 31> is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed.
  • a permanent pattern forming method characterized by heating.
  • the photosensitive film force is laminated on the surface of the substrate under heating and pressing.
  • the photosensitive layer in the laminated photosensitive film is exposed, and the exposed photosensitive layer is developed and heated, whereby the film strength of the cured region of the photosensitive layer is increased.
  • an optimum permanent pattern is formed as a protective film having a high surface hardness, an interlayer insulating film, and a solder resist pattern.
  • ⁇ 33> The permanent pattern forming method according to any one of the above ⁇ 31>, ⁇ 32>, and ⁇ 32>, wherein the base material is a printed wiring board on which wiring has been formed.
  • the permanent pattern forming method high-density mounting of semiconductor components on a multilayer wiring board or a build-up wiring board is possible.
  • ⁇ 34> The method for forming a permanent pattern according to ⁇ 31>, wherein the exposure is performed imagewise based on pattern information to be formed.
  • ⁇ 35> The exposure according to any one of the above items 31> Karaku 34>, wherein the exposure is performed using light modulated based on the pattern information to be generated and modulated according to the control signal. This is a permanent pattern forming method.
  • the exposure is performed using light irradiation means for irradiating light and light modulation means for modulating light emitted from the light irradiation means based on pattern information to be formed.
  • the permanent pattern forming method according to any one of the above.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the light modulation means has n pixel parts, and forms any less than n of the pixel parts continuously arranged from the n pixel parts.
  • the permanent pattern forming method according to any one of 36, 37, 37, which is controllable according to pattern information. In the method for forming a permanent pattern described in 38>, an arbitrary less than n pixel parts continuously arranged from the n picture element parts in the light modulation means are selected according to the pattern information. By controlling the light, the light from the light irradiation means is modulated at high speed.
  • ⁇ 40> The method for forming a permanent pattern according to ⁇ 39>, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • the exposure is performed through a microlens array in which microlenses having aspheric surfaces capable of correcting aberration due to distortion of the exit surface of the picture element portion in the light modulation means are arranged.
  • the method for forming a permanent pattern according to any one of the above 38> Kara 41>.
  • ⁇ 43> The method for forming a permanent pattern according to ⁇ 42>, wherein the aspherical surface is a toric surface.
  • the aspherical surface is a top surface.
  • ⁇ 45> The permanent pattern forming method according to any one of ⁇ 31>, ⁇ 44>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
  • the exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
  • ⁇ 46> The method for forming a permanent pattern according to any one of the above ⁇ 31>, ⁇ 45>, wherein the exposure is performed on a partial region of the photosensitive layer.
  • ⁇ 47> The method for forming a permanent pattern according to any one of the above items, wherein the light irradiation unit can synthesize and irradiate two or more lights.
  • the light irradiation unit can synthesize and irradiate two or more lights.
  • exposure is performed with exposure light having a deep focal depth.
  • the exposure to the photosensitive layer is performed with extremely high definition.
  • the photosensitive layer is developed to form an extremely fine permanent pattern.
  • the light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber.
  • the laser light respectively emitted from the plurality of lasers is condensed by the converging optical system by the light irradiation means and coupled to the multimode optical fiber.
  • exposure is performed with exposure light having a deep focal depth.
  • the photosensitive layer is extremely exposed. And done in high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
  • ⁇ 49> The method for forming a permanent pattern according to ⁇ 31>, wherein the exposure is performed using a laser beam having a wavelength of 395 to 415 nm.
  • ⁇ 50> The method for forming a permanent pattern according to ⁇ 31> to ⁇ 49>, wherein the heating is performed on the entire surface at 120 to 250 ° C.
  • the film strength of the cured film is increased in the entire surface heat treatment performed under the temperature condition.
  • ⁇ 51> The method for forming a permanent pattern according to any one of ⁇ 31> to ⁇ 50>, wherein the photosensitive layer is subjected to a whole surface exposure treatment after development.
  • the permanent pattern forming method described in 51> the development of the photosensitive layer is followed by an overall exposure process to accelerate the curing of the resin in the photosensitive composition. Is done.
  • ⁇ 52> The method for forming a permanent pattern according to any one of the above ⁇ 31> and ⁇ 51>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.
  • the wiring is externally provided due to the insulation property, heat resistance, etc. of the film. Protected from impact and bending.
  • ⁇ 53> A permanent pattern formed by the method for forming a permanent pattern described in ⁇ 31>, wherein the ⁇ 31> force is ⁇ 52>. Since the permanent pattern according to ⁇ 53> is formed by the permanent pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition, and is a multilayer wiring board for semiconductor components. N Build-up Useful for high-density mounting on wiring boards.
  • the permanent pattern according to ⁇ 53> which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
  • the permanent pattern described in ⁇ 54> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Bending and other forces are protected.
  • the invention's effect [0020] According to the present invention, the conventional problems can be solved, no reaction occurs at room temperature during storage, excellent storage stability, a curing promoting effect and a thermal cross-linking effect are exhibited by heating, and an epoxy A curing accelerator that initiates a reaction with a resin such as a resin compound and cures it to obtain good film hardness of the cured film. Using this curing accelerator, it can be cured by heat and has excellent storage stability, after curing.
  • thermosetting resin composition that exhibits excellent chemical resistance, hardness, dielectric properties, electrical insulation, and the like, and the curing accelerator, can form images by UV exposure, and has low surface tack
  • a photosensitive composition that has good laminating and handling properties, excellent storage stability, high sensitivity and excellent developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development, and Photosensitive film using this As well, it is possible to provide high-definition permanent pattern (protective film, an interlayer insulating film, and the like solder resist pattern) and the efficient formation methods.
  • FIG. 1A is an example of a diagram illustrating an example of a DMD usage area.
  • FIG. 1B is an example of a diagram showing an example of a DMD usage area similar to FIG. 1A.
  • FIG. 2A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system.
  • FIG. 2B is an example of a plan view showing an optical image projected onto an exposed surface when a microlens array or the like is not used.
  • FIG. 2C is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is used.
  • FIG. 3 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD by contour lines.
  • FIG. 4A is an example of a graph showing distortion of the reflection surface of the micromirror in two diagonal directions of the mirror.
  • FIG. 4B is an example of a graph showing distortion of the reflection surface of the micromirror similar to that in FIG. 4A in the two diagonal directions of the mirror.
  • FIG. 5A is an example of a front view of a microlens array used in a pattern forming apparatus.
  • FIG. 5B is an example of a side view of a microlens array used in the pattern forming apparatus.
  • FIG. 6A is an example of a front view of a microlens constituting a microlens array.
  • FIG. 6B is an example of a side view of the microlens constituting the microlens array.
  • FIG. 7A is an example of a schematic diagram showing a condensing state by a microlens in one cross section.
  • FIG. 7B is an example of a schematic view showing a condensing state by the microlens in a cross section different from FIG. 7A.
  • FIG. 8A is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention.
  • FIG. 8B is an example of a diagram showing the same simulation results as in FIG. 8A but at different positions.
  • FIG. 8C is an example of a diagram showing the same simulation results as in FIG. 8A but at different positions.
  • FIG. 8D is an example of a diagram showing the same simulation results as in FIG. 8A but at different positions.
  • FIG. 9A is an example of a diagram showing a result of simulating a beam diameter in the vicinity of a condensing position of a microlens in a conventional pattern forming method.
  • FIG. 9B is an example of a diagram showing the same simulation results as in FIG. 9A but at different positions.
  • FIG. 9C is an example of a diagram showing the same simulation results as in FIG. 9A but at different positions.
  • FIG. 9D is an example of a diagram showing the same simulation results as in FIG. 9A but at different positions.
  • FIG. 10A is an example of a front view of a microlens constituting a microlens array.
  • FIG. 10B is an example of a side view of the microlens constituting the microlens array.
  • FIG. 11A is an example of a schematic diagram showing the light collection state by the microlens of FIGS. 10A and 10B in one cross section.
  • FIG. 11B is an example of a schematic diagram showing a cross section different from the example of FIG. 11A.
  • FIG. 12A is a perspective view showing a configuration of a fiber array light source.
  • FIG. 12B is an example of a partially enlarged view of FIG. 12A.
  • FIG. 12C is an example of a plan view showing an array of light emitting points in the laser emitting section.
  • FIG. 12D is an example of a plan view showing an array of light emitting points in the laser emitting section.
  • FIG. 12E is an example of a front view showing the arrangement of light emitting points in the laser emitting section of the fiber array light source.
  • FIG. 13 is an example of a diagram illustrating a configuration of a multimode optical fiber.
  • FIG. 14 is an example of a plan view showing a configuration of a combined laser light source.
  • FIG. 15 is an example of a plan view showing a configuration of a laser module.
  • FIG. 16 is an example of a side view showing the configuration of the laser module shown in FIG.
  • FIG. 17 is a partial side view showing the configuration of the laser module shown in FIG. 15. BEST MODE FOR CARRYING OUT THE INVENTION
  • the curing accelerator of the present invention is a compound having a structure in which an amine is generated by an external stimulus and a carboxynole group and an amide group are in a ratio of 1: 1 in the molecule.
  • the curing accelerator of the present invention can be synthesized, for example, by reacting an acid anhydride with an amine, but is not limited to this synthesis means.
  • the curing accelerator of the present invention expresses a function as a curing accelerator or a crosslinking agent for curing a compound to which the curing accelerator is added by generating an amine by external stimulation. Therefore, it can be suitably used as a resin curing accelerator or thermal crosslinking agent.
  • the external stimulus is not particularly limited and can be appropriately selected according to the purpose. Heating at 80 ° C. or higher is preferable, and heating at 100 ° C. or higher is more preferable.
  • the curing accelerator of the present invention is a compound having a structure having a carboxyl group and an amide group in a ratio of 1: 1.
  • the curing accelerator is preferably represented by any one of the following general formulas (1), (2), (3), (4), (5) and (6).
  • R ⁇ R 18 represents either a hydrogen atom or a substituent
  • Ai A 6 represents a divalent substituent
  • ⁇ ! ⁇ 11 represents one of a single bond, a double bond, and a divalent substituent
  • ⁇ ⁇ 6 are hydrogen atom, unsubstituted alkyl group, aryl group 'alkenyl group, hydroxyl group, alkoxy group, cyano group' no, substituted with rogen atom, oxygen atom 'sulfur atom' carbonyl group 'amide group 'Urethane group' Urea group, Substituent-containing alkyl group which may have divalent group such as ester group, unsubstituted aryl group, alkyl group • aryl group, alkoxy group, cyan group 'Norogen atom is substituted This indicates the level of the reel.
  • unsubstituted alkyl group those having a total number of carbon atoms of 1 to 30 which may have a double bond or a triple bond which may have a branch are preferable:! To 15 are particularly preferable .
  • Examples of such an alkyl group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, an sbutyl group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group. Can be mentioned.
  • aryl substituent in the substituent-containing alkyl group those having a total carbon number of 6 to 30 which may have a double bond or a triple bond are preferred, and 6 to 15 is particularly preferred.
  • substituents include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
  • alkenyl substituent in the substituent-containing alkyl group a total carbon number of 2 to 10 is preferable, and 2 to 6 is particularly preferable.
  • alkoxy substituent in the substituent-containing alkyl group those having a total carbon number of 1 to 10 which may have a branch are preferable:! To 5 are particularly preferable. Examples thereof include a xy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.
  • substituent-containing alkyl group those having a total number of carbon atoms of 2 to 40, which may have a double bond or a triple bond, which may have a branch, are preferred. Particularly preferred.
  • substituent-containing alkyl group include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethylpropyl group, phenylethyl group, cyanopropyl group, and methoxyethyl group.
  • aryl group those having 6 to 30 carbon atoms are preferred, and 6 to 20 are particularly preferred.
  • aryl groups include phenyl, naphthyl, and anthracenyl groups.
  • the alkyl substituent in the substituent-containing aryl group is preferably one having a total of 1 to 20 carbon atoms which may have a double bond or a triple bond which may have a branch:!
  • To 6 are particularly preferred, for example, methyl group, ethyl group, ethynyl group, propyl group, isopropyl group, butyl group, s butynole group, tbutyl group, butyryl group, cyclohexyl group, cyclohexenyl group, etc. Is mentioned.
  • the aryl substituent in the substituent-containing aryl group those having a total carbon number of 6 to 20 are preferred, and 6 to 14 is particularly preferred.
  • the alkoxy substituent in the substituent-containing aryl group may have a branch. Total carbon number:! To 10 is preferable:! To 5 is particularly preferable.
  • Such substituted aryl groups are preferably those having a total carbon number of 6 to 40, particularly preferably 6 to 25 forces, such as ethenylphenyl, biphenyl, nourphenyl, octylphenyl, fluorophenyl, and methoxyphenyl groups. Can be mentioned.
  • R 1 may be a heterocycle that may be an aromatic ring that may be bonded to R 2 to form a ring or may be a double bond or a triple bond in the ring. Can be formed It may be replaced.
  • a 4- to 8-membered ring is preferred, and a 5- to 6-membered ring is particularly preferred.
  • the carbon to which R 1 is bonded and the carbon to which R 2 is bonded may be a single bond or a double bond.
  • R 3 , R 4 may be bonded to form a ring, or the ring may contain a double bond or triple bond, or may be substituted.
  • a 4- to 8-membered ring is preferred.
  • a 5- to 6-membered ring is particularly preferred.
  • R 5 , R 6 may be bonded to form a ring, or a double ring or a triple bond may be included in the ring, or a heterocyclic ring may be substituted. It may be. 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
  • the carbon to which R 5 is bonded and the carbon to which R 6 is bonded may be a single bond or a double bond.
  • R 8 , R 9 may be bonded to form a ring, or a double ring or triple bond may be included in the ring, or a hetero ring may be substituted. It may be. 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
  • R 7 may be bonded to form a ring or a ring may contain a double bond or a triple bond, or may be substituted.
  • a 4- to 8-membered ring is preferred.
  • a 5- to 6-membered ring is particularly preferred.
  • R 11 , R 12 may be bonded to form a ring, or a ring may contain a double bond or a triple bond, or may be substituted.
  • 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
  • R 13 , R 14 may be bonded to form a ring, or a ring may contain a double bond or a triple bond, or may be substituted.
  • 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
  • R 15 , R 16 may be bonded to form a ring, and the ring may contain a double bond or a triple bond, or may be substituted.
  • 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
  • R 17 , R 18 may be bonded to form a ring, or a ring may contain a double bond or a triple bond, or may be substituted. 4-8 member ring is preferred 5-6 member ring Particularly preferred.
  • Alkenyl. Alkoxy-Shiano Substituent-containing divalent alkyl which may be substituted with the group 'Norogen atom' and may have a divalent group of oxygen atom 'sulfur atom' carbonyl group 'amide group' urethane group 'urea group, ester group
  • the unsubstituted divalent alkyl group is preferably one having a total of 1 to 30 carbon atoms which may have a double bond or a triple bond which may have a branch:! Particularly preferred.
  • Examples of such an alkyl group include a methinole group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, an sbutynole group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group.
  • a methinole group an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, an sbutynole group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclo
  • aryl substituent in the substituent-containing divalent alkyl group those having a total carbon number of 6 to 30 which may have double bonds or triple bonds are preferred, and 6 to 15 is particularly preferred.
  • substituents include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
  • alkenyl substituent in the substituent-containing divalent alkyl group those having a total carbon number of 2 to 10 are preferred, and 2 to 6 are particularly preferred. Examples thereof include an ethur group, a propenyl group, and a petityl group. Can be mentioned.
  • alkoxy substituent in the substituent-containing divalent alkyl group those having 1 to 10 total carbon atoms which may have a branch are preferred:! To 5 are particularly preferred.
  • methoxy Group, ethoxy group, propyloxy group, 2_methylpropyloxy group, butoxy group, and the like those having a total number of carbon atoms of 2 to 40, which may have a double bond or a triple bond, may be preferred. Is particularly preferred.
  • Examples of such a substituent-containing divalent alkyl group include a 2-ethylhexyl group, a chlorobutyl group, a benzyl group, a 2-ethylpropyl group, a phenylethyl group, a cyanopropyl group, and a methoxyethyl group.
  • unsubstituted divalent aryl group those having a total carbon number of 6 to 30 are preferred, and 6 to 20 is particularly preferred. Good.
  • aryl groups include a phenyl group, a naphthyl group, and an anthracenyl group.
  • alkyl substituent in the substituent-containing divalent aryl group one having a total carbon number of 1 to 20 which may have a branch, a double bond or a triple bond is preferable.
  • 1 to 6 are particularly preferred, for example, methyl group, ethyl group, ethyl group, propyl group, isopropyl group, butyl group, s_butyl group, t_butyl group, butyryl group, cyclohexyl group, and cyclohexane A xenyl group, and the like.
  • aryl substituent in the substituent-containing divalent aryl group those having a total carbon number of 6 to 20 are preferable, and 6 to 14 is particularly preferable.
  • alkoxy substituent in the substituent-containing divalent aryl group those having a total carbon number of 1 to 10 which may have a branch are preferable:! To 5 are particularly preferable.
  • substituent-containing divalent aryl group those having a total carbon number of 6 to 40 are preferred. 6 to 25 forces S are particularly preferred.
  • ⁇ ⁇ 11 are single bond, double bond, unsubstituted divalent alkyl, aryl group, alkenyl group, alkoxy group, cyan group, substituted with halogen atom, oxygen atom, sulfur atom, carbonyl group, amide Substituent-containing divalent alkyl, unsubstituted divalent aryl, alkyl group 'aryl group', alkenyl group, alkoxy group, which may have a divalent group of a group, urethane group, urea group or ester group.
  • halogen atom has a divalent group of oxygen atom, sulfur atom, carbonyl group, amide group, urethane group, urea group, ester group, or may contain a substituent. Indicates whether the bivalent reel is misaligned.
  • unsubstituted divalent alkyl group those having a total number of carbon atoms of 1 to 15 which may have a branch or may have a double bond or a triple bond are preferred. I like it.
  • alkyl group examples include a methinole group, an ethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butynole group, a t_butyl group, a butyryl group, a cyclohexyl group, a cyclohexenyl group, Etc.
  • aryl substituent in the divalent alkyl group containing a substituent those having a total carbon number of 6 to 30 which may have a double bond or a triple bond are preferred, and 6 to 15 is particularly preferred.
  • substituents include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
  • alkenyl substituent in the above-mentioned divalent alkyl group containing a substituent those having a total carbon number of 2 to 10 are preferable, and 2 to 6 are particularly preferable.
  • an ethyl group, a propenyl group, and a pentyl group are particularly preferable.
  • the alkoxy substituent in the substituent-containing divalent alkyl group preferably has a total number of carbon atoms that may be branched:! To 10 and is particularly preferably: to 5; for example, methoxy Group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
  • a double bond which may have a branch or a group having 2 to 40 total carbon atoms which may have a triple bond is preferable. 25 is particularly preferred.
  • substituent-containing divalent alkyl group examples include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethynylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group, and the like.
  • unsubstituted divalent aryl group those having a total carbon number of 6 to 30 are preferable, and 6 to 20 is particularly preferable.
  • aryl groups include a phenyl group, a naphthyl group, and an anthracenyl group.
  • alkyl substituent in the divalent aryl group containing a substituent one having a total of 1 to 20 carbon atoms which may have a double bond or a triple bond is preferable.
  • ⁇ 6 are particularly preferred, for example, methyl group, ethyl group, ethyl group, propyl group, isopropylinole group, butyl group, s-butynole group, t-butyl group, butyryl group, cyclohexyl group, cyclohexyl A xenyl group, and the like.
  • aryl substituent in the substituent-containing divalent aryl group those having a total carbon number of 6 to 20 are preferable, and 6 to 14 is particularly preferable.
  • a phenyl group, a naphthyl group, an anthracenyl group examples thereof include a methoxyphenyl group and a chlorophenyl group.
  • the alkoxy substituent in the substituent-containing divalent aryl group one having a total carbon number of 1 to 10 which may have a branch is preferable:! To 5 is particularly preferable.
  • substituent-containing divalent aryl group those having a total carbon number of 6 to 40 are preferred. 6 to 25 forces S are particularly preferred, for example, ethenylphenyl, biphenyl, nourphenyl, octylphenyl, fluorophenyl, methoxyphenyl group, etc. Is mentioned.
  • a single bond, a double bond, an unsubstituted divalent alkyl group, and a substituent-containing divalent alkyl group are preferable, and a single bond and a double bond are particularly preferable.
  • Examples of the compounds represented by the general formulas (1) to (6) include compounds represented by the following structural formulas (1) to (33), but are not limited to these compounds. Absent.
  • Structural formula (9) Structural formula (1 0) Structural formula (1 1) Structural formula (1 2)
  • the curing accelerator of the present invention can achieve excellent storage stability of the curing accelerator and a compound using the curing accelerator that do not cause a reaction at a low temperature or normal temperature, and the heat treatment during the heat treatment.
  • a cured product excellent in surface hardness, alkali resistance, etc. is obtained by showing a rapid reaction as a curing accelerator / thermosetting agent at a temperature.
  • displays such as protective films on printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc.
  • the photosensitive composition of the present invention comprises (A) a polymer having one or more carboxynole groups and ester groups in one molecule, (B) a polymerizable compound, and (C) photopolymerization initiation. And (D) the curing accelerator of the present invention, preferably (E) a thermal crosslinking agent, and further, if necessary, a coloring pigment, an extender pigment, a thermal polymerization inhibitor, and a surface active agent Other ingredients such as an agent.
  • the binder is preferably a compound that is soluble in an alkaline aqueous solution, and is preferably a compound that exhibits swelling properties in an alkaline aqueous solution.
  • the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound.
  • the acidic group is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From this point of view, a carboxyl group is preferred.
  • the compound in which an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound is not particularly limited and may be appropriately selected depending on the purpose. It can be obtained by reacting a functional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.
  • Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin ("YX4000; manufactured by Japan Epoxy Resin Co., Ltd.") or a mixture thereof, a heterocyclic group having an isocyanurate skeleton, and the like.
  • Epoxy resin TEPIC Nissan Chemical Industry Co., Ltd., "Araldite PT810: Chinoku 'Specialty' Chemicals Co., Ltd.”), Bisphenol ⁇ type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin Bisphenol S type epoxy resin, phenol novolak type epoxy resin, tale novolol type epoxy resin, halogenated phenol novolak type epoxy resin, glycidylamine type epoxy resin (eg tetraglycidyl diaminodiphenyl methane, etc.), hydantoin type epoxy resin, Cyclic epoxy resin, trihydroxyphenyl methane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylylene ethane resin, naphthalene group containing epoxy resin ( "ESN_190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd
  • Reaction product of polyphenolic compound and epichlorohydrin reaction product of polyphenol compound obtained by addition reaction of phenolic compound and diolefin compound such as dibutenebenzene dicyclopentagen and epichlorochlorohydrin; 4-Buylcyclo Hexene mono 1-oxide ring-opened polymer epoxidized with peracetic acid, etc .; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl meta-atalelate copolymer epoxy resin (“CP — 50S, CP— 50 M; manufactured by NOF Corporation, etc.), cyclohex Such as a copolymer epoxy resins of maleimide and glycidyl methacrylate Atari rate and the like. These may be used alone or in combination of two or more.
  • Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and sorbic acid.
  • ⁇ -cyancinnamic acid acrylic acid dimer; in addition to this, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, etc.
  • the polybasic acid anhydrides include, for example, succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, and anhydrous dodecenyl succinic acid.
  • Nonenyl succinic anhydride maleic anhydride, methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloro maleic acid, bromomaleic anhydride, itaconic anhydride, anhydrous Citraconic acid, anhydrous cis-aco Titanic acid, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride , Methinoredomethylenetetrahydrophthalic anhydride, chlorendic anhydride and 5_ (2,5-dioxotetrahydryl) furan) -1-methinole_3-cyclohex
  • Dibasic acid anhydrides trimellitic anhydride, pyromellitic anhydride, polybasic acid anhydrides such as 3,3 ′, 4,4′_benzophenone tetracarboxylic acid, and the like can also be used. These may be used alone or in combination of two or more.
  • the ability to react each in turn to obtain epoxy acrylates is the ratio of the carboxyl group-containing monomer power to the carboxyoxy group 0.8 to 1 with respect to 1 equivalent of the epoxy group of the polyfunctional epoxy compound. 2 equivalents, preferably ⁇ , 0.9 to: 1.1 equivalents, polybasic acid anhydrides 0.1 to 1.0 equivalents, preferably 0.3 to 1.0 equivalents .
  • epoxy atalytotoy compounds represented by the following structural formulas (III) and (IV) are preferred.
  • X represents any one of a hydrogen atom and a substituent containing at least an acidic group
  • Y represents any one of a methylene group, an isopropylidene group, and a sulfonyl group
  • n represents Represents an integer of 1-20.
  • n represents the integer of:!-20.
  • epoxy ata relay toy compound represented by the structural formula (III) specifically, a bisphenol F type epoxy ata relay toy compound represented by the following structural formula (V), and A bisphenol A type epoxy atelar toy compound represented by the following structural formula (VI) is more preferred.
  • the molecular weight of the epoxy acrylate compound is preferably 1,000-100,000, more preferably 2,000-50,000.
  • the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may deteriorate. , Over 000, developability deteriorates There is power. Also, synthesis of the resin becomes difficult.
  • Examples of the vinyl copolymer having a (meth) atalyloyl group and an acidic group in the side chain include (1) a vinyl monomer having an acidic group, and (2) can be used for a polymer reaction described later if necessary.
  • the (co) polymer obtained by vinyl (co) polymerization of a butyl monomer having a functional group and (3) other copolymerizable vinyl monomer if necessary, and (4) the (co) polymer It is obtained by polymer-reacting a functional group having reactivity with at least one of an acidic group in a polymer or a functional group that can be used for polymer reaction and a compound having a (meth) atalyloyl group.
  • the acidic group of the (1) butyl monomer having an acidic group is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a carboxylate group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable.
  • the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaroleic acid, itaconic acid, crotonic acid, cinnamic acid, attalinoleic acid dimer, and hydroxyl group.
  • a monomer having a monomer for example, 2-hydroxyethyl (meth) acrylate
  • a cyclic anhydride for example, maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic acid anhydride
  • Carboxy-poly-polypropylene mono (meth) acrylate for example, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
  • These monomers may be used alone or in combination of two or more.
  • monomers having anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as the precursor of the carboxyl group.
  • the functional group that can be used for the high molecular reaction includes a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc.
  • the above-mentioned (1) carboxyl group and acid anhydride group are also usable functional groups.
  • Examples of the vinyl monomer having a hydroxyl group include compounds represented by the following structural formulas (34) to (42). [0043] [Chemical 23]
  • R 1 represents a hydrogen atom or a methyl group
  • n, nl, and n2 represent an integer of 1 or more.
  • Examples of the Biel monomer having an amino group include Bielbenzylamine, aminoethyl methacrylate, and the like.
  • Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (43) to (45).
  • R 1 represents a hydrogen atom or a methyl group.
  • Examples of the butyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (46).
  • R represents either H or Me.
  • Examples of the Biel monomer having an acid halide group include (meth) acrylic acid chloride.
  • Biel monomer having an active halide group examples include chloromethylstyrene.
  • Examples of these commercially available products include “Kaneka Resin AX; manufactured by Kaneka Chemical Industry Co., Ltd.”, “CYCLOMER A-200; manufactured by Daicel Chemical Industries, Ltd.”, “CYCLOMER M” 200; manufactured by Daicel Chemical Industries, Ltd. ”,“ SPCP1X, SPCP2X, S PCP3X; manufactured by Showa Polymer Co., Ltd. ”, and the like can be used.
  • Each of the monomers may be used alone or in combination of two or more.
  • the other copolymerizable monomer used as necessary in the above (3) is not particularly limited and may be appropriately selected depending on the purpose.
  • (meth) acrylic acid esters Crotonic acid esters, Bull esters, Maleic acid diesters, Fumaric acid diesters, Itaconic acid diesters, (Meth) acrylamides, Bull ether , Esters of butyl alcohol, styrenes (for example, styrene, styrene derivatives, etc.), (meth) acrylonitrile, heterocyclic groups substituted by bur groups (for example, burpyridine, bulurpyrrolidone, bulur rubazole, etc.), N —Burformamide, N-Burecetamide, N-Buylimidazole, Bulle Prolatatone, 2_Acrylamide-2-Methylpropanesulfonic acid, Monophosphate (2-Ataloyloxetyl ester), Monophosphate (1
  • Examples of the (meth) acrylic acid esters include methyl (meth) acrylate and ethyl.
  • crotonic acid esters examples include butyl crotonic acid and hexyl crotonic acid. Etc.
  • bull esters examples include bull acetate, bull propionate, bull butyrate, bull methoxyacetate, and benzoic acid bull.
  • maleic diesters examples include dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • Examples of the fumaric acid diesters include dimethyl fumarate, jetinole fumarate, and dibutyl fumarate.
  • Examples of the itaconic acid diesters include dimethyl itaconate, dimethyl itaconate, and dibutyl itaconate.
  • Examples of the (meth) acrylamides include (meth) atalinoleamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) ) Acrylamide, N-n-butylacryl (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, Examples include N-dimethyl (meth) acrylamide, N, N-jetyl (meth) atalinoleamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) atalyloylmorpholine, diacetone acrylamide, etc. It is done.
  • styrene examples include, for example, the styrene, the styrene derivative (for example, methino styrene, dimethyl styrene, trimethyl styrene, ethino styrene, isopropyleno styrene, butino styrene, methoxy styrene, butoxy styrene, Cetoxystyrene, chlorostyrene, dichlorostyrene, promostyrene, hydroxystyrene protected with groups that can be deprotected by acidic substances (eg t-Boc), methyl butyl benzoate, a-methylol styrene, etc.), etc. Is mentioned.
  • acidic substances eg t-Boc
  • butyl ethers examples include methyl butyl ether, butyl vinyl ether, hexyl butyl ether, methoxyethyl vinyl ether, and the like.
  • Examples of a method for synthesizing a bulu monomer having a urethane group or a urea group as the functional group include an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an isocyanate group is used. Addition reaction between a monomer having a hydroxyl group and a compound having one hydroxyl group or a compound having one primary or secondary amino group, a monomer having a hydroxyl group, In this case, an addition reaction between a monomer having a primary or secondary amino group and a monoisocyanate is mentioned.
  • Examples of the monomer having an isocyanato group include compounds represented by the structural formulas (43) to (45) in the same manner as described in (2) above.
  • Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.
  • Examples of the monomer having a hydroxyl group include compounds represented by the structural formulas (34) to (42) as in the above-described (2).
  • Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butano-monore, t-butano-monore, n- Xananol, 2-ethynole hexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, Naphthol, etc.) and those further containing a substituent include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, black mouth phenol, dichloro mouth phenol, methoxy phenol and acetophenol.
  • alcohols for example, methanol, ethanol, n-propan
  • Examples of the monomer having a primary or secondary amino group include burbenzylamine.
  • Examples of the compound containing one primary or secondary amino group include alkylamines (methinolamin, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, Xylamine, 2-ethylhexylamine, decynoleamine, dodecylamine, octadecylamine, dimethylamine, jetylamine, dibutylamine, dioctylamine), cyclic alkylamines (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.) Arylamines (aniline, tonorenoleamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and further amines containing substituents (trifluorine,
  • the bull (co) polymer can be prepared by copolymerizing the corresponding monomers according to a conventional method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. In addition, it can be prepared by using IJ for polymerization by so-called emulsion polymerization or the like in a state where the monomer is dispersed in an aqueous medium.
  • the acidic group in these copolymers and, if necessary, a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, an acid halide It can be obtained by polymer-reacting a functional group having reactivity with at least one of the groups and a compound having a (meth) atallyloyl group.
  • a functional group having reactivity with at least one of an acidic group in the (co) polymer of the above (4) or a functional group that can be used in a polymer reaction, and a (meth) allyloyl group As the compound having the above, the compound shown in the above (2) can be used.
  • Examples of combinations of functional groups for performing these polymer reactions include, for example, a copolymer having an acidic group (such as a carboxyl group) and a butyl monomer having an epoxy group, and a copolymer having an amino group. And a combination of a butyl monomer having an epoxy group, a combination of a copolymer having an amino group and a butyl monomer having an isocyanate group, a combination of a copolymer having a hydroxyl group and a butyl monomer having an isocyanate group, a copolymer having a hydroxyl group Combination of a butyl monomer having a polymer and an acid halide group, a combination of a copolymer having an amino group and a vinyl monomer having an active halide group, a combination of a copolymer having an acid anhydride group and a butyl monomer having a hydroxyl group, an isocyanate group
  • the maleamic acid copolymer is a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer.
  • the copolymer is a maleamic acid copolymer comprising at least a maleamic acid unit B having a maleic acid half amide structure and a unit A having no maleic acid half amide structure, represented by the following structural formula (VII).
  • a polymer is preferred.
  • the unit A may be one type or two or more types.
  • the maleamic acid-based copolymer means a binary copolymer
  • the unit When A is two kinds, the maleamic acid copolymer means a terpolymer.
  • the unit A includes an aryl group which may have a substituent and a vinyl monomer which will be described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with a certain bull monomer (c) is preferred.
  • R 3 and R 4 represent either a hydrogen atom or a lower alkyl group.
  • X and y represent mole fractions of the repeating units, for example, when the unit A is one, X is 85-50 Monore 0/0, y is 15 to 50 mole 0/0.
  • R 1 for example, (—COOR 10 ) (—CONRUR 12 ), an aryl group optionally having a substituent, (10C0R 13 ), (—OR 14 ), (— COR 15 ) Examples include a substituent.
  • R 1U to R 15 each represents a hydrogen atom (1H), an optionally substituted alkyl group, an aryl group, or an aralkyl group.
  • the alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
  • R 1 () to R 15 may be, for example, methinole, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, aranole, n- Examples include xyl, cyclohexyl, 2-ethylhexyl, dodecinole, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, and black mouth phenyl.
  • R 1 include, for example, benzen derivatives such as phenyl, a methylphenyl, 2-methylphenyl, 3 methylphenyl, 4 methylphenyl, 2,4 dimethylphenyl; n-propyloxycarbonyl, n-butyloxy Examples thereof include xyloxycarbonyl, pentyloxycanenoboninole, hexinorexicanoreboninole, n-butynoleoxycanoleboninole, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.
  • R 2 examples include an optionally substituted alkyl group, aryl group, aralkyl group, and the like. These may have a cyclic structure or a branched structure. Specific examples of the above include benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenol-1-hexyl, —-Methylbenzyl, 2_methylbenzyl, 3_methylbenzyl, 4_methylbenzyl, 2_ (p-tolyl) ethyl, j3-methylphenethyl, 1_methyl_3_phenylpropyl, 2—clobenbenole 3_Black-and-back Beninole, 4_Black-and-back Beninole, 2_Fluoro-Benzinore, 3_Fluoro-Benzinore, 4-Fluorobenzinole, 4-Bromofenetinor
  • the binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, which is a homopolymer of the bulle monomer.
  • a copolymer obtained by reacting a primary amine compound with a vinyl monomer having a glass transition temperature (Tg) of less than 80 ° C and an anhydride group of a powerful copolymer is a copolymer. preferable.
  • the aromatic vinyl monomer is not particularly limited and can be appropriately selected according to the purpose.
  • the surface hardness of the photosensitive layer formed using the photosensitive composition of the present invention can be increased.
  • compounds having a glass transition temperature (Tg) of the homopolymer of 80 ° C or higher are preferred, and compounds having a temperature of 100 ° C or higher are more preferable.
  • the bull monomer needs to have a glass transition temperature (Tg) of the homopolymer of the bull monomer of less than 80 ° C, preferably 40 ° C or less, more preferably 0 ° C or less. .
  • Tg glass transition temperature
  • Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6 phenyl 1-hexylamine, ⁇ Methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- ( ⁇ -tolyl) ethylamine,; 3-methylphenethylamine, 1-methyl-3-phenylpropylamine Minor, 2-Chlorobenzylamine, 3-Chlorobenzylamine, 4-Chlorobenzylamine, 2-Fluorobenzylamine, 3-Fluorobenzylamine, 4-Fluorobenzylamine, 4-Bromophenethylamine, 2- (2 Black mouth phenyl) ethylamine, 2— (3 Black mouth phenyl) ethylamine, 2— (4 Black mouth phenyl) )
  • the primary amine compounds may be used alone or in combination of two or more.
  • the reaction amount of the primary amine compound is 0.1 to 1.2 equivalents relative to the anhydride group. And 0.1 to: 1.0 equivalent is preferable. When the reaction amount exceeds 1.2 equivalents, when the primary Amin compound was reacted for 1 or more, sometimes force s solubility is significantly deteriorated.
  • the content of (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol%. If the content is less than 15 mol%, alkali developability cannot be imparted, and if it exceeds 50 mol%, alkali resistance deteriorates, and the copolymer becomes difficult to synthesize. Permanent pattern formation may not be possible.
  • the content of (b) the aromatic vinyl monomer and (c) the vinyl monomer having a glass transition temperature (Tg) power of less than 0 ° C. of the homopolymer in the binder is respectively 20-60 mol% and 15-40 mol% are preferred. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.
  • the molecular weight of the maleamic acid copolymer is preferably 3,000 to 500,000 force S, more preferably 8,000 to: 150,000 force S. If the molecular weight is less than 3,000, the film quality becomes brittle and the surface hardness may deteriorate after curing of the photosensitive layer described later. If the molecular weight exceeds 500,000, the photosensitive composition is heated and laminated. The fluidity at the time may be low, and it may be difficult to ensure proper laminating properties, and the developability may deteriorate.
  • a polyamide (imide) resin described in JP-A-11-288087, a polyimide precursor described in JP-A-11-282155, or the like can be used. These may be used alone or as a mixture of two or more.
  • the molecular weight of the binder such as polyamide (imide) or polyimide precursor is preferably 3,000 to 500,000, more preferably 5,000 to 100,000. If the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may increase, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described below. If it exceeds 00,000, developability may deteriorate.
  • the solid content in the photosensitive composition solid content of the binder is preferably 5 to 70 mass%, more preferably 10 to 50 mass%.
  • the solid content is less than 5% by mass
  • the film strength of the photosensitive layer described later is weakened, the tackiness of the surface of the photosensitive layer may be deteriorated, and if it exceeds 70% by mass, the exposure sensitivity may be lowered.
  • the polymerizable compound is not particularly limited and can be appropriately selected according to the purpose.
  • the polymerizable compound has at least one addition-polymerizable group in the molecule, and has a boiling point of 100 ° C. or higher at normal pressure.
  • a certain compound is preferable.
  • at least one selected from monomers having a (meth) acryl group is preferable.
  • the monomer having the (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Monofunctional acrylates and monofunctional methallylates such as rate and phenoxychetyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate Rate, trimethylolpropane diatalylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta erythritol retri (meth) acrylate, dipentaerythritol Oxford
  • the solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
  • the photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound. Those that have photosensitivity to visible light are preferred to photo-excited sensitizers and may act as active agents that generate active radicals. Cationic polymerization is performed depending on the type of monomer. It may be an initiator that initiates.
  • the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 in the range of about 300 to 800 nm (more preferably 330 to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), phosphine oxides, hexarylbiimidazoles, oximes. Derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, metathelones, and the like.
  • halogenated hydrocarbon compound having a triazine skeleton examples include, for example, a halogen having the triazine skeleton described in paragraphs “0290” and “0299” of the specification of JP-A No. 2005-258431. And hydrocarbon compounds.
  • Examples of the phosphine oxide include bis (2, 4, 6_trimethylbenzoyl) monophenylphosphine oxide and bis (2, 6-dimethoxybenzoyl) _2, 4, 4 monotrimethyl. Monopentylphenylphosphine oxide, LucirinTPO, and the like.
  • hexarylbiimidazole examples include hexarylbiimidazole described in paragraph "0288" of the specification of JP-A-2005-258431.
  • Examples of the oxime derivative suitably used in the present invention include, for example, 3_benzoyloxyiminobutane 1_one, 3-acetoxyiminobutane 1_on, 3_propionyloxyiminobutane 1_on , 2-acetoximinopentane 1_one, 2-acetoximino 1_one, 2-vinylpropane 1_on, 2_benzoyloximino 1_phenolinopropane 1_on, 3_ (4 -Toluenesulfonyloxy) iminobutane-2-one and 2-ethoxycarbonyloxyimino-1- 1-phenylpropane-1-one.
  • organic peroxide examples include 3, 3 ', 4, 4'-tetra (t-butylperoxycarbonyl) benzophenone.
  • Examples of the thio compound include 2,4-jetylthioxanthone, 2,4-dichrothioxanthone, 1 chloro-4 propoxythioxanthone, 2 benzoylmethylene 3-methylnaphthothiazoline, and the like.
  • Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methenolebenzophenone, 4-methinolevenzophenone, 4-methoxybenzophenone, 2-clobenzobenzoneone, and 4-clobenzobenzoneone.
  • aromatic onium salt examples include diphenyl rhodonitr tetrafluoroborate, diphenyleno melole phosphonate, triphenylenoles norehonumute traful.
  • aromatic onium salt examples include diphenyl rhodonitr tetrafluoroborate, diphenyleno melole phosphonate, triphenylenoles norehonumute traful.
  • examples include azoborate, triphenylsulfonium hexafluorophosphonate, tetraphenylphosphonium hexafluorophosphate, and the like.
  • metacathenes examples include bis (7) 2,4-cyclopentagen-1-yl) 1-bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, 7] 5 —Cyclopentadiniole ⁇ 6 —Tameninoleiron (1 +) — Hexafluorophosphate (1—), and the like.
  • polyhalogen compounds such as ⁇ phenyldaricin (for example, carbon tetrabromide, phenyl tribumomethylsulfone, phenyl trichloromethyl ketone, etc.), amines (for example, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid ⁇ -butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2-phthalimidoethyl, 4 dimethylaminobenzoic acid 2-metatalyloxyoxyethyl, pentamethylenebis (4-dimethylamino) Benzoate), 3-dimethylaminobenzoic acid phenethyl, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2 -chlor _ 4 _dimethylamin
  • a sensitizer can be added.
  • the sensitizer can be appropriately selected depending on visible light, ultraviolet light, visible light laser or the like as a light irradiation means described later.
  • the sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby causing radicals and It is possible to generate useful groups such as acids.
  • substances for example, radical generator, acid generator, etc.
  • energy transfer, electron transfer, etc. for example, energy transfer, electron transfer, etc.
  • These compounds also have a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation only by improving the sensitivity of the photosensitive layer.
  • the sensitizer can be appropriately selected from known sensitizers that are not particularly limited.
  • known polynuclear aromatics for example, pyrene, perylene, triphenylene
  • Xanthenes for example, fluorescein, eosin, erythrosine synth, rhodamine B, rose bengal
  • cyanines for example, indocarboyanine, thiacarboyanine, oxacarboyanine
  • merocyanines for example, merocyanine, carbomerocyanine
  • Thiazines for example, thionine, methylene blue, toluidine blue
  • atalidines for example, atalidine orange, chloroflavin, acriflavine
  • anthraquinones for example, anthraquinone
  • squaliums for example, squalium
  • Preferred examples of the sensitizer include hetero-fused compounds.
  • the hetero-ring-ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring.
  • Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound, a quinoline compound, and an atalidine compound.
  • hetero-fused ketone compound examples include attaridone compounds such as attaridone, chloroacridone, N-methyl attaridone, N-butyl attalidone, N-butyl monochloro attaridone, etc .; 3- (2 benzofuroyl ) _ 7—Jetylaminocoumarin, 3 _ (2 _Benzofuroyl) — ⁇ — (1—Pyrrolidininole) coumarin, 3 _Benzyl _ 7—Jetyl aminocoumarin, 3-(2 methoxybenzoyl) _ 7—Jet Tyraminocoumarin, 3_ (4-Dimethylaminobenzoyl) _7-Jetylaminocoumarin, 3,3'_Carbonylbis (5,7-di-n-propoxycoumarin), 3, 3, _Carbonylbis (7-Jetylaminocoumarin), 3-Benzyl 7-methoxycoumarin, 3- (2-Furoyl
  • quinoline compound examples include, for example, quinoline, 9-hydroxy-1-1,2-dihydroquinoline 2-one, 9 ethoxy-1, 2-dihydroquinoline 2-one, 9-dibutylamino-1, 2 Dihydroquinoline-2-one, 8 hydroxyquinoline, 8 mercaptoquinoline, quinoline-2-powered rubonic acid, and the like.
  • the atalidine compound examples include 9-phenacridine, 1,7-bis (9,9,1ataridininole) heptane, atalidine orange, chloroflavin, and acriflavine.
  • these hetero-fused compounds those containing a nitrogen element in the ring are more preferable.
  • Preferred examples of the compound containing a nitrogen element in the ring include the acridine compound, a coumarin compound substituted with an amino group, and an attaridone compound.
  • the talidone, the coumarin substituted with an amino group, 9-phenylacridine, and the like are more preferable, and the talidone is particularly preferable.
  • Examples of combinations of the photopolymerization initiator and the sensitizer include, for example, an electron transfer-type initiator system described in JP-A-2001-305734 [(1) an electron-donating initiator and a sensitizing dye , (2) electron accepting initiator and sensitizing dye, (3) electron donating initiator, sensitizing dye and electron accepting initiator (ternary initiation system)].
  • the content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0 to 20% by mass, based on all components in the photosensitive composition. 2 to 10% by mass is particularly preferable. If the content is less than 0.05% by mass, the sensitivity to active energy rays may be reduced, the exposure process may take time, and productivity may be reduced. When present, the sensitizer may precipitate from the photosensitive layer.
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • a halogenated carbon having the phosphine oxides, the triaminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the later-described exposure examples include composite photoinitiators that combine hydrogen compounds and amine compounds, hexaryl biimidazole compounds, hexyl biimidazole compounds and hetero-fused compounds, or meta-octenes. It is done.
  • chain transfer agents for example, mercapto compounds, more specifically 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-menolecaptobenzthiazole, etc.
  • chain transfer agents for example, mercapto compounds, more specifically 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-menolecaptobenzthiazole, etc.
  • the content of the photopolymerization initiator in the photosensitive composition is from 0.:! To 30 masses.
  • 0.5 to 20% by mass is more preferable 0.5 to 15% by mass is particularly preferable.
  • the curing accelerator is added to accelerate the thermosetting reaction of a polymer having one or more carboxyl groups and ester groups in one molecule.
  • the curing accelerator is a latent curing accelerator for epoxy resins composed of a compound sharing at least one carboxyl group and amide group in one molecule of the present invention, and the general formulas (1) to (6) It is preferable that the compound is represented by a deviation.
  • the curing accelerator as a photosensitive composition, particularly a photosensitive film, it is possible to obtain a photosensitive composition that does not cause a reaction during storage, or an excellent storage stability of the photosensitive film.
  • a rapid reaction is exhibited to accelerate the curing of the compound, and the cured film formed has high film hardness, chemical resistance, etc.
  • the photosensitive composition solid content of the curing accelerator As a solid content in it, 0.01 to 40% by mass is preferable. 0.01 to: 15% by mass is more preferable, and 0.05 to 5% by mass is particularly preferable.
  • the content is less than 0.01% by mass, the reaction during the heat treatment is lowered, and the strength of the cured film may not be improved.
  • the content exceeds 40% by mass, the developability and exposure sensitivity are increased. And the hardness of the cured film may be lowered.
  • thermosetting accelerators In order to accelerate the thermal curing of the epoxy compound, a conventionally known thermal crosslinking agent or the like can be blended as a thermal curing accelerator separately from the curing accelerator of the present invention.
  • thermosetting accelerator include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) _N, N-dimethylbenzylamine, 4-methoxy-1-N, N-dimethylbenzylamine, 4_methyl_N.
  • Amine compounds such as N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzil ammonium chloride; blocked isocyanate compounds blocked with dimethylamine; imidazole, 2-methylimidazole, 2-ethyl Imidazoles such as imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanethyl-2-phenylimidazole, 1- (2-cyanethyl) 2-ethyl-4-methylimidazole, etc.
  • thermosetting accelerator is not particularly limited as long as it can accelerate the thermosetting of the epoxy compound, and other compounds that can accelerate the thermosetting may be used. .
  • the solid content of the other thermosetting accelerator in the solid content of the photosensitive composition is preferably 0.01 to 15% by mass.
  • the thermal crosslinking agent is not particularly limited and can be appropriately selected according to the purpose.
  • an epoxy compound having at least two oxsilane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
  • the epoxy compound having at least two oxysilane groups in one molecule include, for example, bixylenol type or biphenol type epoxy resins (“YX4000; manufactured by Japan Epoxy Resin” etc.) or a mixture thereof, isocyanurate skeleton, etc.
  • Heterocyclic epoxy resins (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba“ Specialty Chemicals ”, etc.), bisphenol A type epoxy resins, novolak type epoxy resins, bis Phenolic F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidinoleamine type epoxy resin, hydantoin type epoxy resin, cycloaliphatic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol Enol A novolac epoxy resin, Tet Phenylolethane type epoxy resin, Daricidyl phthalate resin, Tetraglycidino lexylylene ethane resin, Naphthalene group-containing epoxy resin ESN-190, ESN-360; — 4032, EXA— 4750, EXA— 4700; manufactured by Dainippon Ink Chemical Co., Ltd.), epoxy resin having a dicyclopentagen skeleton (“HP-7200
  • an epoxy compound containing at least two epoxy groups having an alkyl group at the / 3-position in one molecule is used.
  • a compound containing an epoxy group substituted at the ⁇ -position with an alkyl group is particularly preferable.
  • epoxy compound containing at least an epoxy group having an alkyl group at the j3 position all of two or more epoxy groups contained in one molecule may be ⁇ -alkyl-substituted glycidyl groups, and at least one epoxy group May be a j3_alkyl-substituted glycidyl group.
  • the epoxy compound containing an epoxy group having an alkyl group at the ⁇ -position is an all-epoxy group in the total amount of the epoxy compound contained in the photosensitive composition. Percentage of alkyl-substituted glycidinole group in 70% or more It is preferable that it is above.
  • the —alkyl-substituted glycidinole group is not particularly limited and may be appropriately selected depending on the purpose.
  • / 3-methyldaricidinole group Is preferred.
  • the epoxy compound containing an epoxy group having an alkyl group at the ⁇ -position is preferably, for example, an epoxy compound derived from a polyhydric phenol compound and an -alkylephalohydrin.
  • the ⁇ -alkylepihalohydrin is not particularly limited and can be appropriately selected according to the purpose.
  • ⁇ -methylepichlorohydrin, ⁇ -methylepibromohydrin, ⁇ -methylepihalohydrin such as ⁇ -methylepifluorohydrin; ⁇ -ethylepichlorohydrin, ethylepive mouth mohydrin, ethylepifluorohydrin, etc.
  • ⁇ -propylepichloro ⁇ -propylepihalohydrin such as hydrin, ⁇ -propylepib mouth mohydrin, ⁇ -propylepifluorohydrin; ⁇ -butylepephalohydrin, ⁇ -butylepive mouth mohydrin, ⁇ -butylepifluorohydrin, etc. Halohydrin; and the like.
  • ⁇ -methylepihalohydrin is preferable from the viewpoints of reactivity with the polyhydric phenol and fluidity.
  • the polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose, for example, bisphenol alcohol.
  • Bisphenol compounds such as ⁇ , bisphenol F and bisphenol S; biphenol compounds such as biphenol and tetramethylbiphenol; naphthol compounds such as dihydroxynaphthalene and binaphthol; phenol novolak resins such as phenol-formaldehyde polycondensates; A monoalkyl-substituted phenol monoformaldehyde polycondensate having 1 to 10 carbon atoms such as formaldehyde polycondensate; a dialkyl-substituted phenol having 1 to 10 carbon atoms such as xylenol monoform aldehyde polycondensate and a formaldehyde polycondensate; Bisphenol A A Holmoor Bisphenol compounds such as aldehyde polyconden
  • Examples of the epoxy compound containing an epoxy group having an alkyl group at the ⁇ -position include di- ⁇ -alkyl glycidyl ethers of bisphenol or bisphenol F, di- ⁇ -alkyl glycidyl ethers of bisphenol F, and bisphenol S.
  • Di- ⁇ -alkyl glycidyl ethers and other bisphenol compounds such as di-alkyl glycidyl ethers; Biphenol diols ⁇ alkyl glycidyl ethers and tetramethylbiphenol diols ⁇ alkyl glycidyl ethers and other biphenol compound diols ⁇ alkyl glycidyl ⁇ ether glycidyl ethers of naphthol compounds such as dihydroxy naphthalene bis ⁇ alkyl glycidyl ether and binaphthol bis ⁇ alkyl glycidyl ether; phenol-formaldehyde polycondensate Poly ⁇ alkyl glycidyl ether; poly ⁇ alkyl glycidyl etherol of 1-10 carbon monoalkyl-substituted phenol-formaldehyde polycondensate such as poly ⁇ alkyl gly
  • the thermal cross-linking agent is preferably an epoxy compound having at least two oxosilane groups in one molecule, and the oxysilane group is a compound having two substituents. Of the two substituents in the oxysilane group, one substituent is for linking two or more oxysilane groups present in the molecule, and It is preferable that a substituent other than the substituent (for linking the oxysilane group) is present in the oxysilane group.
  • Such a thermal crosslinking agent is preferably a compound represented by any one of the following general formulas (7) and (9).
  • P represents an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene group, or an arylene group
  • Q represents boron.
  • W represents naphthalene having a bond with two X 26 s
  • a 21 A 25 represents a single bond, an alkylene group, or an arylene group.
  • X 21 X 26 represents any one of OCONH—NHCOO NHCO— and CONH.
  • R 21 R 26 represents any one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
  • alkylene group in P examples include an unsubstituted alkylene group, an aryl group, an alkenyl group, a hydroxyl group, an alkoxy group, a cyan group, and a substituent-containing alkylene group substituted with a halogen atom.
  • the unsubstituted alkylene group may have a double bond or a triple bond which may have a branch.
  • the unsubstituted alkylene group As the total number of carbon atoms of the unsubstituted alkylene group,:!-20 is preferable:!-8 is particularly preferable.
  • the unsubstituted alkylene group include ethylene, propylene, i_propylene, butylene, i-butylene, cyclohexylene, and the like.
  • aryl substituents in the substituent-containing alkylene group those having a total carbon number of 6 to 30 are preferable, and 6 to 15 is particularly preferable.
  • the aryl substituent include a phenylol group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
  • the alkenyl substituent in the substituent-containing alkylene group preferably has 2 to 6 carbon atoms, particularly preferably 2 to 6 carbon atoms.
  • Examples of the alkenyl substituent include an ethur group, a propenyl group, a petityl group, and the like.
  • the alkoxy substituent in the substituent-containing alkylene group preferably has a total carbon number of! To 10 which may have a branch:! To 5 is particularly preferable.
  • Examples of the alkoxy substituent include a methoxy group, an ethoxy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.
  • the substituent-containing alkylene group may have a double bond or a triple bond which may have a branch.
  • the total number of carbon atoms of the substituent-containing alkylene group is preferably 2 to 40 forces S, and particularly preferably 2 to 25.
  • substituent-containing alkylene group examples include 2_ethylhexenole group, chlorobutyl group, benzyl group, 2-ethylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group, and the like.
  • the arylene group for P has the same meaning as the arylene group for A 21 to A 25 described later.
  • Examples of the alkylene group for Q include an unsubstituted alkylene group for P.
  • the unsubstituted alkylene group may have, for example, a double bond or a triple bond that may have a branch.
  • a total carbon number of the said unsubstituted alkylene group 2-30 are preferable, for example.
  • unsubstituted alkylene group examples include ethylene, propylene, i_propylene, butylene, i-butylene, cyclohexylene, and the like.
  • the arylene group of Q has the same meaning as the arylene group of A 21 to A 25 described later.
  • binding site with the X moiety in W examples include, for example, 1, 2 position, 1, 3 position, 1, 5 position, 1, 6 position, 1, 7 position, 1, 8 position, 2, 3rd, 2, 4th, 2, 5th, 2, 7th place S
  • the W may be an alkyl group, an aryleno group, an alkoxy group, or a halogen atom, which may be substituted.
  • Examples of the arylene group in A 21 to A 25 include, for example, a benzene ring and an alkyl group, an aryl group, an alkenyl group, an alkoxy group, a cyan group, and a substituent that is substituted with a rogen atom.
  • the alkyl substituent in the substituent-containing arylene group is preferably one having a total number of carbon atoms of 1 to 20 which may have a double bond or a triple bond which may have a branch. 1 to 10 is particularly preferable.
  • the alkyl substituent include a methyl group, an ethyl group, an ethynino group, a propyl group, an isopropyl group, a butyl group, an sbutyl group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group. .
  • aryl substituents in the substituent-containing arylene group those having a total carbon number of 6 to 30 are preferable, and 6 to 15 is particularly preferable.
  • the aryl substituent include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
  • the alkenyl substituent in the substituent-containing arylene group preferably has 2 to 6 carbon atoms, particularly preferably 2 to 6 carbon atoms.
  • Examples of the alkenyl substituent include an ethur group, a propenyl group, a petityl group, and the like.
  • the alkoxy substituent in the substituent-containing arylene group may have a branch, but preferably has a total carbon number:! To 10 and particularly preferably! To 5.
  • Examples of the alkoxy substituent include a methoxy group, an ethoxy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.
  • the substituent-containing arylene group is particularly preferably 2 to 25, preferably a total of 2 to 40 carbon atoms which may have a double bond or a triple bond.
  • substituent-containing arylene group examples include, for example, a methyl phenyl ring, a dimethyl phenyl ring, a dibutyl phenyl ring, a methoxy phenyl ring, a cyclohexyl phenyl ring, And biphenyl structure, dichlorophenyl ring, tribromophenyl ring, chlorocyanophenyl ring, and the like.
  • the alkylene group for A 21 to A 25 has the same meaning as the alkylene group for P.
  • X 21 to X 26 represent any one of 10C 0 NH-, 1 NHCOO, 1 NHCO, and _C 0 NH_.
  • Examples of the alkyl group in R 21 to R 26 include, for example, an unsubstituted alkyl group, and an aryl group, an alkenyl group, a hydroxyl group, an alkoxy group, a cyan group, and a halogen atom.
  • Examples thereof include a substituent-containing alkyl group which may have a divalent group of oxygen atom, sulfur atom, carbonyl group, amide group, urethane group, urea group and ester group.
  • the unsubstituted alkyl group is preferably one having a total number of carbon atoms of 1 to 20 which may have a double bond or a triple bond which may have a branch: preferable.
  • Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, a sbutyl group, a tbutyl group, a butyryl group, a cyclohexynole group, a cyclohexenyl group, Etc.
  • aryl substituent in the substituent-containing alkyl group those having a total carbon number of 6 to 30 are preferable, and 6 to 15 is particularly preferable.
  • the aryl substituent include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
  • the alkenyl substituent in the substituent-containing alkyl group preferably has a total carbon number of 2 to 10 and particularly preferably 2 to 6.
  • Examples of the alkenyl substituent include an ethur group, a propenyl group, a butyryl group, and the like.
  • alkoxy substituent in the substituent-containing alkyl group a total carbon number of 1 to 10 which may have a branch is preferable:! To 5 is particularly preferable.
  • alkoxy substituent include methoxy group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
  • substituted alkyl group examples include 2-ethylhexyl group, chlorobutyl Group, benzyl group, 2-ethylpropyl group, phenylethyl group, cyanopropyl group, methoxetyl group, and the like.
  • Examples of the compound represented by any one of the general formulas (7) to (9) include a compound represented by the following formula.
  • Examples of the oxetane compound include bis [(3-methyl_3-oxetanylmethoxy) methyl] ether, bis [(3_ethyl_3-oxetanylmethoxy) methyl] ether, 4_bis [(3-methyl_3-oxetanylmethoxy) methyl] benzene, 1,4_bis [(3_ethyl_3-oxetanylmethoxy) methyl] benzene, (3_methyl_3_oxe Tanyl) methyl atallylate, —ethyl _ 3—oxetanyl) methyl atylate, (3-methyl _3-oxetaninole) methyl metatalylate, (3-ethyl _3-oxetaninole) methyl metatalylate or oligomers or co-polymers thereof In addition to polyfunctional oxetanes such as polymers, oxetanes such
  • a melamine derivative can be used as the thermal crosslinking agent.
  • the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, etc.). These may be used alone or in combination of two or more. Of these, alkylated methylol melamine is preferred and hexamethylated methylol melamine is particularly preferred because of its good storage stability and effectiveness in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.
  • thermal crosslinking agent a compound represented by any one of the following structural formulas (I) and (II) can be used.
  • R represents either a hydrogen atom or an alkyl group having from 6 to 6 carbon atoms, and n represents an integer of 0 to 20.
  • the solid content in the solid content of the photosensitive composition of the thermal crosslinking agent is preferably 3 to 30% by mass, preferably:! When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not observed, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.
  • the other components include thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and further, adhesion promoters to the substrate surface and other assistants.
  • Agents e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • properties such as the stability, photographic properties, and film properties of the target photosensitive composition or photosensitive film.
  • the thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
  • thermal polymerization inhibitor examples include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4 methoxy-2-hydroxybenzophenone, Cuprous, phenothiazine, chlorael, naphthylamine, ⁇ -naphthol, 2, 6-di_t_butyl _4 —taresol, 2, 2'-methylenebis (4 methyl _6 _t_butylphenol), pyridine, nitrobenzene, dinitrobenzene, Picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nito Examples include chelates of losso compounds and Al.
  • the content of the thermal polymerization inhibitor is preferably from 0.00:! To 5 mass% relative to the polymerizable compound, more preferably from 0.005 to 2 mass% force S, and 0.01. ⁇ :!% By mass is particularly preferred. If the content is less than 0.001% by mass, the stability during storage may be reduced, and if it exceeds 5% by mass, the sensitivity to active energy rays may be reduced.
  • the coloring pigment is not particularly limited and can be appropriately selected according to the purpose.
  • Victoria 'Pure One Blue BO CI 42595
  • Auramin CI 41000
  • Fat' Black HB CI 26150
  • Mono Light Yellow GT CI Pigment Yellow 12
  • Permanent Yellow GR CI Pigment Yellow 17
  • Permanent Yellow HR CI Pigment Yellow 83
  • Permanent Carmine FBB CI Pigment Red 146
  • Hoster Balm Red ESB CI Pigment 'Violet 19
  • Permanent' Ruby FBH CI Pigment 'Red 11
  • Huster's' Pink B Supra CI Pigment' Red 81
  • Monastral First 'Blue CI Pigment' Blue 15
  • Monolite 'First' Black B CI Pigment 'Black 1
  • Carbon CI Pigment 'Let 97
  • CI Pic Men' Red 122, CI Pic, Men 'Red 149, CI Pic, Men' Red 168, CI Pigment 'Red 177
  • the solid content in the solid content of the photosensitive composition of the coloring pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during the formation of a permanent pattern. Different forces depending on the type of facial material Generally 0.01 to 10% by mass is preferred, and 0.05 to 5% by mass is more preferred.
  • Inorganic pigments and organic fine particles can be added for the purpose of keeping the linear expansion coefficient low or keeping the dielectric constant and dielectric loss tangent of the cured film itself low.
  • the inorganic pigment can be appropriately selected from known ones that are not particularly limited, and examples thereof include kaolin, barium sulfate, noble titanate, key oxide powder, fine powder oxide oxide, vapor phase method silica, Amorphous silica, crystalline silica, fused silica, spherical silica, Tanolec, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, My strength, and the like can be mentioned.
  • the average particle size of the inorganic pigment is preferably 3 ⁇ or less, preferably less than 10 ⁇ . If the average particle size is 10 ⁇ m or more, resolution may deteriorate due to light scattering.
  • the organic fine particles are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. In addition, silica having an average particle diameter of 1 to 5 / im, an oil absorption of about 100 to 200 m 2 / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.
  • the amount of the extender pigment added is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function as a wiring protective film may be impaired.
  • adhesion promoter In order to improve the adhesion between the layers or between the photosensitive layer and the substrate, a known adhesion promoter or a so-called adhesion promoter can be used for each layer.
  • adhesion promoter examples include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzoximidazole, 2_mercaptobenzoxazole, 2_mercaptobenzthiazole, 3_morpholinomethyl _ 1 _phenol ritriazole _ 2-thione , 3 _ morpholino methinore _ 5 _ phenyloloxadiazole-2-thione, 5-amino _ 3-morpholinomethyl-thiadiazole-2 thione, and 2 mercapto-5 methylthio —Thiadiazole, triazolole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.
  • the content of the adhesion promoter is preferably 0.001% by mass to 20% by mass with respect to all components in the photosensitive composition, and more preferably 0.01% to 10% by mass. More preferably, 1% by mass to 5% by mass is particularly preferable.
  • the photosensitive composition of the present invention can form an image by UV exposure, has low surface tackiness, good laminating properties and handling properties, excellent storage stability, high sensitivity, and excellent developability. It exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, etc. after development. For this reason, protective materials for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, color filters, pillar materials, rib materials, spacers, partition walls, and other display members It can be widely used for forming permanent patterns such as holograms, micromachines, and proofs, and can be particularly suitably used for the photosensitive film, permanent pattern, and method for forming the same of the present invention.
  • the curing accelerator of the present invention contained in the photosensitive composition functions as a thermal crosslinking agent, excellent film hardness of the cured film can be obtained without adding a thermal crosslinking agent separately.
  • a particularly sensitive photosensitive composition can be obtained and widely used for forming the permanent pattern.
  • the photosensitive film of the present invention, the permanent pattern and the formation thereof It can be particularly preferably used in the method.
  • thermosetting resin composition of the present invention includes at least an epoxy resin compound and the curing accelerator of the present invention, and may further include a curing agent as necessary.
  • the content of the curing accelerator is preferably 0.0 :! to 50% by mass, more preferably 0.01 to 40% by mass with respect to the content of the epoxy resin compound.
  • the content When the content is less than 0.01% by mass, the reactivity during the heat treatment may decrease, and the strength of the cured film may not be improved. When the content exceeds 50% by mass, developability, It may cause a decrease in exposure sensitivity and a decrease in film hardness of the cured film.
  • Examples of the epoxy resin compound include those used in the photosensitive composition of the present invention. Similar epoxy resin compounds can be used.
  • the curing agent is not particularly limited as long as it can react with the epoxy resin without limitation, and can be appropriately selected from known curing agents.
  • phenolic resins amine compounds, acid anhydrides. , Active esters, carboxylic acid compounds, sulfonic acid compounds, and the like.
  • compounds having two or more phenolic hydroxyl groups in one molecule and amine-based curing agents are particularly preferred.
  • the phenolic novolac resin, the cresolone novolak resin, and the alkyl-modified are used.
  • Preferable examples include novolak resins, phenol aralkyl resins, resins obtained by co-condensation of naphthols and phenols with a carbonyl group-containing compound, and co-condensates of dicyclopentagen and phenols.
  • aromatic diamines such as diaminodiphenol, aniline resins, dicyandiamide, guanidine and derivatives thereof are preferably exemplified.
  • curing agent is not restricted to the said illustration.
  • the content of the curing agent is preferably from 0.3 to 3.0 equivalents, more preferably from 0.5 to 2.5 equivalents, and from 0.8 to 2.0 equivalents per 1 equivalent of epoxy group. Particularly preferred.
  • thermosetting resin composition of the present invention does not cause a curing reaction at room temperature during storage, can be cured by heating, has excellent storage stability, and has excellent chemical resistance, hardness, heat resistance, dielectric after curing. Since characteristics, electrical insulation, etc. can be expressed, it can be suitably used for adhesives and the like.
  • the photosensitive film of the present invention includes at least a support and a photosensitive layer, preferably includes a protective film, and further includes a cushion layer, an oxygen barrier layer (PC layer) and the like as necessary. It has other layers.
  • the form of the photosensitive film is not particularly limited and may be appropriately selected depending on the purpose.
  • the photosensitive film and the protective film are provided on the support in this order.
  • Form Form in which the PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film on the support. In this order.
  • the photosensitive layer may be a single layer or a plurality of layers.
  • the photosensitive layer is formed by the photosensitive composition of the present invention.
  • the portion of the photosensitive layer provided in the photosensitive film is not particularly limited, and can be appropriately selected according to the purpose.
  • the photosensitive layer laminated on the support is an exposure step described later.
  • the aberration due to the distortion of the emission surface in the picture element It is preferable to be exposed to light through a microlens array in which microlenses having an aspheric surface capable of correcting are arranged.
  • the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 100 (mj / cm 2 ) is preferred:! ⁇ 80 mj / cm 2 is more preferred. If the minimum energy force of light used for the exposure is less than 0.1 lmj / cm 2 , the processing margin may be narrowed, and if it exceeds 100 mj / cm 2 , the tact time becomes long, which is not preferable.
  • the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is so-called development sensitivity. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure when exposed and the thickness of the cured layer generated by the development process following the exposure. .
  • the thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure.
  • the development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
  • the thickness of the cured layer is not changed by exposure and development.
  • a method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the intended purpose. (For example, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) can be used.
  • the thickness of the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose. For example, 3 to: 100 ⁇ m is preferable, and 570 ⁇ m is more preferable.
  • a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support.
  • coating a solution directly and drying is mentioned.
  • the solvent of the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol, n-propanol, isopropanol n-butanol, sec butanol, and n-xanol. Alcohols: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone, etc.
  • ketones ethyl acetate, butyl acetate, namyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate And esters such as methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methyl chloride, monochrome Halogens such as mouth benzene Hydrocarbons such as tetrahydrofuran, jetyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy_2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. Can be mentioned. These may be used alone or in combination of two or more
  • the coating method can be appropriately selected depending on the purpose without any particular limitation.
  • coating directly to a support body is mentioned.
  • the drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.
  • the support is not particularly limited and can be appropriately selected according to the purpose. It is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and it is more preferable that the surface smoothness is good.
  • the support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic. Alkyl ester, poly (meth) acrylate ester copolymer, polychlorinated butyl, polybutyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride. Butyl acetate Various plastic films such as polymers, polytetrafluoroethylene, polytrifluoroethylene, cellulose-based films, nylon films and the like can be mentioned. Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
  • Examples of the support include, for example, JP-A-4 208940 and JP-A-5-8050.
  • the thickness of the support is not particularly limited, and can be appropriately selected according to the purpose. For example, 4 to 300 ⁇ m is preferable, and 5 to 175 ⁇ m is more preferable.
  • the shape of the support is not particularly limited, and is preferably a long and long force that can be appropriately selected according to the purpose.
  • the length of the long support is not particularly limited.
  • the length of the long support is 10 m to 20,000 m.
  • the protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
  • the portion of the protective film provided in the photosensitive film is not particularly limited and may be appropriately selected according to the purpose. Usually, it is provided on the photosensitive layer.
  • protective film examples include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film, polypropylene, etc. Renfinorem is preferred.
  • the thickness of the protective film is not particularly limited and may be appropriately selected depending on the purpose. For example, 5 to 100 zm force is preferable, and 8 to 30 zm is more preferable.
  • the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
  • Examples of the combination of the support and the protective film include, for example, polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate. Etc.
  • a surface treatment to at least one of the support and the protective film, it is possible to satisfy the adhesive force relationship as described above.
  • the surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer.
  • a primer layer for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • ultraviolet irradiation treatment for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment,
  • One discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like can be mentioned.
  • the coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2.
  • the photosensitive film is preferably wound and stored in a long roll shape, for example, wound around a cylindrical core.
  • the length of the long photosensitive film is not particularly limited, and can be appropriately selected from a range of 10 m to 20,000 m, for example.
  • slitting may be performed so that it is easy for the user to use, and a long body in the range of 100 m to l, 000 m may be rolled. In this case, it is preferable that the support is scraped off so as to be the outermost side.
  • the roll-shaped photosensitive film may be slit into a sheet.
  • the packaging is low in moisture permeability, and it is preferable to use materials.
  • the protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer.
  • an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polybutyl alcohol is formed on the surface of the protective film.
  • the undercoat layer is formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C (especially 50 to 120 ° C) for 1 to 30 minutes. Can be made.
  • a cushion layer In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.
  • PC layer oxygen blocking layer
  • a release layer In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.
  • PC layer oxygen blocking layer
  • a release layer an adhesive layer, a light absorption layer, a surface protective layer, and the like.
  • the cushion layer is a layer that melts and flows when laminated under vacuum and heating conditions that have no tackiness at room temperature.
  • the PC layer is usually a film of about 0.5 to 5 / im formed with polyvinyl alcohol as a main component.
  • the photosensitive film of the present invention has low surface tackiness, good laminating properties and handleability, excellent storage stability, high sensitivity and excellent developability, and excellent chemical resistance after development. It has a photosensitive layer on which a photosensitive composition exhibiting surface hardness, heat resistance, dielectric properties and the like is laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for a permanent pattern and a method for forming the permanent pattern. Further, when no amine thermosetting agent is used, a photosensitive film having particularly high sensitivity can be obtained, and can be particularly suitably used for the above-mentioned use.
  • the photosensitive film of the present invention since the photosensitive film of the present invention has a uniform thickness, the film is more precisely laminated on the substrate when the permanent pattern is formed.
  • the permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
  • the photosensitive composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed and developed.
  • the method for forming a permanent pattern of the present invention includes, as a second aspect, the photosensitive film of the present invention.
  • the film is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed.
  • the base material can be appropriately selected from publicly known materials that are not particularly limited to those having a high surface smoothness and a surface having a rough surface, and a plate-like base material (substrate) is preferred.
  • Specific examples include known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic resin films, paper, metal plates, etc.
  • the printed wiring board forming substrate has already been formed in that it can be mounted on a multilayer wiring board where a printed wiring board forming substrate is preferred, such as a semiconductor on a built-up wiring substrate. It is especially preferred to have it.
  • the substrate is a laminate in which a photosensitive layer made of the photosensitive composition is formed on the substrate as the first aspect, or the photosensitive film in the photosensitive film as the second aspect. It is possible to form and use a laminated body in which the layers are laminated so as to overlap each other. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed area can be cured, and a permanent pattern can be formed by development to be described later.
  • the method for forming the laminate of the first aspect is not particularly limited and can be appropriately selected according to the purpose, but the photosensitive composition is applied and dried on the substrate. It is preferable to laminate a photosensitive layer.
  • the method for coating and drying can be appropriately selected according to the purpose without any particular limitation.
  • the method for forming the photosensitive composition solution in the photosensitive film can be performed when the photosensitive layer is formed on the photosensitive film.
  • a method of applying the photosensitive composition solution by using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like can be used.
  • the method for forming the laminate of the second aspect is not particularly limited.
  • the force can be appropriately selected according to the purpose.
  • the photosensitive film is heated and pressed little on the substrate. It is preferable to stack while performing at least one of them.
  • the heating temperature is not particularly limited and can be appropriately selected according to the purpose. ⁇ ⁇ ⁇ 70, 70 ⁇ : 130 o C ⁇ ; childlike, 80 ⁇ : 110 o C .
  • the pressure of the pressurization is not particularly limited, and can be appropriately selected according to the purpose. ⁇ column-excluded, 0.01-: 1. OMPa is preferable, 0.05-: 1. OMPa More preferred.
  • the apparatus for performing at least one of the heating and pressurization can be appropriately selected depending on the purpose, and for example, a heat press, a heat roll laminator (for example, Taisei Laminate Earthen, VP 11), a vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho) and the like are preferable.
  • a heat press for example, Taisei Laminate Earthen, VP 11
  • a vacuum laminator for example, MVLP500 manufactured by Meiki Seisakusho
  • the exposure step is a step of exposing the photosensitive layer.
  • the subject of the exposure is not particularly limited as long as it is a material having a photosensitive layer, and can be appropriately selected depending on the purpose.
  • the photosensitive composition or the photosensitive composition described above is formed on a substrate. It is preferable to perform with respect to the said laminated body in which a conductive film is formed.
  • the exposure of the laminate is not particularly limited and may be appropriately selected depending on the purpose.
  • the photosensitive layer may be exposed through the support, the cushion layer, and the PC layer. After peeling off the support, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling off the support and cushion layer, the photosensitive layer is exposed through the PC layer. The photosensitive layer may be exposed after the support, cushion layer and PC layer are peeled off.
  • the exposure is not particularly limited and can be appropriately selected according to the purpose. Among these, digital exposure, analog exposure, and the like are preferred. Digital exposure is preferable among these.
  • the digital exposure is a force that can be appropriately selected according to the purpose without any particular limitation.
  • a control signal is generated based on pattern formation information to be formed, and is modulated according to the control signal. It is preferable to use light.
  • the means for digital exposure is not particularly limited, and may be appropriately selected according to the purpose.
  • a light irradiating means for irradiating light a light modulating means for modulating light emitted from the light irradiating means based on pattern information to be formed, and the like can be mentioned.
  • the light modulating means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose.
  • it preferably has n pixel portions.
  • the light modulation means having the n picture element portions can be appropriately selected according to the purpose without any particular limitation.
  • a spatial light modulation element is preferable.
  • Examples of the spatial light modulation element include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM; Special Light Modulator), and transmission by an electro-optic effect.
  • Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
  • the light modulation means has a pattern signal generation means for generating a control signal based on pattern information to be formed.
  • the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
  • the control signal is not particularly limited and can be appropriately selected according to the purpose.
  • a digital signal is preferable.
  • examples of the light modulation means include the light modulation means described in paragraphs “0016” to “0047” of the specification of JP-A-2005-258431.
  • the light irradiation means is not particularly limited and can be appropriately selected according to the purpose.
  • (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, photocopier fluorescent lamp, LED A known light source such as a semiconductor laser or means capable of combining and irradiating two or more lights can be mentioned. Among these, means capable of combining and irradiating two or more lights are preferable.
  • the light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support.
  • laser light that is preferred by laser light is more preferable laser light that combines two or more lights (hereinafter sometimes referred to as “combined laser light”).
  • similar light can be used even when light irradiation is performed after the support is peeled off.
  • the wavelength of the ultraviolet to visible light is, for example, preferably 300-1,500 nm, more preferably 320-800 nm, particularly preferably 330-650 nm.
  • the wavelength of the laser beam is preferably 200 to 1,500 nm, more preferably 300 to 800 nm, further preferably 330 to 500 nm, and particularly preferably 395 to 415 nm.
  • Examples of means capable of irradiating the combined laser light include, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces to collect the multimode optical fiber.
  • a means having a collective optical system to be coupled to is preferable.
  • the means (fiber array light source) capable of irradiating the combined laser beam is described in paragraphs “0130” to “0177” of the specification of JP-A-2005-316431, for example.
  • the exposure is preferably performed through the microlens array with the modulated light, and may be performed through an aperture array, an imaging optical system, or the like.
  • the microlens array is not particularly limited and can be appropriately selected according to the purpose.
  • the microlens array has an aspheric surface that can correct aberration due to distortion of the exit surface in the pixel portion.
  • Preferred examples include those in which
  • the aspherical surface is not particularly limited and can be appropriately selected according to the purpose.
  • a toric surface is preferable.
  • FIG. 2 (A) shows DMD50, light irradiating means 144 for irradiating DMD50 with laser light, and a lens system (imaging optical system) 454, 458 for enlarging the laser light reflected by DMD50.
  • FIG. 3 shows the result of measuring the flatness of the reflection surface of the micromirror 62 constituting the DMD 50.
  • the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm.
  • the X direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction as described above.
  • 4A and 4B show the height position displacement of the reflecting surface of the micromirror 62 along the X direction and the y direction, respectively.
  • the microlens 55a of the microlens array 55 has a special shape different from the conventional one. This point will be explained in detail below.
  • FIGS. 5A and 5B respectively show the front and side shapes of the entire microlens array 55 in detail. These figures also show the dimensions of each part of the microlens array 55, and their units are mm.
  • FIG. 1 1,024 ⁇ 256 rows of micromirrors 62 of DMD50 are driven, and correspondingly, microlens array 55 is formed in the horizontal direction.
  • 1,024 microlenses 55a are arranged in 256 rows in the vertical direction.
  • FIG. A the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.
  • FIG. 6 show the front shape and side shape of one microphone opening lens 55a in the microlens array 55, respectively.
  • the contour lines of the micro lens 55a are also shown.
  • the end surface of each microlens 55a on the light emission side has an aspherical shape that corrects aberration due to distortion of the reflection surface of the micromirror 62.
  • the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction is roughly as shown in FIGS. 7A and 7B, respectively. That is, when comparing the cross section parallel to the x direction and the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. ing.
  • FIGS. 8A to 8D show the simulation results of the beam diameter in the vicinity of the condensing position (focus position) of the microlens 55a when the microlens 55a has the above-described shape.
  • the surface shape of the microlens 55a used in the simulation is calculated by the following calculation formula.
  • X is the X direction.
  • Y means the distance from the lens optical axis O with respect to the y direction.
  • the microlens 55a has a focal length in the cross section parallel to the y direction.
  • a toric lens smaller than the focal length in the cross section parallel to the beam, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, the photosensitive layer 150 can be exposed to a finer image without distortion.
  • the present embodiment shown in FIGS. 8A to 8D can be characterized in that the region where the beam diameter is small is wider, that is, the depth of focus is larger.
  • the focal length in the cross section parallel to the X direction is parallel to the y direction. If the microlens is made up of a toric lens that is smaller than the focal length in the cross section, similarly, a higher-definition image without distortion can be exposed on the photosensitive layer 150.
  • the aperture array 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged so that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. . That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to enhance the extinction ratio.
  • the microlens 55a may have a higher-order (fourth-order, sixth-order ...) aspherical shape, which may be a second-order aspherical shape. There may be.
  • the beam shape can be further refined.
  • the end surface of the microlens 55a on the light exit side is an aspherical surface.
  • a microlens array can be constructed from microlenses in which one of the two light-passing end surfaces is a spherical surface and the other is a cylindrical surface, and the same effect as in the above embodiment can be obtained. it can.
  • the microlens 55a of the microlens array 55 has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62.
  • Such an aspherical shape The same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution that corrects aberration due to distortion of the reflection surface of the micromirror 62 instead of adopting the above.
  • FIG. (A) and (B) in the figure are Each shows a front shape and a side shape of the microlens 155a. As shown, the outer shape of the microlens 155a is a parallel plate. The X and y directions in the figure are as described above.
  • FIG. 11 schematically show the condensing state of the laser light B in the cross section parallel to the X direction and the y direction by the microlens 155a.
  • the microlens 155a has a refractive index distribution that gradually increases outward from the optical axis O.
  • the broken line shown in the microlens 155a in FIG. The position changed with the pitch is shown.
  • the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and The distance is getting shorter. Even when a microlens array having such a gradient index lens force is used, the same effect as that obtained when the microlens array 55 is used can be obtained.
  • the refractive index distribution as described above is also given, and the surface shape and the refractive index component are given.
  • the aberration due to the distortion of the reflection surface of the micromirror 62 may be corrected by both the cloths.
  • the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected.
  • the permanent pattern forming method of the present invention using a spatial light modulation element other than the DMD is also used. If there is distortion on the surface of the picture element portion of the spatial light modulator, the present invention can be applied to correct the aberration caused by the distortion and prevent the beam shape from being distorted.
  • the cross-sectional area force of the light beam reflected in the ON direction by the DMD 50 is enlarged several times (for example, two times) by the lens systems 454 and 458. Is done.
  • the expanded laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50, and passes through the corresponding aperture of the aperture array 476.
  • the laser beam that has passed through the aperture is imaged on the exposed surface 56 by the lens systems 480 and 482.
  • the laser beam reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. .
  • the microlens array 472 and the aperture array 476 are not arranged, as shown in FIG. 2B, one pixel size (spot size) of each beam spot BS projected onto the exposed surface 56 Becomes larger depending on the size of the exposure area 468, and the MTF (Modulation Transfer Function) characteristic representing the sharpness of the exposure area 468 is degraded.
  • MTF Modulation Transfer Function
  • the laser light reflected by the DMD50 corresponds to each pixel part of the DMD50 by each microlens of the microlens array 472. And condensed.
  • the spot size of each beam spot BS can be reduced to a desired size (for example, 10 / im ⁇ 10 / im). It is possible to perform high-definition exposure by preventing the deterioration of MTF characteristics.
  • the exposure area 468 is tilted because the DMD 50 is tilted in order to eliminate the gap between the pixels.
  • the aperture array can shape the beam so that the spot size on the exposed surface 56 is constant. At the same time, by passing through an aperture array provided corresponding to each pixel, crosstalk between adjacent pixels can be prevented.
  • the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. It is possible to prevent a part of the light beam from entering. That is, a high extinction ratio can be realized.
  • the permanent pattern forming method of the present invention may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light quantity distribution correction optical system composed of a pair of combination lenses. .
  • the light quantity distribution correcting optical system is configured so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller at the exit side than at the entrance side.
  • the light quantity distribution on the irradiated surface is corrected so as to be substantially uniform. Examples of the light amount distribution correcting optical system include those described in paragraphs “0090” to “0105” of the specification of JP-A-2005-258431.
  • the developing step is a step of exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region to form a permanent pattern.
  • the method for removing the uncured region is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include a method for removing the uncured region using a developer.
  • the developer is not particularly limited and can be appropriately selected according to the purpose.
  • alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, quaternary Preferable examples include an aqueous solution of ammonium salt.
  • an aqueous sodium carbonate solution is particularly preferable.
  • the developer includes a surfactant, an antifoaming agent, and an organic base (for example, pendinoleamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triphenyl). Ethanolamine) and organic solvents (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination to accelerate development.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or an organic solvent alone.
  • the permanent pattern forming method of the present invention further includes a heat treatment as a curing treatment step, and further includes an entire surface exposure treatment as necessary.
  • the curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.
  • the heat treatment is performed to sufficiently improve the film hardness due to the thermal crosslinking effect of the curing accelerator of the present invention.
  • the heat treatment may be a whole surface heat treatment Of these, heat treatment in a pattern may be performed, and among these, heat treatment on the entire surface is preferable.
  • Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
  • the caloric temperature in the whole surface caloric fever 120 to 250 ° C., preferably 120 to 200 ° C. is preferable.
  • the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment.
  • the heating temperature exceeds 250 ° C, the resin in the photosensitive composition is decomposed and the film quality is weak. May become brittle.
  • the heating time in the entire surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
  • the apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
  • Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. By this overall exposure, curing of the resin in the photosensitive composition forming the photosensitive layer is accelerated, and the surface of the permanent pattern is cured.
  • the apparatus for performing the entire surface exposure can be appropriately selected according to the purpose without any particular limitation.
  • a UV exposure machine such as an ultra-high pressure mercury lamp is preferably used.
  • the base material is a printed wiring board such as a multilayer wiring board
  • the permanent pattern of the present invention is formed on the printed wiring board, and soldering may be performed as follows. it can.
  • the hardened layer which is the permanent pattern is formed by the developing step, and the metal layer is exposed on the surface of the printed wiring board.
  • Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, semiconductors and parts are mounted on the soldered parts.
  • the permanent pattern by the hardened layer is It functions as a protective film or insulating film (interlayer insulating film), and prevents external shocks and conduction between adjacent electrodes.
  • the permanent pattern formation method of the present invention it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
  • the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, it is possible to protect the wiring from external impact and bending force, and particularly when the permanent pattern is the interlayer insulating film. Is useful for high-density mounting of semiconductor components on, for example, multilayer wiring boards and build-up wiring boards.
  • the permanent pattern forming method of the present invention enables pattern formation at a high speed, it can be widely used for forming various patterns, and can be particularly suitably used for forming wiring patterns.
  • the permanent pattern formed by the method for forming a permanent pattern of the present invention has excellent surface hardness, insulation, heat resistance, etc., and is suitably used as a protective film, an interlayer insulating film, and a solder resist pattern. be able to.
  • a photosensitive composition was prepared based on the following composition.
  • methyl ethyl ketone was used as a dispersion solvent, and the solid content concentration was adjusted to 55% by mass.
  • Dispersion was performed using a bead mill, and the obtained dispersion was confirmed to be free from aggregation by a particle gauge.
  • the curing accelerator represented by the structural formula (1) was synthesized as follows.
  • the curing accelerator represented by the structural formula (1) is a 1 H-NMR spectrum using CHC1 as a solvent.
  • the pectinore (300 MHz) was measured and identified. Each peak in the spectrum is 5.85-5.65 (m; 2H), 3.63-3.52 (m; lH), 3.44—3.32 (m; lH), 3.26— 3.10 (m; 2H), 3.01-2.87 (m; lH) , 2.51-2.40 (m; lH), 2.72-2.13 (m; 2H), 1.6 6-1.52 (m; 4H), 1.36-1.23 (m; 12H), 0.94-0.88 (m; 6H) .
  • the content of the curing accelerator represented by the structural formula (1) in the photosensitive composition is 0.42% by mass.
  • the obtained photosensitive composition was mixed with 20 ⁇ m thick PET (polyethylene film) as the support.
  • the film was coated on a (phthalate) film and dried to form a photosensitive layer having a thickness of 30 zm.
  • a polypropylene film having a thickness of 12 zm was laminated as a protective film on the photosensitive layer to produce a photosensitive film.
  • a surface of a copper-clad laminate (with no through holes and a copper thickness of 12 ⁇ m) on which wiring was formed was prepared by chemical polishing treatment.
  • a vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd., MVLP500) is peeled off on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film is in contact with the copper clad laminate.
  • MVLP500 vacuum laminator
  • a laser exposure device 405 nm laser light is irradiated from the polyethylene terephthalate film (support) side so that a pattern in which holes having different diameters are formed is applied to the photosensitive layer in the prepared laminate. Then, a portion of the photosensitive layer was cured.
  • the polyethylene terephthalate film (support) is peeled off from the laminate, and 1% by weight aqueous sodium carbonate solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Used and shower developed for 60 seconds at 30 ° C to dissolve and remove uncured areas. Thereafter, it was washed with water and dried to form a permanent pattern.
  • the entire surface of the laminate on which the permanent pattern was formed was heated at 160 ° C. for 60 minutes to cure the surface of the permanent pattern and increase the film strength. When the permanent pattern was visually observed, no bubbles were observed on the surface of the permanent pattern.
  • the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is added to the entire surface of the photosensitive layer on the copper clad laminate at 0.15 MPa. Spraying was performed under pressure, and the time required from the start of spraying of the sodium hydrogen carbonate solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.
  • the photosensitive film described above produced, from the polyethylene terephthalate film (supporting bearing member) side, different amount of light energy from 0. LMJ / cm 2 to 100 mj / cm 2 at 2 1/2 times intervals by using the exposure apparatus Exposure was performed by irradiating light, and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive film, and an aqueous sodium bicarbonate solution (30 ° C, 1 ° C) was applied to the entire photosensitive layer on the copper-clad laminate.
  • the sensitivity curve force obtained in this way was the amount of light energy when the thickness of the cured region was the same as that before exposure, and the amount of light energy required to cure the photosensitive layer.
  • the surface of the printed circuit board on which the permanent pattern had been formed was observed with an optical microscope, and no residual film was found in the hole portion of the cured layer pattern.
  • the minimum hole diameter was measured, and this was taken as the resolution. The smaller the numerical value, the better the resolution. As a result, the resolution was 70 zm.
  • the relative speed of moving the exposure light and the photosensitive layer was determined by changing the degree.
  • the exposure was performed from the polyethylene terephthalate film (support) side to the photosensitive layer in the prepared laminate. It should be noted that an efficient permanent pattern can be formed at a higher setting speed.
  • the 405 nm laser exposure apparatus had a light modulation means composed of the DMD, and the exposure speed was 13 mmZsec.
  • the produced photosensitive film was stored for 2 days under accelerated conditions of 60 ° C drying. Two days later, exposure sensitivity and resolution were measured, and storage stability was evaluated based on the following criteria.
  • the exposure sensitivity was 30 mj / cm 2 and the resolution was 70 ⁇ m, indicating excellent storage stability.
  • Exposure sensitivity and resolution are remarkably lowered, and storage stability is extremely inferior or cannot be stored.
  • the printed wiring board on which the permanent pattern had been formed was subjected to gold plating according to a conventional method, and then subjected to a water-soluble flux treatment. Next, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the pencil hardness was measured about the permanent pattern after this flux removal based on JIS K-5400.
  • the pencil hardness was 5H or higher. Further, when visually observed, no peeling, blistering, or discoloration of the cured film in the permanent pattern was observed.
  • the dielectric properties of a cured film with a thickness of 500 am are:
  • the dielectric constant at 1 GHz is 3.3.
  • the dielectric loss tangent was 0.013.
  • Example 2 A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • the unit A consists of two structural units, R 1 to definitive one of the structural units of which are phenyl, R 1 in the other structural units are butyl O alkoxycarbonyl, R 3 and R 4 are a hydrogen atom is there.
  • R 2 in unit B is benzyl.
  • the mole fraction X of the repeating unit in Unit A is 40 mol% for the one constituent unit and 28 mol% for the other constituent unit, and the mole fraction of the repeating unit in Unit B is the same.
  • the rate y is 32 mol%.
  • the reaction amount of the benzylamine with respect to the anhydride group of the styrene / maleic anhydride / butyl acrylate copolymer is 1.0 equivalent.
  • the glass transition temperature (Tg) of the homopolymer of butyl acrylate, which is the bulle monomer, is _54 ° C.
  • Example 2 the content of the curing accelerator represented by the structural formula (1) in the photosensitive composition is 0.42% by mass.
  • Example 1 15.7 parts by mass of the thermal crosslinking agent, 2,2-bis (4-glycidylphenyl) propane, in the photosensitive composition was added to the thermal crosslinking agent (TEPIC) represented by the following structural formula (X).
  • TEPIC thermal crosslinking agent
  • a photosensitive composition was prepared in the same manner as in Example 1 except that the amount was changed to 8.2 parts by mass.
  • a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern. Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 3.
  • Example 1 except that the thermal crosslinking agent, 2,2-bis (4-glycidylphenyl) propane, in the photosensitive composition was changed to Epicoat YX4000 (Japan Epoxy Resin, Epoxy resin).
  • a photosensitive composition was prepared in the same manner as in Example 1, and a photosensitive film and laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Example 1 except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to a curing accelerator represented by the following structural formula (2), Example 1 and A photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Example 2 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 4.
  • the curing accelerator represented by the structural formula (2) was synthesized as follows. Add 7.7 parts by mass of cis_4-cyclohexene-1,2-dicarboxylic anhydride and 30 parts by mass of acetonitrile to the eggplant flask, and after the cis_4-cyclohexene-1,2-dicarboxylic acid anhydride has dissolved, Dioctylamine 12.1 parts by mass was added and stirred for 2 hours. Thereafter, the solvent was removed in vacuo, and 9.1 parts by mass of the compound represented by the structural formula (2) was obtained by silica gel column chromatography. The yield at this time was 46%.
  • the curing accelerator represented by the structural formula (1) is a 1 H-NMR spectrum using CHC1 as a solvent.
  • the pectinore (300 MHz) was measured and identified. Each peak of the spectrum is 5.85-5.60 (m; 2H), 3.62-3.52 (m; lH), 3.43—3.32 (m; lH), 3.26— 3.10 (m; 3H), 3.05-2.87 (m; 2H) , 2.51-2.35 (m; lH), 2.22-2.13 (m; 2H), 1.7 0-1.50 (m; 4H), 1.36-1.23 (m; 20H), 0.94-0.85 (m; 6H) .
  • the content of the curing accelerator represented by the structural formula (2) in the photosensitive composition is 0.42% by mass.
  • Example 1 it is represented by the structural formula (1) in the photosensitive composition in the photosensitive composition.
  • a photosensitive composition was prepared in the same manner as in Example 1 except that the curing accelerator was changed to a curing accelerator represented by the following structural formula (3).
  • a photosensitive film and a laminate were prepared to form a permanent pattern.
  • Example 2 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 4.
  • the curing accelerator represented by the structural formula (3) was synthesized as follows. Place 2.92 parts by mass of cis_4-cyclohexene-1,2-dicarboxylic acid anhydride and 30 parts by mass of cycloform in an eggplant flask and dissolve the cis_4-cyclohexene-1,2-dicarboxylic acid anhydride. 4) 3.37 parts by mass of benzylpiperidine was added and stirred for 2 hours. Thereafter, the solvent was distilled off in vacuo, and recrystallization was performed with ethyl acetate to obtain 4.5 parts by mass of the compound represented by the structural formula (3). The yield at this time was 72%.
  • the curing accelerator represented by the structural formula (3) is a 1 H-NMR spectrum using CHC1 as a solvent.
  • the pectinore (300 MHz) was measured and identified. Each peak in the spectrum is 7.32-7.19 (m; 4H), 7.14 (d; lH), 5.84-5.77 (m; lH), 5.72-5.62 (m; lH), 4.71 -4.62 (m; lH), 3.87 (d; lH), 3.23-3.03 (m; 3H), 2.85 (d; lH), 2.69 -2.50 (m; lH), 2.46-2.28 (m; lH), 1.86-1.76 (m; 3H), 1.26 — 1.1 6 (m; 2H).
  • the content of the curing accelerator represented by the structural formula (3) in the photosensitive composition is 0.42% by mass.
  • Example 1 except that the curing accelerator represented by the structural formula (1) in the photosensitive composition in the photosensitive composition was changed to a curing accelerator represented by the following structural formula (4).
  • a photosensitive composition in the same manner as in Example 1, prepared a photosensitive film and laminate in the same manner as in Example 1, and formed a permanent pattern.
  • the curing accelerator represented by the structural formula (4) was synthesized as follows. Place 5 parts by mass of cis-1,4-cyclohexene-1,2-dicarboxylic acid anhydride and 40 parts by mass of acetonitrile in the eggplant flask and dissolve the cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. , N-methyl monopendinoleamine 3. 97 parts by weight was added and stirred for 2 hours. As a result, 4.5 parts by mass of the compound represented by the structural formula (4) was obtained. The yield at this time was 76%.
  • the curing accelerator represented by the structural formula (4) is a 1 H-NMR spectrum using CHC1 as a solvent.
  • the pectinore (300 MHz) was measured and identified. Each peak in the spectrum is 7.44-7.15 (m; 5H), 5.86-5.67 (m; 2H), 4.75—4.51 (m; 2H), 3.31—3.24 (m ; lH), 3.13-3.00 (m; 4H), 2.92— 2.81 (m; lH), 2.51— 2.37 (m; lH), 2.3 3 1-2.18 ( m; lH), 2. 10-2.04 (m; lH).
  • the content of the curing accelerator represented by the structural formula (4) in the photosensitive composition is 0.42% by mass.
  • Example 1 except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to a curing accelerator represented by the following structural formula (5), Example 1 and A photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Example 2 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 4.
  • the curing accelerator represented by the structural formula (5) was identified by measuring 1 H-NMR spectrum (300 MHz) using DMSO as a solvent. Each peak in the spectrum is 5.69-5.55 (m; 4H), 3.57-3.22 (m; 14H), 2.72—2.40 (m; 8H), 2.40—2 15 (m; 6 H).
  • the content of the curing accelerator represented by the structural formula (5) in the photosensitive composition is 0.42% by mass.
  • Example 1 the exposure sensitivity of the photosensitive composition and the photosensitive film produced in the same manner as in Example 2 except that the exposure apparatus was replaced with the pattern forming apparatus described below. Then, resolution and exposure speed were evaluated, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. The results are shown in Table 5.
  • DMD50 controlled to drive only 1,024 x 256 rows, and microlens 474 whose one side is toric as shown in FIG.
  • a pattern forming apparatus having optical systems 480 and 482 for forming an image is used.
  • the strain on the exit surface was measured.
  • the results are shown in FIG. In FIG. 3, the same height position of the reflecting surface is shown connected by contour lines, and the pitch of the contour lines is 5 nm.
  • the X direction and the y direction shown in the figure are the two diagonal directions of the micromirror 62, and The mouth mirror 62 rotates about a rotation axis extending in the y direction.
  • 4A and 4B show the height position displacement of the reflection surface of the micromirror 62 along the X direction and the y direction, respectively.
  • FIGS. 5A and 5B show the front and side shapes of the entire microlens array 55 in detail.
  • the dimensions of each part of the microlens array 55 are also entered, and their unit is mm.
  • 1,024 ⁇ 256 rows of micromirrors 62 of DMD50 are driven.
  • microphone mouth lens array 55 has 1,024 in the horizontal direction.
  • the microlenses 55a are arranged in a row with 256 rows arranged in the vertical direction.
  • FIG. A the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.
  • FIGS. 6A and 6B show a front shape and a side shape of one microlens 55a in the microlens array 55, respectively.
  • the contour lines of the microlens 55a are also shown.
  • the end surface on the light exit side of each microlens 55a has an aspherical shape that corrects aberration due to distortion of the reflection surface of the microphone mirror 62.
  • the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction is roughly as shown in FIGS. 7A and 7B, respectively.
  • the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. I understand that.
  • X is the lens light in the X direction. This means the distance from the axis O
  • Y means the distance from the lens optical axis O in the y direction.
  • the microlens 55a has a focal length force in the cross section parallel to the y direction, and is smaller than the focal length in the cross section parallel to the direction.
  • the aperture array 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged so that only light that has passed through the corresponding microlens 55a is incident on each aperture 59a. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to enhance the extinction ratio.
  • Example 1 the photosensitive composition was the same as Example 1 except that the addition amount of the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to 21.3 parts by mass. A photosensitive film and a laminate were prepared in the same manner as in Example 1, and a permanent pattern was formed. . In Example 13, the content of the curing accelerator represented by the structural formula (1) in the photosensitive composition was 16.0% by mass.
  • Example 2 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 6.
  • the photosensitive composition was the same as in Example 1, except that the addition amount of the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to 0.005 parts by mass in Example 1.
  • a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • the content of the curing accelerator represented by the structural formula (1) in the photosensitive composition is 0.000048% by mass.
  • Example 2 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 6.
  • a photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the permanent pattern thus formed was measured for pencil hardness, And dielectric properties were evaluated.
  • the results are shown in Table 6.
  • the content of the curing accelerator represented by the structural formula (1) in the photosensitive composition is 0.42% by mass.
  • Binder 40.0 parts by mass represented by the following structural formula (V)
  • Example 15 was changed except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to the curing accelerator represented by the structural formula (2).
  • a photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Example 2 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 6.
  • Example 15 except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to the curing accelerator represented by the structural formula (3).
  • a photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Example 15 the binder represented by the structural formula (V) in the photosensitive composition was changed to styrene Z maleic anhydride Z butyl acrylate copolymer (mono ratio 40Z32Z28) and benzylamine (anhydrous copolymer).
  • a photosensitive composition was prepared in the same manner as in Example 15 except that it was changed to an addition reaction product of 1.0 equivalent to the physical group).
  • a body was prepared to form a permanent pattern.
  • Example 7 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 7.
  • Example 1 40 parts by mass of the binder represented by the structural formula (47) in the photosensitive composition is changed to 20 parts by mass, and the allyl resin having an unsaturated group obtained in Synthesis Example 1 shown below.
  • a photosensitive composition was prepared in the same manner as in Example 1 except that 20 parts by mass of (B1) was added, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern. .
  • Example 7 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 7.
  • Methyl metatalylate 45.1 parts by weight, methacrynoreic acid 47.3 parts by weight, azoisovalero nitrinole 1 part by weight, propylene glycol monomethyl ether 215 parts by weight
  • methacrynoreic acid 47.3 parts by weight
  • azoisovalero nitrinole 1 part by weight
  • propylene glycol monomethyl ether 215 parts by weight
  • acrylic resin (A1) solution was charged with 54.7 parts by mass of cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd.), 0.2 part by mass of hydroquinone monomethyl ether, and 1 part by mass of triphenylphosphine. , React for 8 hours at 80 ° C while blowing air.
  • Acrylic resin having an unsaturated group (Bl) to obtain a solution of (acid value of solid content;; 111, Mw 18, 000 , double bonds eq 2. 3mmolZg, propylene glycol monomethyl ether 41 mass 0/0 solution).
  • Example 1 40 parts by mass of the binder represented by the structural formula (47) in the photosensitive composition was changed to 20 parts by mass, and the allyl resin having an unsaturated group obtained in Synthesis Example 2 shown below.
  • a photosensitive composition was prepared in the same manner as in Example 1 except that 20 parts by mass of (B2) was added, and a photosensitive film and laminate were prepared in the same manner as in Example 1 to form a permanent pattern. .
  • Example 7 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 7.
  • a mixed solution consisting of 45.1 parts by weight of methyl metatalylate, 47.3 parts by weight of methacrylic acid, 1 part by weight of azoisovaleronitryl, and 215 parts by weight of propylene glycol monomethyl ether was placed in a 90 ° C reaction vessel under a nitrogen gas atmosphere It was dripped over 3 hours. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin (A2).
  • Example 1 except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was 0.47 parts by mass, 1.24 parts by mass, and dicyandiamide was not added.
  • a photosensitive composition was prepared in the same manner as in Example 1, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Example 2 except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was 0.47 parts by mass, 1.24 parts by mass, and dicyandiamide was not added.
  • a photosensitive composition was prepared in the same manner as in Example 1, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Example 1 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 8.
  • a photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • thermosetting accelerator in the photosensitive composition 2 ⁇ 4 ⁇
  • a photosensitive composition was prepared in the same manner as in Example 1 except that it was changed to an isocyanuric acid adduct of ethyl _ s _triazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.).
  • a photosensitive film and a laminate were prepared and a permanent pattern was formed.
  • Example 1 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 8.
  • a photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • thermosetting accelerator represented by the structural formula (48) 0.16 parts by mass
  • a photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
  • Binder represented by the structural formula (47) 40.0 parts by mass Thermal crosslinking agent (TEPIC) represented by the structural formula (X) 5.6 parts by mass Monomer represented by the structural formula (XI) 16. 0 parts by mass
  • thermosetting agent 0.60 parts by mass
  • thermosetting accelerator represented by the structural formula (49) 0.40 parts by mass
  • Sensitivity Structural formula (47) Copolymer Light 2,2-bis 2,2-bis property Thermal cross-linking agent (4-Gelicy's Ruf 1 Le) (4-Gelicy's Ruf I Nyl) ⁇ '
  • thermosetting resin composition Preparation of one thermosetting resin composition
  • thermosetting composition was prepared based on the following composition.
  • thermosetting resin composition [Composition of thermosetting resin composition]
  • Curing accelerator represented by the structural formula (1) 4.5 parts by mass By mixing the epoxy resin, curing agent and curing accelerator with the above composition, and stirring with a mixer (7, OOOrpm, 1 minute) A thermosetting resin of Example 23 was prepared.
  • thermosetting resin composition produced was evaluated for gelation time, heat resistance and storage stability. The results are shown in Table 10.
  • thermosetting resin composition The gelling time of the obtained thermosetting resin composition was measured by a hot plate method at 150 ° C. according to JIS K5059 (1997).
  • thermosetting resin composition the heat deformation temperature which is an index of the heat resistance of the cured resin was measured.
  • the heat distortion temperature is in accordance with JIS K7207 (1997), HDT tester S-3 Measurement was performed using M (Toyo Seiki).
  • the resin was cured at 150 ° C for 2 hours. ⁇ Storage stability>
  • thermosetting resin composition stored at 40 ° C
  • the viscosity of the resin composition was measured using a B-type viscometer, and the time when the resin viscosity was twice the initial viscosity was taken as the evaluation time. Based on this evaluation time, storage stability was evaluated according to the following evaluation criteria.
  • Example 23 the heat curing of Examples 24-26 was performed in the same manner as in Example 23 except that the curing accelerator represented by the structural formula (1) was replaced with the curing accelerator shown in Table 9. Resin composition was prepared. In Example 26, the curing agent was not added, and the addition amount of the curing accelerator was 20 parts by mass.
  • thermosetting resin composition obtained was evaluated in the same manner as in Example 23 for gelation time, heat resistance, and storage stability. The results are shown in Table 10.
  • Example 23 the curing accelerator represented by the structural formula (1) was replaced with the conventional curing accelerator shown in Table 10, and an amine was generated by external stimulation, and a carboxyl group and an amide group were formed in the molecule.
  • Thermosetting resin compositions of Comparative Examples 5 to 6 were prepared in the same manner as in Example 23 except that a curing accelerator composed of a compound having a structure having a ratio of 1 to 1 was not used.
  • Each thermosetting resin composition obtained was evaluated in the same manner as in Example 23 for gelation time, heat resistance, and storage stability. The results are shown in Table 11.
  • the curing accelerator of the present invention comprising an amine generated by an external stimulus and composed of a compound having a structure having a carboxynole group and an amide group in a 1: 1 ratio in the molecule was used.
  • the photosensitive composition of Examples 1 to 22 and the photosensitive layer in the photosensitive film produced using this photosensitive composition are excellent in storage stability, exposure sensitivity and resolution, and are formed using the photosensitive film. It was confirmed that the surface hardness and dielectric properties of the cured layer in the permanent pattern were good.
  • the photosensitive film of Examples 1 to 12 in which the content of the curing accelerator in the photosensitive composition is 0.01 to 15% by mass is extremely excellent in both storage stability and dielectric properties. It turned out to be excellent.
  • Examples 9 to 12 using the same photosensitive film as Examples 1, 2, 5 and 6, A high-intensity light source and high-speed modulation is possible, and a pattern forming device that can correct optical distortion with a toric lens is used. was confirmed.
  • thermosetting resin compositions of Examples 23 to 26 using the curing accelerator of the present invention were comparative examples 5 to 5 in which the curing accelerator of the present invention was not used. Compared to 6, it has half the storage stability.
  • the curing accelerator of the present invention does not react at room temperature during storage, is excellent in storage stability, exhibits a curing acceleration effect and a thermal cross-linking effect by heating, and is effective with a resin such as an epoxy resin compound.
  • the protective film of the printed wiring board (multilayer wiring board, build-up wiring board, etc.), interlayer insulating film, sono-redder resist pattern, and Suitable for display members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, adhesives, thermosetting compositions, photosensitive compositions for permanent pattern formation, etc. Can be used.
  • thermosetting resin composition of the present invention using the curing accelerator of the present invention is curable by heat and has excellent storage stability. After curing, it has excellent chemical resistance, hardness, heat resistance, Since it can exhibit dielectric properties, electrical insulation, etc., it can be suitably used for adhesives.
  • the photosensitive composition of the present invention using the curing accelerator of the present invention and the photosensitive film using the photosensitive composition are capable of forming an image by UV exposure and have a laminating property and a small surface tackiness.
  • Printed wiring board multi-layer wiring board because it has good handling properties, excellent storage stability, high sensitivity, excellent developability, and excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development.
  • the permanent pattern of the present invention has chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation. Excellent edge. For this reason, it is used for protective films on printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, and displays such as color filters, pillar materials, rib materials, spacers, and partition walls. It can be used suitably as it can be widely used for forming permanent patterns such as members, holograms, micromachines, and proofs.

Abstract

Disclosed is a curing accelerator composed of a compound which generates an amine upon external stimulation and has carboxyl groups and amide groups in a molecule at a ratio of 1:1. Also disclosed is a photosensitive composition characterized by containing such a curing accelerator, a polymer having one or more of carboxyl groups or one or more of ester groups in a molecule, a polymerizable compound, and a photopolymerization initiator. This photosensitive composition is excellent in storage stability and can be used as a photosensitive film. Further disclosed is a method for forming a permanent pattern wherein such a photosensitive film is arranged on the surface of a base, and then exposed, developed and heated thereon.

Description

明 細 書  Specification
硬化促進剤、熱硬化性樹脂組成物、感光性組成物及び感光性フィルム、 並びに、永久パターン及びその形成方法  Curing accelerator, thermosetting resin composition, photosensitive composition and photosensitive film, and permanent pattern and method for forming the same
技術分野  Technical field
[0001] 本発明は、保存時の常温下では反応を生じず、保存安定性に優れ、加熱により硬 化促進効果及び熱架橋効果を発現し、樹脂との反応を開始して硬化し、硬化膜の良 好な膜硬度が得られる硬化促進剤、この硬化促進剤を使用し、熱によって硬化可能 で保存安定性に優れ、硬化後は優れた耐薬品性、硬度、誘電特性及び電気絶縁性 などを発現する熱硬化性樹脂組成物、前記硬化促進剤を使用し、 UV露光により画 像形成可能で、表面のタック性が小さぐラミネート性及び取扱い性が良好で、保存 安定性に優れ、高感度で現像性にも優れ、現像後に優れた耐薬品性、表面硬度、 耐熱性、誘電特性、電気絶縁性などを発現する感光性組成物、及びこれを用いた感 光性フィルム、並びに高精細な永久パターン (保護膜、層間絶縁膜、ソルダーレジス トパターンなど）及びその効率的な形成方法に関する。  [0001] The present invention does not cause a reaction at room temperature during storage, is excellent in storage stability, exhibits a curing acceleration effect and a thermal crosslinking effect by heating, initiates a reaction with a resin, cures, and cures A curing accelerator that provides good film hardness of the film, and using this curing accelerator, it can be cured by heat and has excellent storage stability.After curing, it has excellent chemical resistance, hardness, dielectric properties, and electrical insulation. It is possible to form an image by UV exposure using the above-mentioned curing accelerator, the surface tackiness is small, the laminate and handling properties are good, and the storage stability is excellent. Highly sensitive and developable, photosensitive composition exhibiting excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, etc. after development, photosensitive film using the same, and high Fine permanent pattern (protective film, interlayer insulation film, solderale It is sampled patterns) and its efficient formation methods.
背景技術  Background art
[0002] プリント配線基板の分野では、半導体やコンデンサ、抵抗等の部品がプリント配線 基板の上に、半田付けされる。この場合、例えば、 IRリフロー等のソルダリング工程に おいて、半田が、半田付けの不必要な部分に付着するのを防ぐため、保護膜、絶縁 膜として、前記半田付けの不要部分に相当する永久パターンを形成する方法が採用 されている。また、保護膜の永久パターンとしては、ソルダーレジストが好適に用いら れている。  In the field of printed wiring boards, components such as semiconductors, capacitors and resistors are soldered on the printed wiring board. In this case, for example, in a soldering process such as IR reflow, in order to prevent solder from adhering to an unnecessary part of soldering, it corresponds to the unnecessary part of soldering as a protective film and an insulating film. A method of forming a permanent pattern is adopted. Also, a solder resist is preferably used as the permanent pattern of the protective film.
[0003] 従来、ソルダーレジストとしては、熱硬化型の材料が多く用いられ、これをスクリーン 印刷法で印刷して施す方法が一般的であった。しかし、近年、プリント配線板の配線 の高密度化に伴い、スクリーン印刷法では解像度の点で限界が生じ、フォトリソグラフ ィ一法で画像形成を行うフォトソルダーレジストが盛んに用いられるようになつてきて いる。中でも、炭酸ソーダ溶液等の弱アルカリ溶液で現像可能なアルカリ現像型のフ オトソルダーレジストが、作業環境、地球環境保全の点で主流になっている。また、一 般には液状ソルダーレジストをスクリーン印刷、スプレーコート、ディップコート等によ り配線形成済みの基板の片面に塗布して乾燥し、引き続き反対面に塗布して乾燥す る製造方法が用いられている。 [0003] Conventionally, as the solder resist, a thermosetting material is often used, and a method in which this is applied by screen printing is generally used. However, in recent years, with the increase in the wiring density of printed wiring boards, the screen printing method has a limit in terms of resolution, and a photo solder resist that forms an image by the photolithographic method has been actively used. ing. Among them, alkali development type photo solder resists that can be developed with a weak alkali solution such as sodium carbonate solution are mainly used in terms of working environment and global environment conservation. Also one In general, a manufacturing method is used in which a liquid solder resist is applied to one side of a substrate on which wiring has been formed by screen printing, spray coating, dip coating, and the like, and then dried on the opposite side. .
[0004] また、前記のようなアルカリ現像型のフォトソルダーレジストとしては、主成分として エポキシ化合物にエチレン性不飽和二重結合及びアルカリ現像性を付与するため の酸基を導入した化合物（エポキシアタリレート）と、エチレン性不飽和二重結合を有 する付加重合性化合物（モノマー）と、を含む組成物が一般に用いられており、具体 的には特許文献 1に開示されている。しかし、特許文献 1に記載のソルダーレジスト は、ポストべイク後に高い表面硬度が得られ、耐薬品性に優れるものの、表面のタツ クが残り、ゴミが付着し易くなり欠陥が増大する、あるいはフォトマスクを汚染するなど 、取扱い性を悪化させるという問題がある。ここで、表面にタックが残るのは、アルカリ 水溶液に可溶性のバインダーであるエポキシアタリレートの分子量が数 100程度と低 分子量であり、モノマーが通常沸点の高い液体又は半固体であることによるものであ ると考えられる。 [0004] Also, as the alkali development type photo solder resist as described above, as a main component, a compound in which an acid group for imparting an ethylenically unsaturated double bond and alkali developability to an epoxy compound is introduced (epoxy acrylate). And an addition-polymerizable compound (monomer) having an ethylenically unsaturated double bond is generally used, and specifically disclosed in Patent Document 1. However, the solder resist described in Patent Document 1 has a high surface hardness after post-baking and excellent chemical resistance, but the surface tack remains and dust tends to adhere to increase the defects, or the photo resist. There is a problem of deteriorating handling properties such as contamination of the mask. Here, the tack remains on the surface because the molecular weight of epoxy acrylate, which is a binder soluble in an alkaline aqueous solution, is as low as several hundreds, and the monomer is usually a liquid or semi-solid with a high boiling point. It is believed that there is.
また、このようなソルダーレジストの露光感度は通常 300〜1 , 000mj/cm2と低く、 製造ラインのスピードアップのネックになりつつあり、更に感度アップが要請されてい る。該感度アップのためにはモノマーの配合量の増量が効果的である力 モノマー 類を多く配合してしまうと前記表面タックが更に悪化するという問題が生じ、解決策が 見出されていない。 In addition, the exposure sensitivity of such a solder resist is usually as low as 300 to 1,000 mj / cm 2, which is becoming a bottleneck in speeding up the production line, and further sensitivity improvement is required. The ability to increase the blending amount of the monomer is effective for increasing the sensitivity. When a large amount of monomers are blended, the problem that the surface tack is further deteriorated occurs, and no solution has been found.
[0005] また、近年高密度実装が急速に進みつつあり、高密度実装を実現する上での、ソ ルダーレジストの課題は、ウエット現像やウエットエッチングを繰り返す、フォトリソダラ フィープロセス中での基板の伸縮やフォトマスクフィルムの温湿度変化に基づく伸縮 に起因する配線パターンやスルーホールランドパターンの位置ズレである。  [0005] Also, in recent years, high-density mounting has been rapidly progressing, and the problem of solder resist in realizing high-density mounting is that the substrate is being processed during the photolithography process, in which wet development and wet etching are repeated. This is the misalignment of wiring patterns and through-hole land patterns due to expansion and contraction due to expansion and contraction and changes in temperature and humidity of the photomask film.
位置ズレ防止には、これまでは、基板の変形度の少ないロットを選別したり、予め各 種のパラメータで修正した複数のフィルムマスクを準備したり、高価なガラスマスクを 使用するといつた対策が採られてきた。また、この位置ズレ問題の解決のため、レー ザ一ダイレクトイメージングシステム（LDI)の適用が進んでいる。ここで、 LDIは、デジ タルデータの高速処理による補正により、基板の変形に対応した露光パターンを形 成する技術に基づくものである。 To prevent misalignment, it has been necessary to select lots with a low degree of substrate deformation, prepare multiple film masks that have been corrected in advance using various parameters, or use expensive glass masks. Have been taken. In addition, the application of laser direct imaging system (LDI) is progressing to solve this misalignment problem. Here, LDI forms an exposure pattern corresponding to the deformation of the substrate by correcting digital data at high speed. It is based on the technology to be achieved.
[0006] 前記 LDIに用いられるソルダーレジストには、 365nm、あるいは 405nmなどの UV レーザーに対応するため、 100mj/cm2以上の露光感度が要求される。このため、 高感度が得られやすいフィルムタイプのソルダーレジストが必要となってきている。し かし、特許文献 1に記載のソルダーレジストをフィルム化すると、表面のタック性が強く 、支持体や保護膜と感光層とが剥離しにくぐ取扱い性が悪ぐ更に— 20°C以下の 冷凍保存でも 2、 3ヶ月の保存しか出来ず、保存安定性の問題がある。また波長 405 nmのレーザ光に対する感度が無いとレ、う欠点を有してレ、る。 [0006] The solder resist used in the LDI is required to have an exposure sensitivity of 100 mj / cm 2 or more in order to cope with a UV laser of 365 nm or 405 nm. For this reason, a film-type solder resist that is easy to obtain high sensitivity is required. However, when the solder resist described in Patent Document 1 is made into a film, the tackiness of the surface is strong, the support or protective film is difficult to peel off from the photosensitive layer, and the handling property is poor. Even frozen storage can only be stored for a few months, and there is a problem of storage stability. In addition, if there is no sensitivity to laser light having a wavelength of 405 nm, it has a drawback.
[0007] 一方、特許文献 2には、分子量 10, 000以上の比較的高分子量のアルカリ水溶液 に可溶性のバインダーを用いた、表面のタック性が小さぐ耐熱性に優れ、比較的保 存安定性が良好なソルダーレジストが開示されている。し力しながら、該ソルダーレジ ストは表面硬度が低ぐラミネート性に劣るという問題がある。したがって、気泡を生ず ることなぐ配線形成済みのプリント配線基板の最外層に予め液状のモノマーを下引 き層として塗布しておく必要があり、工程が煩雑になり、取扱い性に劣るという欠点を 有している。その理由としては、メチルメタタリレート、スチレンという硬質のポリマーを 形成する共重合成分 (各々のホモポリマーの Tgは 105°C以上、 100°Cである）を用 いた結果、硬化膜が柔軟性に欠けて脆くなり、表面硬度が上がらず、また、真空条件 下の加熱積層工程で、十分な流動性が得られず、気泡発生を弓 Iき起こしていること が考えられる。更に、波長 405nmのレーザ光に対する感度が無いという欠点を有し ている。  [0007] On the other hand, Patent Document 2 uses a binder soluble in a relatively high molecular weight alkaline aqueous solution having a molecular weight of 10,000 or more, has a small surface tackiness, excellent heat resistance, and relatively storage stability. Has disclosed a good solder resist. However, the solder resist has a problem that the surface hardness is low and the laminate property is inferior. Therefore, it is necessary to apply a liquid monomer as an undercoat layer in advance to the outermost layer of a printed wiring board on which wiring has been formed without generating bubbles, which makes the process complicated and inferior in handleability. have. The reason is that the cured film is flexible as a result of the use of a copolymer component that forms a rigid polymer such as methyl methacrylate and styrene (Tg of each homopolymer is 105 ° C or higher and 100 ° C). It is considered that the surface hardness does not increase due to chipping, and that sufficient fluidity cannot be obtained in the heating and laminating process under vacuum conditions, causing bubble generation. Furthermore, there is a drawback that there is no sensitivity to laser light having a wavelength of 405 nm.
[0008] また、先端電子機器分野では、高周波環境での高速伝搬性が要求されており、特 に電子計算機や移動体通信機器に代表される電子機器においては、処理速度や信 号伝播速度の高速化、使用帯域の高周波化に伴い、積層板用材料には低誘電率 ィ匕、低誘電正接化が求められている。プリント配線板製造におけるソルダーレジスト にも低誘電率化、低誘電正接化が求められてきている。し力 ながら、現状のアル力 リ現像型のソルダーレジストでは、高周波数領域での誘電特性が悪ぐ高周波数用 樹脂として満足な特性が得られてレ、なレ、のが現状である。  [0008] In the field of advanced electronic equipment, high-speed propagation characteristics in a high-frequency environment are required. Especially in electronic equipment represented by electronic computers and mobile communication equipment, processing speed and signal propagation speed are low. With higher speeds and higher frequency bands, laminated board materials are required to have low dielectric constant and low dielectric loss tangent. Lowering the dielectric constant and lowering the dielectric loss tangent are also required for solder resists in the production of printed wiring boards. However, the current Al-re-developable solder resists are capable of obtaining satisfactory characteristics as high-frequency resins with poor dielectric characteristics in the high-frequency region.
[0009] また、前記フィルムタイプのソルダーレジストとして、一般に市販されている製品では 、このフィルム化に伴レ、、感光層中においてバインダー及びモノマーと、熱架橋剤と が混在するため、架橋反応が生じて保存安定性に乏しいことが問題となっている。 一方、エポキシ樹脂組成物などの熱硬化性樹脂組成物の硬化促進剤として、前記 保存安定性の観点から、保存時には反応を生じないが、加熱により反応して硬化す る性質を持つ、いわゆる潜在性硬化促進剤を使用した提案がされている。例えば、 2 —ェチルへキシル酸亜鉛とトリエタノールァミンからなる塩、トリエチレンジァミンと脂 肪族カルボン酸からなる塩を配合した提案がされている（非特許文献 1及び特許文 献 3参照）。これらは、硬化促進剤を錯塩とすることにより、溶解性を低下させて、反応 活性を抑制し、保存安定性を向上させようとするものである。 [0009] In addition, as the film-type solder resist, As a result of this film formation, a binder and a monomer and a thermal cross-linking agent are mixed in the photosensitive layer, so that a cross-linking reaction occurs and storage stability is poor. On the other hand, as a curing accelerator for a thermosetting resin composition such as an epoxy resin composition, from the viewpoint of the storage stability, a reaction does not occur during storage, but it has a property of reacting and curing by heating, so-called latent. Proposals have been made using photocuring accelerators. For example, proposals have been made that contain a salt composed of zinc 2-ethylhexylate and triethanolamine, and a salt composed of triethylenediamine and an aliphatic carboxylic acid (Non-patent Document 1 and Patent Document 3). reference). These are intended to reduce solubility, suppress reaction activity, and improve storage stability by using a complex accelerator as a curing accelerator.
また、エポキシ樹脂にジメチルァミンや時アルキルアミンを反応させて得られる付加 物（特許文献 4及び 5参照）、エポキシ樹脂に 3級ァミンを反応させて得られる付加物 (特許文献 6、 7参照）などを使用した提案もされている。このようにエポキシ樹脂にァ ミン化合物を付加させて高分子化、不溶化させることにより、保存安定性の向上を図 つている。  Also, adducts obtained by reacting epoxy resins with dimethylamine and sometimes alkylamines (see Patent Documents 4 and 5), adducts obtained by reacting epoxy resins with tertiary amines (see Patent Documents 6 and 7), etc. There is also a proposal using. In this way, an amine compound is added to an epoxy resin to make it polymerized and insolubilized to improve storage stability.
し力 ながら、これらの文献では、ソルダーレジストに使用した開示がないし、十分 満足し得る高い保存安定性能が得られ、かつ、安価な原料を用いて簡単に得られる 硬化促進剤は未だ提供されておらず、更なる改良が望まれてレ、る。  However, in these documents, there is no disclosure used for a solder resist, a sufficiently satisfactory storage stability performance is obtained, and a curing accelerator that can be easily obtained using inexpensive raw materials has not yet been provided. No further improvement is desired.
また、ソルダーレジストの硬化膜物性を高める観点から、アミン系化合物を熱硬化 剤として使用するのが一般的であるが、該ァミン系化合物は、ラジカル重合を抑制す る作用があるため、感度の高い向上が図れないことが問題となっている。  Also, from the viewpoint of improving the cured film physical properties of the solder resist, it is common to use an amine compound as a thermosetting agent. However, since the amine compound has an action of suppressing radical polymerization, it has a sensitivity. The problem is that high improvement cannot be achieved.
したがって、保存安定性が高く簡単で安価な材料を用いた硬化促進剤、及び該硬 化促進剤を使用し、熱によって硬化可能で保存安定性に優れ、硬化後は優れた耐 薬品性、硬度、誘電特性及び電気絶縁性などを発現する熱硬化性樹脂組成物、前 記硬化促進剤を使用し、 UV露光により画像形成可能で、表面のタック性が小さぐラ ミネート性及び取扱い性が良好で、保存安定性に優れ、高感度で現像性にも優れ、 現像後に優れた耐薬品性、表面硬度、耐熱性、誘電特性などを発現可能な感光性 組成物、及びこれを用いた感光性フィルム、並びに、高精細な永久パターン及びそ の効率的な形成方法も、未だ十分満足し得るものが提供されてレ、なレ、のが現状であ る。 Therefore, a curing accelerator using a simple, inexpensive material with high storage stability, and a curing accelerator that can be cured by heat and excellent in storage stability, and excellent in chemical resistance and hardness after curing. , Thermosetting resin composition that exhibits dielectric properties and electrical insulation, etc., and the above accelerator can be used to form an image by UV exposure. And a photosensitive composition capable of exhibiting excellent chemical resistance, surface hardness, heat resistance, dielectric properties and the like after development, and excellent in storage stability, high sensitivity and developability, and photosensitivity using the same. Films, high-definition permanent patterns, and their efficient forming methods are still being provided with satisfactory results. The
[0011] 特許文献 1 :特開昭 61— 243869号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 61-243869
特許文献 2：特開平 02— 097502号公報  Patent Document 2: Japanese Patent Laid-Open No. 02-097502
特許文献 3 :特開平 11一 246651号公報  Patent Document 3: Japanese Patent Laid-Open No. 11-246651
特許文献 4：特開昭 56— 155222号公報  Patent Document 4: Japanese Patent Laid-Open No. 56-155222
特許文献 5 :特開昭 57— 100127号公報  Patent Document 5: Japanese Unexamined Patent Publication No. 57-100127
特許文献 6：特開昭 59— 053526号公報  Patent Document 6: Japanese Unexamined Patent Publication No. 59-053526
特許文献 7 :特開 2000— 001526号公報  Patent Document 7: Japanese Unexamined Patent Publication No. 2000-001526
非特許文献 1 :日本油脂、遠藤岡 IJ (東工大)ネットワークポリマー voll 9, No. 4, P2 28— 235、 1998  Non-Patent Document 1: Nippon Oil & Fats, Endooka IJ (Tokyo Tech) Network Polymer voll 9, No. 4, P2 28—235, 1998
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0012] 本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題と する。即ち、本発明は、保存時の常温下では反応を生じず、保存安定性に優れ、加 熱により硬化促進効果及び熱架橋効果を発現し、エポキシ樹脂化合物などとの反応 を開始して、硬化膜の良好な膜硬度が得られる硬化促進剤、この硬化促進剤を使用 し、熱によって硬化可能で保存安定性に優れ、硬化後は優れた耐薬品性、硬度、誘 電特性及び電気絶縁性などを発現する熱硬化性樹脂組成物、前記硬化促進剤を使 用し、 UV露光により画像形成可能で、表面のタック性が小さぐラミネート性及び取 扱い性が良好で、保存安定性に優れ、高感度で現像性にも優れ、現像後に優れた 耐薬品性、表面硬度、耐熱性、誘電特性などを発現する感光性組成物、及びこれを 用いた感光性フィルム、並びに、高精細な永久パターン (保護膜、層間絶縁膜、及び ソルダーレジストパターンなど)及びその効率的な形成方法を提供することを目的と する。 [0012] An object of the present invention is to solve the conventional problems and achieve the following object. That is, the present invention does not cause a reaction at room temperature during storage, has excellent storage stability, exhibits a curing acceleration effect and a thermal crosslinking effect by heating, initiates a reaction with an epoxy resin compound, and cures. A curing accelerator that provides good film hardness of the film, and using this curing accelerator, it can be cured by heat and has excellent storage stability.After curing, it has excellent chemical resistance, hardness, dielectric properties and electrical insulation. A thermosetting resin composition that expresses the above, and the above-mentioned curing accelerator can be used to form an image by UV exposure, the surface tackiness is small, the laminate and handling properties are good, and the storage stability is excellent. , High sensitivity, excellent developability, and a photosensitive composition that exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development, a photosensitive film using the same, and a high-definition permanent Pattern (protective film, interlayer insulation film, And to provide a Zehnder resist pattern, etc.) and its efficient formation methods.
課題を解決するための手段  Means for solving the problem
[0013] 本発明者らは、前記課題に鑑み鋭意検討を重ねた結果、以下の知見を得た。即ち 、外部刺激によりアミンを生成し、分子内にカルボキシノレ基とアミド基とを 1対 1の比で 有する構造の化合物からなる硬化促進剤では、低温又は常温では反応を生じること がなぐ優れた保存安定性を有するとともに、加熱処理時には、該熱処理温度で速 やかな反応を示して硬化し、表面硬度、及び耐アルカリ性などに優れる硬化物が得 られることを知見した。 [0013] As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. That is, a curing accelerator made of a compound having a structure having a carboxylate group and an amide group in a ratio of 1: 1 in the molecule that generates an amine by external stimulation causes a reaction at low or normal temperature. It has been found that a cured product having excellent storage stability, curing at a rapid reaction at the heat treatment temperature and excellent in surface hardness, alkali resistance and the like can be obtained during heat treatment.
また、本発明者らは、当該硬化促進剤と、エポキシ樹脂化合物とを少なくとも有する 熱硬化性樹脂組成物では、熱によって硬化可能で保存安定性に優れ、硬化後は優 れた耐薬品性、硬度、誘電特性及び電気絶縁性などを発現することを知見した。さら に、本発明者らは、前記該硬化促進剤と、 1分子中に 1個以上のカルボキシル基及 びエステル基のいずれかを有する重合体と、重合性化合物と、光重合開始剤と、熱 架橋剤とを少なくとも有する感光性組成物では、保存安定性に優れ、高感度で現像 性にも優れ、現像後に優れた耐薬品性、表面硬度、耐熱性、誘電特性などを発現す ること力 Sでき、特にフィルムタイプのソルダーレジストの保存安定性の向上が図れるこ とを知見した。  Further, the present inventors have found that the thermosetting resin composition having at least the curing accelerator and the epoxy resin compound can be cured by heat and has excellent storage stability, and excellent chemical resistance after curing. It has been found that it exhibits hardness, dielectric properties and electrical insulation. Furthermore, the inventors of the present invention, the curing accelerator, a polymer having one or more carboxyl groups and ester groups in one molecule, a polymerizable compound, a photopolymerization initiator, A photosensitive composition having at least a thermal crosslinking agent has excellent storage stability, high sensitivity and excellent developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development. It was found that the storage stability of film-type solder resists can be improved.
本発明は、本発明者らの前記知見に基づくものであり、前記課題を解決するための 手段としては、以下の通りである。即ち、  The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
< 1 > 外部刺激によりアミンを生成し、分子内にカルボキシノレ基とアミド基とを 1対 1の比で有する構造であることを特徴とする硬化促進剤である。該 < 1 >に記載の硬 化促進剤においては、低温又は常温では反応を生じることがなぐ該硬化促進剤及 び該硬化促進剤を使用した化合物の優れた保存安定性が図れるとともに、加熱処理 時には、該熱処理温度で速やかな反応を示し、表面硬度、及び耐アルカリ性などに 優れる硬化物が得られる。  <1> A curing accelerator characterized by having a structure in which an amine is generated by an external stimulus and a carboxynole group and an amide group are in a ratio of 1: 1 in the molecule. In the curing accelerator according to <1>, the curing accelerator which does not cause a reaction at a low temperature or a normal temperature and a compound using the curing accelerator can be excellent in storage stability, and can be subjected to heat treatment. In some cases, a cured product exhibiting a rapid reaction at the heat treatment temperature and excellent in surface hardness, alkali resistance and the like can be obtained.
< 2 > 外部刺激が、 80°C以上の加熱である前記 < 1 >に記載の硬化促進剤であ る。  <2> The curing accelerator according to <1>, wherein the external stimulus is heating at 80 ° C or higher.
< 3 > 下記一般式（1)、（2)、（3)、（4)、 （5)及び (6)のいずれかで表される前記 < 1 >から < 2 >のいずれかに記載の硬化促進剤である。  <3> According to any one of the above <1> to <2> represented by any one of the following general formulas (1), (2), (3), (4), (5) and (6) It is a curing accelerator.
[化 1] —般式 （ 1 )[Chemical formula 1] — General formula (1)
Figure imgf000008_0001
Figure imgf000008_0001
[化 2] —般式 （2)[Chemical 2] —General formula (2)
Figure imgf000009_0001
Figure imgf000009_0001
[化 3]  [Chemical 3]
—般式 (3)
Figure imgf000009_0002
—General formula (3)
Figure imgf000009_0002
[化 4]  [Chemical 4]
—般式 （4)
Figure imgf000009_0003
—General formula (4)
Figure imgf000009_0003
[化 5]  [Chemical 5]
—般式 (5)
Figure imgf000009_0004
—General formula (5)
Figure imgf000009_0004
[化 6]  [Chemical 6]
—般式 （6)
Figure imgf000009_0005
—General formula (6)
Figure imgf000009_0005
ただし、前記一般式（1)、（2)、 （3)、 (4)、 (5)及び (6)中、 R^R18は、水素原子、 及び置換基のいずれかを表し、 Ai A6は、 2価の置換基を表し、 〜 1は、単結合 、二重結合、及び 2価の置換基のいずれかを表す。 However, in the general formulas (1), (2), (3), (4), (5) and (6), R ^ R 18 represents either a hydrogen atom or a substituent, and Ai A 6 represents a divalent substituent, and 1 is a single bond, double bond, and represents one of the divalent substituent.
<4> エポキシ樹脂化合物と、前記 1から 3のいずれかに記載の硬化促進剤と、を 少なくとも含むことを特徴とする熱硬化性樹脂組成物である。該 < 4 >に記載の熱硬 化性樹脂組成物においては、熱によって硬化可能で保存安定性に優れ、硬化後は 優れた耐薬品性、硬度、耐熱性、誘電特性、電気絶縁性などを発現できる。 <4> A thermosetting resin composition comprising at least an epoxy resin compound and the curing accelerator according to any one of 1 to 3 above. The thermosetting resin composition according to <4> is curable by heat and has excellent storage stability. Excellent chemical resistance, hardness, heat resistance, dielectric properties, electrical insulation, etc. can be expressed.
<5> 硬化促進剤の含有量が、 0.01〜50質量％である前記 <4>に記載の熱 硬化性樹脂組成物である。  <5> The thermosetting resin composition according to <4>, wherein the content of the curing accelerator is 0.01 to 50% by mass.
<6> (A)l分子中に 1個以上のカルボキシル基及びエステル基のいずれかを有 する重合体と、（B)重合性化合物と、（C)光重合開始剤と、 （D)前記 <1>から <3 >のいずれかに記載の硬化促進剤と、を少なくとも含むことを特徴とする感光性組成 物である。該 < 6 >に記載の感光性組成物においては、前記 <1>から <3>のい ずれかに記載の硬化促進剤を含有するので、保存安定性及び安全性に優れ、誘電 率が低ぐ前記感光性組成物を用いて永久パターンを形成した場合、硬化膜の耐薬 品性、表面硬度、耐熱性、誘電特性の向上が図られる。また、前記効果促進剤が熱 架橋剤として機能するため、熱架橋剤を別個に添加しなくても、前記感光層の硬化 領域の膜強度が高められる。  <6> (A) a polymer having one or more carboxyl groups and ester groups in one molecule, (B) a polymerizable compound, (C) a photopolymerization initiator, (D) <1> to <3> A photosensitive composition comprising at least the curing accelerator according to any one of <1> to <3>. In the photosensitive composition according to <6>, since it contains the curing accelerator according to any one of <1> to <3>, it has excellent storage stability and safety, and has a low dielectric constant. When a permanent pattern is formed using the photosensitive composition, the chemical resistance, surface hardness, heat resistance, and dielectric properties of the cured film are improved. Further, since the effect accelerator functions as a thermal crosslinking agent, the film strength of the cured region of the photosensitive layer can be increased without adding a thermal crosslinking agent separately.
<7> (E)熱架橋剤を更に含む前記 < 6 >に記載の感光性組成物である。該く 7 >に記載の感光性組成物においては、硬化促進剤の熱架橋効果と、該熱架橋剤と の相乗効果で、前記感光層の硬化領域の膜強度のより高い向上が図られる。  <7> The photosensitive composition according to <6>, further including (E) a thermal crosslinking agent. In the photosensitive composition described in 7>, the film strength in the cured region of the photosensitive layer can be further improved by the synergistic effect of the thermal crosslinking effect of the curing accelerator and the thermal crosslinking agent.
<8> (D)硬化促進剤の含有量力 0.01〜40質量％である前記 <6>からく 7 >のいずれかに記載の感光性組成物である。  <8> The photosensitive composition according to any one of <6> Karaku 7>, wherein the content power of (D) the curing accelerator is 0.01 to 40% by mass.
<9> (E)熱架橋剤が、エポキシ化合物、ォキセタン化合物、ポリイソシァネート 化合物、ポリイソシァネートィヒ合物にブロック剤を反応させて得られる化合物、及びメ ラミン誘導体から選択される少なくとも 1種である前記 < 6 >から < 8 >のいずれかに 記載の感光性組成物である。  <9> (E) The thermal crosslinking agent is at least selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The photosensitive composition according to any one of <6> to <8>, which is one kind.
<10> (E)熱架橋剤が、下記一般式（7)〜（9)のいずれかで表される化合物で ある前記 < 7 >から < 9 >のいずれかに記載の感光性組成物である。  <10> (E) The photosensitive composition according to any one of <7> to <9>, wherein the thermal crosslinking agent is a compound represented by any one of the following general formulas (7) to (9): is there.
[化 7] 一般式（7) [Chemical 7] General formula (7)
Figure imgf000010_0001
一般式 (8)
Figure imgf000010_0001
General formula (8)
Figure imgf000011_0001
Figure imgf000011_0001
ただし、前記一般式（7)、（8)、及び（9)中、 Pは、酸素原子、カルボニル基、アミド 基、ウレタン基、アルキレン基、及びァリーレン基のいずれかを表し、 Qは、ホウ素原 子、窒素原子、アルキレン基、及びァリーレン基のいずれかを表し、 Wは、 2つの X26 と結合を有するナフタレンを表し、 A21 A25は、単結合、アルキレン基、及びァリーレ ン基のいずれかを表し、 X21 X26は、 OCONH― NHCOO NHCO— However, in the general formulas (7), (8), and (9), P represents an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene group, or an arylene group, and Q represents boron. Represents an atom, a nitrogen atom, an alkylene group, or an arylene group, W represents naphthalene having a bond with two X 26 s , A 21 A 25 represents a single bond, an alkylene group, or an arylene group. X 21 X 26 represents either OCONH— NHCOO NHCO—
26  26
、及び CONH のいずれかを表す。 R R。は、水素原子、ハロゲン原子、アル キル基、及びァリール基のいずれかを表す。  , And CONH. R R. Represents one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
< 11 > (E)熱架橋剤が、分子内に 2つ以上のォキシラン基を有するエポキシ化 合物である前記 < 6 >から < 10 >のいずれかに記載の感光性組成物である。  <11> (E) The photosensitive composition according to any one of <6> to <10>, wherein the thermal crosslinking agent is an epoxy compound having two or more oxosilane groups in the molecule.
< 12 > (E)熱架橋剤が、分子内に 2つ以上のォキセタニル基を有するォキセタン 化合物である前記 < 6 >からく 11 >のいずれかに記載の感光性組成物である。  <12> (E) The photosensitive composition according to any one of <6> to 11, wherein the thermal crosslinking agent is an oxetane compound having two or more oxetanyl groups in the molecule.
< 13 > (E)熱架橋剤が、下記構造式 (I)及び (II)のいずれかで表される前記く 6 >から < 12 >のいずれかに記載の感光性組成物である。  <13> The photosensitive composition according to any one of <6> to <12>, wherein (E) the thermal crosslinking agent is represented by any one of the following structural formulas (I) and (II):
[化 8] [Chemical 8]
0  0
R
Figure imgf000011_0002
OH 」π 構造式 (I)R
Figure imgf000011_0002
OH '' π Structural formula (I)
[化 9] 構造式 （Π)[Chemical 9] Structural formula (Π)
Figure imgf000012_0001
Figure imgf000012_0001
ただし、前記構造式 (I)及び (II)中、 Rは水素原子及び炭素数:!〜 6のアルキル基 のいずれかを表し、 nは 0〜20の整数を表す。  In the structural formulas (I) and (II), R represents either a hydrogen atom or an alkyl group having from 6 to 6 carbon atoms, and n represents an integer of 0 to 20.
<14> (E)熱架橋剤が、へキサメチルイ匕メチロールメラミンである前記く 6 >から < 9 >のレ、ずれかに記載の感光性組成物である。  <14> The photosensitive composition according to any one of <6> to <9>, wherein (E) the thermal crosslinking agent is hexamethyl dimethylol melamine.
<15> (A)重合体力 エポキシアタリレート化合物である前記 < 6 >力 く 13 > のいずれかに記載の感光性組成物である。  <15> (A) Polymer strength The photosensitive composition according to any one of the above <6> strength 13> which is an epoxy acrylate compound.
く 16 > (A)重合体が、側鎖に (メタ）アタリロイル基、及び酸性基を有するビュル 共重合体の少なくとも 1種を含む前記く 6 >からく 13 >のいずれかに記載の感光性 組成物である。  <16> The photosensitivity according to any one of <6>, <13>, wherein the polymer (A) contains at least one of a butyl copolymer having a (meth) ataryloyl group and an acidic group in the side chain. It is a composition.
<17> (A)重合体力 エポキシアタリレートイ匕合物と、側鎖に (メタ）アタリロイル基 、及び酸性基を有するビュル共重合体の少なくとも 1種を含む前記 <6>から < 13 >のいずれかに記載の感光性組成物である。  <17> (A) Polymer strength comprising at least one of an epoxy attareito toy compound, a butyl copolymer having a (meth) atalyloyl group and an acidic group in the side chain, from the above <6> to <13> It is the photosensitive composition in any one.
<18> (A)重合体力 下記構造式 (III)で表される前記く 6>からく 15>に記載 の感光性組成物である。  <18> (A) Polymer power The photosensitive composition according to <6 >> <15> represented by the following structural formula (III).
[化 10]
Figure imgf000012_0002
[Chemical 10]
Figure imgf000012_0002
構造式  Structural formula
ただし、前記構造式 (m)中、 Xは水素原子、及び少なくとも酸性基を含む置換基の いずれかを表し、 γはメチレン基、イソプロピリデン基、及びスルホニル基のいずれか を表し、 nは、 1〜20の整数を表す。  However, in the structural formula (m), X represents any of a hydrogen atom and a substituent containing at least an acidic group, γ represents any of a methylene group, an isopropylidene group, and a sulfonyl group, and n is Represents an integer of 1-20.
<19> (A)重合体が、無水マレイン酸共重合体の無水物基に対して 0.：!〜 1.2 当量の 1級ァミン化合物を反応させて得られる共重合体である前記 <6>から <9> 及び < 14 >のレ、ずれかに記載の感光性組成物である。 <19> The above-mentioned <6>, wherein the polymer (A) is a copolymer obtained by reacting 0.:! To 1.2 equivalents of a primary amine compound to the anhydride group of the maleic anhydride copolymer. To <9> And <14>, the photosensitive composition according to any one of the above.
<20> (A)重合体が、（a)無水マレイン酸と、（b)芳香族ビュル単量体と、 （c)ビ 二ル単量体であって、該ビュル単量体のホモポリマーのガラス転移温度（Tg)が 80 °C未満であるビニル単量体とからなる共重合体の無水物基に対して 0.1〜： 1.0当量 の 1級ァミン化合物を反応させて得られる共重合体である前記 <6>から <9>、 <1 4 >及びく 19 >のいずれかに記載の感光性組成物である。  <20> (A) The polymer is (a) maleic anhydride, (b) an aromatic bull monomer, and (c) a vinyl monomer, which is a homopolymer of the bull monomer. A copolymer obtained by reacting 0.1 to 1.0 equivalents of primary amine compound to the anhydride group of a copolymer comprising a vinyl monomer having a glass transition temperature (Tg) of less than 80 ° C The photosensitive composition according to any one of <6> to <9>, <14> and <19>.
<21> (B)重合性化合物が、（メタ）アクリル基を有するモノマーから選択される 少なくとも 1種を含む前記 < 6 >から < 20 >のいずれかに記載の感光性組成物であ る。  <21> The photosensitive composition according to any one of <6> to <20>, wherein the polymerizable compound (B) includes at least one selected from monomers having a (meth) acryl group.
<22> (C)光重合開始剤が、ハロゲン化炭化水素誘導体、ホスフィンオキサイド 、へキサァリールビイミダゾール、ォキシム誘導体、有機過酸化物、チォ化合物、ケト ン化合物、芳香族ォニゥム塩及びケトォキシムエーテルから選択される少なくとも 1種 を含む前記 < 6 >から < 21 >のレ、ずれかに記載の感光性組成物である。  <22> (C) The photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexarylbiimidazole, oxime derivative, organic peroxide, thio compound, keton compound, aromatic onium salt, or ketoxime. The photosensitive composition according to <6> to <21> above, which contains at least one selected from ethers.
<23> 支持体と、該支持体上に、前記 <6>から <22>のいずれかに記載の感 光性組成物が積層されてなる感光層とを有することを特徴とする感光性フィルムであ る。  <23> A photosensitive film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to any one of <6> to <22> on the support. It is.
<24> 感光層を露光し現像する場合において、該感光層の露光する部分の厚 みを該露光及び現像後において変化させない前記露光に用いる光の最小エネルギ 一が 0.1〜： 100 (mj/cm2)である前記く 23 >に記載の感光性フィルムである。 <24> In the case where the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 100 (mj / cm 2 ) The photosensitive film according to the above item 23>.
<25> 支持体が、合成樹脂を含み、かつ透明である前記く 23 >からく 24>の レ、ずれかに記載の感光性フィルムである。  <25> The photosensitive film according to any one of the items <23> to <24>, wherein the support contains a synthetic resin and is transparent.
<26> 支持体が、長尺状である前記く 23 >力 く 25 >のいずれかに記載の感 光性フィルムである。  <26> The light-sensitive film according to any one of the above items 23> strength 25>, wherein the support is long.
<27> 長尺状であり、ロール状に巻かれてなる前記 < 23 >から < 26 >のいず れかに記載の感光性フィルムである。  <27> The photosensitive film according to any one of <23> to <26>, which is long and wound in a roll.
<28> 感光層上に保護フィルムを有してなる前記く 23>力 く 27>のレ、ずれ かに記載の感光性フィルムである。  <28> The photosensitive film according to <23>, <27>, wherein the protective film is provided on the photosensitive layer.
<29> 感光層の厚みが、 3〜100/1111でぁる前記<23>から<28>のぃずれ かに記載の感光性フィルムである。 <29> The thickness of the photosensitive layer is 3 to 100/1111. A photosensitive film according to any one of the above.
< 30 > 感光層が、光照射手段からの光を受光し出射する描素部を n個有する光 変調手段により、前記光照射手段からの光を変調させた後、前記描素部における出 射面の歪みによる収差を補正可能な非球面を有するマイクロレンズを配列したマイク 口レンズアレイを通した光で、露光される前記く 23 >からく 29 >に記載の感光性フ イノレムである。  <30> After the photosensitive layer modulates the light from the light irradiating means by the light modulating means having n picture elements for receiving and emitting the light from the light irradiating means, the light is emitted from the light emitting means. The photosensitive fine film according to the above item 23> Karaku 29>, which is exposed with light passing through a microphone lens array in which microlenses having aspherical surfaces capable of correcting aberration due to surface distortion are arranged.
< 31 > 前記 < 6 >から < 22 >のいずれかに記載の感光性組成物を、基材の表 面に塗布し、乾燥して感光層を形成した後、露光し、現像し、加熱することを特徴とす る永久パターン形成方法である。該く 31 >に記載の永久パターン形成方法におい ては、前記感光性組成物が前記基材の表面に塗布され、該塗布された感光性組成 物が乾燥されて前記感光層が形成される。該感光層が露光され、該露光された感光 層が現像され、加熱されることにより、感光層の硬化領域の膜強度が高められる。そ の結果、表面硬度が高ぐ保護膜、層間絶縁膜、及びソルダーレジストパターンなど に最適な永久パターンが形成される。  <31> The photosensitive composition according to any one of <6> to <22> is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated. This is a permanent pattern forming method characterized by this. In the permanent pattern forming method described in 31>, the photosensitive composition is applied to the surface of the substrate, and the applied photosensitive composition is dried to form the photosensitive layer. The photosensitive layer is exposed, and the exposed photosensitive layer is developed and heated, whereby the film strength of the cured region of the photosensitive layer is increased. As a result, an optimum permanent pattern is formed as a protective film having a high surface hardness, an interlayer insulating film, and a solder resist pattern.
< 32 > 前記 < 23 >から < 31 >のレ、ずれかに記載の感光性フィルムを、加熱及 び加圧の少なくともいずれかの下において基材の表面に積層した後、露光し、現像 し、加熱することを特徴とする永久パターン形成方法である。該く 32 >に記載の永 久パターン形成方法においては、前記感光性フィルム力 加熱及び加圧下にて前記 基材の表面に積層される。該積層された感光性フィルムにおける前記感光層が露光 され、該露光された感光層が現像され、加熱されることにより、感光層の硬化領域の 膜強度が高められる。その結果、表面硬度が高ぐ保護膜、層間絶縁膜、及びソルダ 一レジストパターンなどに最適な永久パターンが形成される。  <32> The photosensitive film according to any one of the above items <23> to <31> is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed. And a permanent pattern forming method characterized by heating. In the permanent pattern forming method described in 32>, the photosensitive film force is laminated on the surface of the substrate under heating and pressing. The photosensitive layer in the laminated photosensitive film is exposed, and the exposed photosensitive layer is developed and heated, whereby the film strength of the cured region of the photosensitive layer is increased. As a result, an optimum permanent pattern is formed as a protective film having a high surface hardness, an interlayer insulating film, and a solder resist pattern.
< 33 > 基材が、配線形成済みのプリント配線基板である前記く 31 >からく 32 > のいずれかに記載の永久パターン形成方法である。該永久パターン形成方法を利 用することにより、半導体部品の多層配線基板ゃビルドアップ配線基板などへの高 密度実装が可能である。  <33> The permanent pattern forming method according to any one of the above <31>, <32>, and <32>, wherein the base material is a printed wiring board on which wiring has been formed. By using the permanent pattern forming method, high-density mounting of semiconductor components on a multilayer wiring board or a build-up wiring board is possible.
< 34 > 露光が、形成するパターン情報に基づいて像様に行われる前記く 31 > 力ら< 33 >のレ、ずれかに記載の永久パターン形成方法である。 < 35 > 露光が、形成するパターン情報に基づいて制御信号を生成し、該制御信 号に応じて変調させた光を用いて行われる前記く 31 >からく 34 >のいずれかに記 載の永久パターン形成方法である。 <34> The method for forming a permanent pattern according to <31>, wherein the exposure is performed imagewise based on pattern information to be formed. <35> The exposure according to any one of the above items 31> Karaku 34>, wherein the exposure is performed using light modulated based on the pattern information to be generated and modulated according to the control signal. This is a permanent pattern forming method.
< 36 > 露光が、光を照射する光照射手段と、形成するパターン情報に基づいて 前記光照射手段から照射される光を変調させる光変調手段とを用いて行われる前記 く 31 >力 く 35 >のいずれかに記載の永久パターン形成方法である。  <36> The exposure is performed using light irradiation means for irradiating light and light modulation means for modulating light emitted from the light irradiation means based on pattern information to be formed. The permanent pattern forming method according to any one of the above.
< 37 > 光変調手段が、形成するパターン情報に基づいて制御信号を生成する パターン信号生成手段を更に有してなり、前記光照射手段から照射される光を該パ ターン信号生成手段が生成した制御信号に応じて変調させる前記 < 36 >に記載の 永久パターン形成方法である。  <37> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit. The method for forming a permanent pattern according to <36>, wherein modulation is performed according to a control signal.
< 38 > 光変調手段が、 n個の描素部を有してなり、該 n個の描素部の中から連続 的に配置された任意の n個未満の前記描素部を、形成するパターン情報に応じて制 御可能である前記く 36 >からく 37 >のいずれかに記載の永久パターン形成方法 である。該く 38 >に記載の永久パターン形成方法においては、前記光変調手段に おける n個の描素部の中から連続的に配置された任意の n個未満の描素部をパター ン情報に応じて制御することにより、前記光照射手段からの光が高速で変調される。  <38> The light modulation means has n pixel parts, and forms any less than n of the pixel parts continuously arranged from the n pixel parts. 38. The permanent pattern forming method according to any one of 36, 37, 37, which is controllable according to pattern information. In the method for forming a permanent pattern described in 38>, an arbitrary less than n pixel parts continuously arranged from the n picture element parts in the light modulation means are selected according to the pattern information. By controlling the light, the light from the light irradiation means is modulated at high speed.
< 39 > 光変調手段が、空間光変調素子である前記 < 36 >から < 38 >のいずれ に記載の永久パターン形成方法である。  <39> The permanent pattern forming method according to any one of <36> to <38>, wherein the light modulation means is a spatial light modulation element.
<40 > 空間光変調素子が、デジタル 'マイクロミラー'デバイス（DMD)である前 記 < 39 >に記載の永久パターン形成方法である。  <40> The method for forming a permanent pattern according to <39>, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
<41 > 描素部が、マイクロミラーである前記く 38 >からく 40 >のいずれかに記 載の永久パターン形成方法である。  <41> The permanent pattern forming method according to any one of the above 38> Karaku 40>, wherein the pixel part is a micromirror.
<42 > 露光が、光変調手段により光を変調させた後、前記光変調手段における 描素部の出射面の歪みによる収差を補正可能な非球面を有するマイクロレンズを配 列したマイクロレンズアレイを通して行われる前記く 38 >からく 41 >のいずれかに 記載の永久パターン形成方法である。  <42> After the light is modulated by the light modulation means, the exposure is performed through a microlens array in which microlenses having aspheric surfaces capable of correcting aberration due to distortion of the exit surface of the picture element portion in the light modulation means are arranged. The method for forming a permanent pattern according to any one of the above 38> Kara 41>.
<43 > 非球面が、トーリック面である前記 < 42 >に記載の永久パターン形成方 法である。該く 43 >に記載の永久パターン形成方法においては、前記非球面がト 一リック面であることにより、前記描素部における放射面の歪みによる収差が効率よく 補正され、前記感光層上に結像させる像の歪みが効率よく抑制される。その結果、前 記感光層への露光が高精細に行われる。その後、前記感光層を現像することにより、 高精細な永久パターンが形成される。 <43> The method for forming a permanent pattern according to <42>, wherein the aspherical surface is a toric surface. In the permanent pattern forming method described in 43>, the aspherical surface is a top surface. By using the single lick surface, the aberration due to the distortion of the radiation surface in the pixel portion is efficiently corrected, and the distortion of the image formed on the photosensitive layer is efficiently suppressed. As a result, the photosensitive layer is exposed with high definition. Thereafter, the photosensitive layer is developed to form a high-definition permanent pattern.
<44 > 露光が、アパーチャアレイを通して行われる前記く 31 >からく 43 >のい ずれかに記載の永久パターン形成方法である。該く 44 >に記載の永久パターン形 成方法においては、露光が前記アパーチャアレイを通して行われることにより、消光 比が向上する。その結果、露光が極めて高精細に行われる。その後、前記感光層を 現像することにより、極めて高精細な永久パターンが形成される。  <44> The method for forming a permanent pattern according to any one of the above items <31>, <43>, wherein exposure is performed through an aperture array. In the permanent pattern forming method described in 44>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<45 > 露光が、露光光と感光層とを相対的に移動させながら行われる前記く 31 >からく 44 >のいずれかに記載の永久パターン形成方法である。該<45 >に記載 の永久パターン形成方法においては、前記変調させた光と前記感光層とを相対的に 移動させながら露光することにより、露光が高速に行われる。  <45> The permanent pattern forming method according to any one of <31>, <44>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer. In the method for forming a permanent pattern according to <45>, the exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
<46 > 露光が、感光層の一部の領域に対して行われる前記く 31 >力らく 45 > のいずれかに記載の永久パターン形成方法である。  <46> The method for forming a permanent pattern according to any one of the above <31>, <45>, wherein the exposure is performed on a partial region of the photosensitive layer.
<47 > 光照射手段が、 2以上の光を合成して照射可能である前記く 36 >からく 46 >のレ、ずれかに記載の永久パターン形成方法である。該< 47 >に記載の永久 パターン形成方法においては、前記光照射手段が 2以上の光を合成して照射可能 であることにより、露光が焦点深度の深い露光光で行われる。その結果、前記感光層 への露光が極めて高精細に行われる。その後、前記感光層を現像することにより、極 めて高精細な永久パターンが形成される。  <47> The method for forming a permanent pattern according to any one of the above items, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern according to <47>, since the light irradiation means can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form an extremely fine permanent pattern.
<48 > 光照射手段が、複数のレーザと、マルチモード光ファイバと、該複数のレ 一ザからそれぞれ照射されたレーザ光を集光して前記マルチモード光ファイバに結 合させる集合光学系とを有する前記く 36 >からく 47 >のいずれかに記載の永久パ ターン形成方法である。該く 47 >に記載の永久パターン形成方法においては、前 記光照射手段により、前記複数のレーザからそれぞれ照射されたレーザ光が前記集 合光学系により集光され、前記マルチモード光ファイバに結合可能とすることにより、 露光が焦点深度の深い露光光で行われる。その結果、前記感光層への露光が極め て高精細に行われる。その後、前記感光層を現像することにより、極めて高精細な永 久パターンが形成される。 <48> The light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. The method for forming a permanent pattern according to any one of the above 36> Karaku 47> having the above. In the permanent pattern forming method described in 47>, the laser light respectively emitted from the plurality of lasers is condensed by the converging optical system by the light irradiation means and coupled to the multimode optical fiber. By making it possible, exposure is performed with exposure light having a deep focal depth. As a result, the photosensitive layer is extremely exposed. And done in high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<49 > 露光が、 395〜415nmの波長のレーザ光を用いて行われる前記 < 31 > 力 く 48 >のレ、ずれかに記載の永久パターン形成方法である。  <49> The method for forming a permanent pattern according to <31>, wherein the exposure is performed using a laser beam having a wavelength of 395 to 415 nm.
< 50 > 加熱が、 120〜250°Cで行われる全面加熱処理である前記 < 31 >から < 49 >のレ、ずれかに記載の永久パターン形成方法である。該< 50 >に記載の永 久パターン形成方法では、前記温度条件で行われる全面加熱処理において、硬化 膜の膜強度が高められる。  <50> The method for forming a permanent pattern according to <31> to <49>, wherein the heating is performed on the entire surface at 120 to 250 ° C. In the permanent pattern formation method according to <50>, the film strength of the cured film is increased in the entire surface heat treatment performed under the temperature condition.
< 51 > 現像が行われた後、感光層に対して全面露光処理を行う前記 < 31 >か らく 50 >のいずれかに記載の永久パターン形成方法である。該く 51 >に記載の永 久パターン形成方法においては、現像が行われた後、前記感光層に対して全面露 光処理が行われることにより、前記感光性組成物中の樹脂の硬化が促進される。  <51> The method for forming a permanent pattern according to any one of <31> to <50>, wherein the photosensitive layer is subjected to a whole surface exposure treatment after development. In the permanent pattern forming method described in 51>, the development of the photosensitive layer is followed by an overall exposure process to accelerate the curing of the resin in the photosensitive composition. Is done.
< 52 > 保護膜、層間絶縁膜、及びソルダーレジストパターンの少なくともいずれ かを形成する前記く 31 >からく 51 >のいずれかに記載の永久パターン形成方法 である。該く 52 >に記載の永久パターン形成方法では、保護膜、層間絶縁膜及び ソルダーレジストパターンの少なくともいずれかが形成されるので、該膜の有する絶 縁性、耐熱性などにより、配線が外部からの衝撃や曲げなどから保護される。  <52> The method for forming a permanent pattern according to any one of the above <31> and <51>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. In the permanent pattern forming method described in 52>, since at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed, the wiring is externally provided due to the insulation property, heat resistance, etc. of the film. Protected from impact and bending.
< 53 > 前記 < 31 >力ら< 52 >のレ、ずれかに記載の永久パターン形成方法によ り形成されることを特徴とする永久パターンである。該< 53 >に記載の永久パターン は、前記永久パターン形成方法により形成されるので、優れた耐薬品性、表面硬度、 耐熱性などを有し、かつ高精細であり、半導体部品の多層配線基板ゃビルドアップ 配線基板などへの高密度実装に有用である。  <53> A permanent pattern formed by the method for forming a permanent pattern described in <31>, wherein the <31> force is <52>. Since the permanent pattern according to <53> is formed by the permanent pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition, and is a multilayer wiring board for semiconductor components. N Build-up Useful for high-density mounting on wiring boards.
< 54 > 保護膜、層間絶縁膜、及びソルダーレジストパターンの少なくともいずれ かである前記 < 53 >に記載の永久パターンである。該< 54 >に記載の永久パター ンは、保護膜、層間絶縁膜及びソルダーレジストパターンの少なくともいずれかであ るので、該膜の有する絶縁性、耐熱性などにより、配線が外部からの衝撃や曲げなど 力 保護される。  <54> The permanent pattern according to <53>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. The permanent pattern described in <54> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Bending and other forces are protected.
発明の効果 [0020] 本発明によると、従来における問題を解決することができ、保存時の常温下では反 応を生じず、保存安定性に優れ、加熱により硬化促進効果及び熱架橋効果を発現し 、エポキシ樹脂化合物などの樹脂との反応を開始して硬化させ、硬化膜の良好な膜 硬度が得られる硬化促進剤、この硬化促進剤を使用し、熱によって硬化可能で保存 安定性に優れ、硬化後は優れた耐薬品性、硬度、誘電特性及び電気絶縁性などを 発現する熱硬化性樹脂組成物、及び前記硬化促進剤を使用し、 UV露光により画像 形成可能で、表面のタック性が小さぐラミネート性及び取扱い性が良好で、保存安 定性に優れ、高感度で現像性にも優れ、現像後に優れた耐薬品性、表面硬度、耐 熱性、誘電特性などを発現する感光性組成物、及びこれを用いた感光性フィルム、 並びに、高精細な永久パターン (保護膜、層間絶縁膜、及びソルダーレジストパター ンなど）及びその効率的な形成方法を提供することができる。 The invention's effect [0020] According to the present invention, the conventional problems can be solved, no reaction occurs at room temperature during storage, excellent storage stability, a curing promoting effect and a thermal cross-linking effect are exhibited by heating, and an epoxy A curing accelerator that initiates a reaction with a resin such as a resin compound and cures it to obtain good film hardness of the cured film. Using this curing accelerator, it can be cured by heat and has excellent storage stability, after curing. Uses a thermosetting resin composition that exhibits excellent chemical resistance, hardness, dielectric properties, electrical insulation, and the like, and the curing accelerator, can form images by UV exposure, and has low surface tack A photosensitive composition that has good laminating and handling properties, excellent storage stability, high sensitivity and excellent developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development, and Photosensitive film using this As well, it is possible to provide high-definition permanent pattern (protective film, an interlayer insulating film, and the like solder resist pattern) and the efficient formation methods.
図面の簡単な説明  Brief Description of Drawings
[0021] [図 1A]図 1Aは、 DMDの使用領域の例を示す図の一例である。 FIG. 1A is an example of a diagram illustrating an example of a DMD usage area.
[図 1B]図 1Bは、図 1Aと同様の DMDの使用領域の例を示す図の一例である。  FIG. 1B is an example of a diagram showing an example of a DMD usage area similar to FIG. 1A.
[図 2A]図 2Aは、結合光学系の異なる他の露光ヘッドの構成を示す光軸に沿った断 面図の一例である。  FIG. 2A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system.
[図 2B]図 2Bは、マイクロレンズアレイ等を使用しない場合に被露光面に投影される 光像を示す平面図の一例である。  [FIG. 2B] FIG. 2B is an example of a plan view showing an optical image projected onto an exposed surface when a microlens array or the like is not used.
[図 2C]図 2Cは、マイクロレンズアレイ等を使用した場合に被露光面に投影される光 像を示す平面図の一例である。  [FIG. 2C] FIG. 2C is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is used.
[図 3]図 3は、 DMDを構成するマイクロミラーの反射面の歪みを等高線で示す図の一 例である。  [FIG. 3] FIG. 3 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD by contour lines.
[図 4A]図 4Aは、前記マイクロミラーの反射面の歪みを、該ミラーの 2つの対角線方向 につレ、て示すグラフの一例である。  FIG. 4A is an example of a graph showing distortion of the reflection surface of the micromirror in two diagonal directions of the mirror.
[図 4B]図 4Bは、図 4Aと同様の前記マイクロミラーの反射面の歪みを、該ミラーの 2つ の対角線方向について示すグラフの一例である。  FIG. 4B is an example of a graph showing distortion of the reflection surface of the micromirror similar to that in FIG. 4A in the two diagonal directions of the mirror.
[図 5A]図 5Aは、パターン形成装置に用いられたマイクロレンズアレイの正面図の一 例である。 [図 5B]図 5Bは、パターン形成装置に用いられたマイクロレンズアレイの側面図の一 例である。 FIG. 5A is an example of a front view of a microlens array used in a pattern forming apparatus. FIG. 5B is an example of a side view of a microlens array used in the pattern forming apparatus.
[図 6A]図 6Aは、マイクロレンズアレイを構成するマイクロレンズの正面図の一例であ る。  [FIG. 6A] FIG. 6A is an example of a front view of a microlens constituting a microlens array.
[図 6B]図 6Bは、マイクロレンズアレイを構成するマイクロレンズの側面図の一例であ る。  [FIG. 6B] FIG. 6B is an example of a side view of the microlens constituting the microlens array.
[図 7A]図 7Aは、マイクロレンズによる集光状態を 1つの断面内について示す概略図 の一例である。  [FIG. 7A] FIG. 7A is an example of a schematic diagram showing a condensing state by a microlens in one cross section.
[図 7B]図 7Bは、マイクロレンズによる集光状態を図 7Aとは別の断面内について示す 概略図の一例である。  [FIG. 7B] FIG. 7B is an example of a schematic view showing a condensing state by the microlens in a cross section different from FIG. 7A.
[図 8A]図 8Aは、本発明のマイクロレンズの集光位置近傍におけるビーム径をシミュ レーシヨンした結果を示す図の一例である。  FIG. 8A is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention.
[図 8B]図 8Bは、図 8Aと同様のシミュレーション結果を、別の位置について示す図の 一例である。  [FIG. 8B] FIG. 8B is an example of a diagram showing the same simulation results as in FIG. 8A but at different positions.
[図 8C]図 8Cは、図 8Aと同様のシミュレーション結果を、別の位置について示す図の 一例である。  [FIG. 8C] FIG. 8C is an example of a diagram showing the same simulation results as in FIG. 8A but at different positions.
[図 8D]図 8Dは、図 8Aと同様のシミュレーション結果を、別の位置について示す図の 一例である。  [FIG. 8D] FIG. 8D is an example of a diagram showing the same simulation results as in FIG. 8A but at different positions.
[図 9A]図 9Aは、従来のパターン形成方法において、マイクロレンズの集光位置近傍 におけるビーム径をシミュレーションした結果を示す図の一例である。  FIG. 9A is an example of a diagram showing a result of simulating a beam diameter in the vicinity of a condensing position of a microlens in a conventional pattern forming method.
[図 9B]図 9Bは、図 9Aと同様のシミュレーション結果を、別の位置について示す図の 一例である。 [FIG. 9B] FIG. 9B is an example of a diagram showing the same simulation results as in FIG. 9A but at different positions.
[図 9C]図 9Cは、図 9Aと同様のシミュレーション結果を、別の位置について示す図の 一例である。  [FIG. 9C] FIG. 9C is an example of a diagram showing the same simulation results as in FIG. 9A but at different positions.
[図 9D]図 9Dは、図 9Aと同様のシミュレーション結果を、別の位置について示す図の 一例である。  [FIG. 9D] FIG. 9D is an example of a diagram showing the same simulation results as in FIG. 9A but at different positions.
[図 10A]図 10Aは、マイクロレンズアレイを構成するマイクロレンズの正面図の一例で ある。 [図 10B]図 10Bは、マイクロレンズアレイを構成するマイクロレンズの側面図の一例で ある。 [FIG. 10A] FIG. 10A is an example of a front view of a microlens constituting a microlens array. [FIG. 10B] FIG. 10B is an example of a side view of the microlens constituting the microlens array.
[図 11A]図 11Aは、図 10A及び図 10Bのマイクロレンズによる集光状態を 1つの断面 内につレ、て示す概略図の一例である。  [FIG. 11A] FIG. 11A is an example of a schematic diagram showing the light collection state by the microlens of FIGS. 10A and 10B in one cross section.
[図 11B]図 11Bは、図 11Aの一例とは別の断面内について示す概略図の一例である  FIG. 11B is an example of a schematic diagram showing a cross section different from the example of FIG. 11A.
[図 12A]図 12Aは、ファイバアレイ光源の構成を示す斜視図である。 FIG. 12A is a perspective view showing a configuration of a fiber array light source.
[図 12B]図 12Bは、図 12Aの部分拡大図の一例である。 FIG. 12B is an example of a partially enlarged view of FIG. 12A.
[図 12C]図 12Cは、レーザ出射部における発光点の配列を示す平面図の一例である  [FIG. 12C] FIG. 12C is an example of a plan view showing an array of light emitting points in the laser emitting section.
[図 12D]図 12Dは、レーザ出射部における発光点の配列を示す平面図の一例である [FIG. 12D] FIG. 12D is an example of a plan view showing an array of light emitting points in the laser emitting section.
[図 12E]図 12Eは、ファイバアレイ光源のレーザ出射部における発光点の配列を示す 正面図の一例である。 [FIG. 12E] FIG. 12E is an example of a front view showing the arrangement of light emitting points in the laser emitting section of the fiber array light source.
[図 13]図 13は、マルチモード光ファイバの構成を示す図の一例である。  FIG. 13 is an example of a diagram illustrating a configuration of a multimode optical fiber.
[図 14]図 14は、合波レーザ光源の構成を示す平面図の一例である。  FIG. 14 is an example of a plan view showing a configuration of a combined laser light source.
[図 15]図 15は、レーザモジュールの構成を示す平面図の一例である。  FIG. 15 is an example of a plan view showing a configuration of a laser module.
[図 16]図 16は、図 15に示すレーザモジュールの構成を示す側面図の一例である。  FIG. 16 is an example of a side view showing the configuration of the laser module shown in FIG.
[図 17]図 17は、図 15に示すレーザモジュールの構成を示す部分側面図である。 発明を実施するための最良の形態  FIG. 17 is a partial side view showing the configuration of the laser module shown in FIG. 15. BEST MODE FOR CARRYING OUT THE INVENTION
(硬化促進剤） (Curing accelerator)
本発明の硬化促進剤は、外部刺激によりアミンを生成し、分子内にカルボキシノレ基 とアミド基とを 1対 1の比で有する構造の化合物である。  The curing accelerator of the present invention is a compound having a structure in which an amine is generated by an external stimulus and a carboxynole group and an amide group are in a ratio of 1: 1 in the molecule.
前記本発明の硬化促進剤は、例えば、酸無水物にアミンを反応させて合成すること ができるが、この合成手段に限定されるものではない。  The curing accelerator of the present invention can be synthesized, for example, by reacting an acid anhydride with an amine, but is not limited to this synthesis means.
本発明の硬化促進剤は、外部刺激によりアミンを生成することにより、該硬化促進 剤を添加した化合物を硬化させるための硬化促進剤や架橋剤としての機能を発現す る。そのため、樹脂の硬化促進剤又は熱架橋剤として好適に使用できる。 前記外部刺激としては、特に制限はなぐ 目的に応じて適宜選択することができる 力 80°C以上の加熱が好ましぐ 100°C以上の加熱がより好ましい。 The curing accelerator of the present invention expresses a function as a curing accelerator or a crosslinking agent for curing a compound to which the curing accelerator is added by generating an amine by external stimulation. Therefore, it can be suitably used as a resin curing accelerator or thermal crosslinking agent. The external stimulus is not particularly limited and can be appropriately selected according to the purpose. Heating at 80 ° C. or higher is preferable, and heating at 100 ° C. or higher is more preferable.
該加熱により、ァミンが生成され、優れた硬化促進効果や熱架橋効果が得られる。 前記本発明の硬化促進剤が、分子内にカルボキシル基とアミド基とを 1対 1の比で 有する構造の化合物であることは、 ^— NMRスペクトルを測定して同定することが できる。  By the heating, amine is generated, and an excellent curing acceleration effect and thermal crosslinking effect are obtained. It can be identified by measuring the ^ -NMR spectrum that the curing accelerator of the present invention is a compound having a structure having a carboxyl group and an amide group in a ratio of 1: 1.
前記硬化促進剤としては、下記一般式（1)、（2)、（3)、（4)、（5)及び (6)のいずれ かで表されるのが好ましい。  The curing accelerator is preferably represented by any one of the following general formulas (1), (2), (3), (4), (5) and (6).
[化 11]  [Chemical 11]
R  R
Ri R3 Ri R 3
HO- -N —般式 （ 1 )  HO- -N — General formula (1)
O 〇' R4 O ○ 'R 4
[化 12]  [Chemical 12]
—般式 （2 )—General formula (2)
Figure imgf000021_0001
Figure imgf000021_0001
[化 13]  [Chemical 13]
—般式 ( 3 )
Figure imgf000021_0002
—General formula (3)
Figure imgf000021_0002
[化 14]  [Chemical 14]
—般式 （4 )
Figure imgf000021_0003
—General formula (4)
Figure imgf000021_0003
[化 15] —般式 （5 )[Chemical 15] —General formula (5)
Figure imgf000022_0001
Figure imgf000022_0001
[化 16]  [Chemical 16]
—般式 （6 )—General formula (6)
Figure imgf000022_0002
Figure imgf000022_0002
ただし、前記一般式（1)、（2)、 （3)、（4)、（5)及び (6)中、 R^R18は、水素原子、 及び置換基のいずれかを表し、 Ai A6は、 2価の置換基を表し、 〜!^11は、単結合 、二重結合、及び 2価の置換基のいずれかを表す。 However, in said general formula (1), (2), (3), (4), (5) and (6), R ^ R 18 represents either a hydrogen atom or a substituent, and Ai A 6 represents a divalent substituent, and ~! ^ 11 represents one of a single bond, a double bond, and a divalent substituent.
前記一般式（1)〜（6)中、！^〜 6は、水素原子、無置換アルキル基、ァリール基' アルケニル基 .ヒドロキシル基、アルコキシ基 .シァノ基 'ノ、ロゲン原子で置換されてお り、酸素原子'硫黄原子'カルボニル基 'アミド基'ウレタン基 'ゥレア基、エステル基の 2価の基を有していてもよい置換基含有アルキル基、無置換ァリール基、アルキル基 •ァリール基 ·アルコキシ基 ·シァノ基 'ノヽロゲン原子で置換されてレ、るァリール基のレヽ ずれかを表す。 In the general formulas (1) to (6),! ^ ~ 6 are hydrogen atom, unsubstituted alkyl group, aryl group 'alkenyl group, hydroxyl group, alkoxy group, cyano group' no, substituted with rogen atom, oxygen atom 'sulfur atom' carbonyl group 'amide group 'Urethane group' Urea group, Substituent-containing alkyl group which may have divalent group such as ester group, unsubstituted aryl group, alkyl group • aryl group, alkoxy group, cyan group 'Norogen atom is substituted This indicates the level of the reel.
前記無置換アルキル基としては、分岐を有していてもよぐ二重結合、三重結合を 有していてもよぐ総炭素数 1〜30のものが好ましぐ：!〜 15が特に好ましい。  As the unsubstituted alkyl group, those having a total number of carbon atoms of 1 to 30 which may have a double bond or a triple bond which may have a branch are preferable:! To 15 are particularly preferable .
このようなアルキル基としては、メチル基、ェチル基、ェチニル基、プロピル基、イソ プロピル基、ブチル基、 s ブチル基、 t ブチル基、ブチリル基、シクロへキシル基、 シクロへキセニル基、などが挙げられる。  Examples of such an alkyl group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, an sbutyl group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group. Can be mentioned.
前記置換基含有アルキル基中のァリール置換基としては、二重結合、三重結合を 有していてもよぐ総炭素数 6〜30のものが好ましぐ 6〜： 15が特に好ましい。前記置 換基としては、例えば、フエニル基、ナフチル基、アントラセニル基、メトキシフエニル 基、クロロフヱニル基、などが挙げられる。置換基含有アルキル基中のアルケニル置 換基としては、総炭素数 2〜： 10が好まし 2〜6が特に好ましぐ例えば、ェチュル 基、プロぺニル基、プチリル基、などが挙げられる。 As the aryl substituent in the substituent-containing alkyl group, those having a total carbon number of 6 to 30 which may have a double bond or a triple bond are preferred, and 6 to 15 is particularly preferred. Examples of the substituent include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like. As the alkenyl substituent in the substituent-containing alkyl group, a total carbon number of 2 to 10 is preferable, and 2 to 6 is particularly preferable. Group, propenyl group, pentyl group, and the like.
前記置換基含有アルキル基中のアルコキシ置換基としては、分岐を有していてもよ ぐ総炭素数 1〜： 10のものが好ましぐ：!〜 5が特に好まし 例えば、メトキシ基、エト キシ基、プロピルォキシ基、 2 _メチルプロピルォキシ基、ブトキシ基、などが挙げら れる。  As the alkoxy substituent in the substituent-containing alkyl group, those having a total carbon number of 1 to 10 which may have a branch are preferable:! To 5 are particularly preferable. Examples thereof include a xy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.
このような置換基含有アルキル基としては、分岐を有していてもよぐ二重結合、三 重結合を有していてもよぐ総炭素数 2〜40のものが好まし 2〜25が特に好ましい 。このような置換されているアルキル基は、例えば、 2—ェチルへキシル基、クロロブ チル基、ベンジル基、 2—ェチュルプロピル基、フエニルェチル基、シァノプロピル基 、メトキシェチル基、などが挙げられる。  As such a substituent-containing alkyl group, those having a total number of carbon atoms of 2 to 40, which may have a double bond or a triple bond, which may have a branch, are preferred. Particularly preferred. Examples of such a substituted alkyl group include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethylpropyl group, phenylethyl group, cyanopropyl group, and methoxyethyl group.
前記無置換ァリール基としては、総炭素数 6〜30のものが好ましぐ 6〜20が特に 好ましい。このようなァリール基としては、例えば、フエニル基、ナフチル基、アントラセ ニル基、などが挙げられる。  As the unsubstituted aryl group, those having 6 to 30 carbon atoms are preferred, and 6 to 20 are particularly preferred. Examples of such aryl groups include phenyl, naphthyl, and anthracenyl groups.
置換基含有ァリール基中のアルキル置換基としては、分岐を有していてもよぐ二 重結合、三重結合を有していてもよぐ総炭素数 1〜20のものが好ましぐ：!〜 6が特 に好ましく、例えば、メチル基、ェチル基、ェチニル基、プロピル基、イソプロピル基、 ブチル基、 s ブチノレ基、 t ブチル基、ブチリル基、シクロへキシル基、シクロへキセ ニル基、などが挙げられる。前記置換基含有ァリール基中のァリール置換基としては 、総炭素数 6〜20のものが好ましぐ 6〜： 14が特に好ましぐ例えば、フエ二ル基、ナ フチル基、アントラセニル基、メトキシフエ二ル基、クロ口フエ二ル基、などが挙げられ る。前記置換基含有ァリール基中のアルコキシ置換基としては、分岐を有していても よ 総炭素数:!〜 10が好まし ：!〜 5が特に好ましぐ例えば、メトキシ基、エトキシ 基、プロピルォキシ基、 2 _メチルプロピルォキシ基、ブトキシ基、などが挙げられる。 このような置換されているァリール基としては、総炭素数 6〜40のものが好ましぐ 6 〜25力 S特に好ましく、例えば、ェチルフエニル、ビフエニル、ノユルフェニル、ォクチ ルフヱニル、フルオロフヱニル、メトキシフヱニル基、などが挙げられる。  The alkyl substituent in the substituent-containing aryl group is preferably one having a total of 1 to 20 carbon atoms which may have a double bond or a triple bond which may have a branch:! To 6 are particularly preferred, for example, methyl group, ethyl group, ethynyl group, propyl group, isopropyl group, butyl group, s butynole group, tbutyl group, butyryl group, cyclohexyl group, cyclohexenyl group, etc. Is mentioned. As the aryl substituent in the substituent-containing aryl group, those having a total carbon number of 6 to 20 are preferred, and 6 to 14 is particularly preferred. For example, a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenol Diyl group, black mouth phenyl group, and the like. The alkoxy substituent in the substituent-containing aryl group may have a branch. Total carbon number:! To 10 is preferable:! To 5 is particularly preferable. For example, methoxy group, ethoxy group, propyloxy Group, 2-methylpropyloxy group, butoxy group, and the like. Such substituted aryl groups are preferably those having a total carbon number of 6 to 40, particularly preferably 6 to 25 forces, such as ethenylphenyl, biphenyl, nourphenyl, octylphenyl, fluorophenyl, and methoxyphenyl groups. Can be mentioned.
また、前記 R1としては、 R2が結合して環を形成していてもよ 環内に二重結合、三 重結合を含んでいてもよぐ芳香環であってもよぐヘテロ環を形成していてもよぐ置 換されていてもよレ、。 4〜8員環が好まし 5〜6員環が特に好ましい。 In addition, the R 1 may be a heterocycle that may be an aromatic ring that may be bonded to R 2 to form a ring or may be a double bond or a triple bond in the ring. Can be formed It may be replaced. A 4- to 8-membered ring is preferred, and a 5- to 6-membered ring is particularly preferred.
また、前記 R1が結合している炭素と、前記 R2が結合している炭素間は単結合であ つてもょレヽし、二重結合であってもよい。 The carbon to which R 1 is bonded and the carbon to which R 2 is bonded may be a single bond or a double bond.
前記 R3としては、 R4が結合して環を形成していてもよぐ環内に二重結合、三重結 合を含んでいてもよぐ置換されていてもよレ、。 4〜8員環が好ましぐ 5〜6員環が特 に好ましい。 As R 3 , R 4 may be bonded to form a ring, or the ring may contain a double bond or triple bond, or may be substituted. A 4- to 8-membered ring is preferred. A 5- to 6-membered ring is particularly preferred.
前記 R5としては、 R6が結合して環を形成していてもよぐ環内に二重結合、三重結 合を含んでいてもよぐヘテロ環を形成していてもよぐ置換されていてもよい。 4〜8 員環が好ましぐ 5〜6員環が特に好ましい。 As R 5 , R 6 may be bonded to form a ring, or a double ring or a triple bond may be included in the ring, or a heterocyclic ring may be substituted. It may be. 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
また、前記 R5が結合している炭素と、前記 R6が結合している炭素間は単結合であ つてもよいし、二重結合であってもよい。 Further, the carbon to which R 5 is bonded and the carbon to which R 6 is bonded may be a single bond or a double bond.
前記 R8としては、 R9が結合して環を形成していてもよぐ環内に二重結合、三重結 合を含んでいてもよぐヘテロ環を形成していてもよぐ置換されていてもよい。 4〜8 員環が好ましぐ 5〜6員環が特に好ましい。 As R 8 , R 9 may be bonded to form a ring, or a double ring or triple bond may be included in the ring, or a hetero ring may be substituted. It may be. 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
前記 R7としては、 が結合して環を形成していてもよぐ環内に二重結合、三重結 合を含んでいてもよぐ置換されていてもよい。 4〜8員環が好ましぐ 5〜6員環が特 に好ましい。 R 7 may be bonded to form a ring or a ring may contain a double bond or a triple bond, or may be substituted. A 4- to 8-membered ring is preferred. A 5- to 6-membered ring is particularly preferred.
前記 R11としては、 R12が結合して環を形成していてもよぐ環内に二重結合、三重 結合を含んでいてもよぐ置換されていてもよレ、。 4〜8員環が好ましぐ 5〜6員環が 特に好ましい。 As R 11 , R 12 may be bonded to form a ring, or a ring may contain a double bond or a triple bond, or may be substituted. 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
前記 R13としては、 R14が結合して環を形成していてもよぐ環内に二重結合、三重 結合を含んでいてもよぐ置換されていてもよレ、。 4〜8員環が好ましぐ 5〜6員環が 特に好ましい。 As R 13 , R 14 may be bonded to form a ring, or a ring may contain a double bond or a triple bond, or may be substituted. 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
前記 R15としては、 R16が結合して環を形成していてもよぐ環内に二重結合、三重 結合を含んでいてもよぐ置換されていてもよレ、。 4〜8員環が好ましぐ 5〜6員環が 特に好ましい。 As R 15 , R 16 may be bonded to form a ring, and the ring may contain a double bond or a triple bond, or may be substituted. 4- to 8-membered rings are preferred. 5- to 6-membered rings are particularly preferred.
前記 R17としては、 R18が結合して環を形成していてもよぐ環内に二重結合、三重 結合を含んでいてもよぐ置換されていてもよい。 4〜8員環が好ましぐ 5〜6員環が 特に好ましい。 As R 17 , R 18 may be bonded to form a ring, or a ring may contain a double bond or a triple bond, or may be substituted. 4-8 member ring is preferred 5-6 member ring Particularly preferred.
前記一般式（1)、 （2)、（3)、 (4)、 (5)及び (6)中、 〜八6は、無置換 2価アルキ ル、ァリール基 .アルケニル基 .アルコキシ基 ·シァノ基 'ノヽロゲン原子で置換されてお り、酸素原子'硫黄原子'カルボニル基 'アミド基'ウレタン基'ウレァ基、エステル基の 2価の基を有していてもよい置換基含有 2価アルキル、無置換 2価ァリール、アルキ ル基 .ァリール基 .アルケニル基 .アルコキシ基 ·シァノ基 'ノヽロゲン原子で置換されて おり、酸素原子'硫黄原子'カルボニル基 'アミド基'ウレタン基'ウレァ基、エステル基 の 2価の基を有してレ、てもよレ、置換基含有 2価ァリールのレ、ずれかを表す。 Formula (1), (2), (3), (4), (5) and (6), - eight 6, unsubstituted divalent alkyl Le, Ariru group. Alkenyl. Alkoxy-Shiano Substituent-containing divalent alkyl which may be substituted with the group 'Norogen atom' and may have a divalent group of oxygen atom 'sulfur atom' carbonyl group 'amide group' urethane group 'urea group, ester group An unsubstituted divalent aryl, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, a cyano group, which is substituted with a norogen atom, an oxygen atom, a sulfur atom, a carbonyl group, an amido group, a urethane group, a urea group, It represents an ester group having a divalent group, or may represent a divalent aryl containing a substituent.
前記無置換 2価アルキル基としては、分岐を有していてもよぐ二重結合、三重結合 を有していてもよぐ総炭素数 1〜30のものが好ましぐ：!〜 15が特に好ましい。この ようなアルキル基としては、メチノレ基、ェチル基、ェチニル基、プロピル基、イソプロピ ル基、ブチル基、 s ブチノレ基、 t ブチル基、ブチリル基、シクロへキシル基、シクロ へキセニル基、などが挙げられる。  The unsubstituted divalent alkyl group is preferably one having a total of 1 to 30 carbon atoms which may have a double bond or a triple bond which may have a branch:! Particularly preferred. Examples of such an alkyl group include a methinole group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, an sbutynole group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group. Can be mentioned.
前記置換基含有 2価アルキル基中のァリール置換基としては、二重結合、三重結 合を有していてもよぐ総炭素数 6〜30のものが好ましぐ 6〜： 15が特に好ましぐ前 記置換基としては、例えば、フエニル基、ナフチル基、アントラセニル基、メトキシフエ ニル基、クロロフヱニル基、などが挙げられる。前記置換基含有 2価アルキル基中の アルケニル置換基としては、総炭素数 2〜： 10のものが好まし 2〜6が特に好ましく 、例えば、ェチュル基、プロぺニル基、プチリル基、などが挙げられる。前記置換基 含有 2価アルキル基中のアルコキシ置換基としては、分岐を有していてもよぐ総炭 素数 1〜： 10のものが好ましぐ：!〜 5が特に好ましぐ例えば、メトキシ基、エトキシ基、 プロピルォキシ基、 2 _メチルプロピルォキシ基、ブトキシ基、などが挙げられる。 このような置換基含有 2価アルキル基としては、分岐を有していてもよぐ二重結合、 三重結合を有していてもよぐ総炭素数 2〜40のものが好まし 2〜25が特に好ま しレ、。このような置換基含有 2価アルキル基としては、例えば、 2 _ェチルへキシル基 、クロロブチル基、ベンジル基、 2—ェチュルプロピル基、フエニルェチル基、シァノ プロピル基、メトキシェチル基、などが挙げられる。  As the aryl substituent in the substituent-containing divalent alkyl group, those having a total carbon number of 6 to 30 which may have double bonds or triple bonds are preferred, and 6 to 15 is particularly preferred. Further, examples of the substituent include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like. As the alkenyl substituent in the substituent-containing divalent alkyl group, those having a total carbon number of 2 to 10 are preferred, and 2 to 6 are particularly preferred. Examples thereof include an ethur group, a propenyl group, and a petityl group. Can be mentioned. As the alkoxy substituent in the substituent-containing divalent alkyl group, those having 1 to 10 total carbon atoms which may have a branch are preferred:! To 5 are particularly preferred. For example, methoxy Group, ethoxy group, propyloxy group, 2_methylpropyloxy group, butoxy group, and the like. As such a substituent-containing divalent alkyl group, those having a total number of carbon atoms of 2 to 40, which may have a double bond or a triple bond, may be preferred. Is particularly preferred. Examples of such a substituent-containing divalent alkyl group include a 2-ethylhexyl group, a chlorobutyl group, a benzyl group, a 2-ethylpropyl group, a phenylethyl group, a cyanopropyl group, and a methoxyethyl group.
無置換 2価ァリール基としては、総炭素数 6〜30のものが好ましぐ 6〜20が特に好 ましい。このようなァリール基としては、例えば、フエニル基、ナフチル基、アントラセニ ル基、などが挙げられる。 As the unsubstituted divalent aryl group, those having a total carbon number of 6 to 30 are preferred, and 6 to 20 is particularly preferred. Good. Examples of such aryl groups include a phenyl group, a naphthyl group, and an anthracenyl group.
前記置換基含有 2価ァリール基中のアルキル置換基としては、分岐を有していても よ 二重結合、三重結合を有していてもよぐ総炭素数 1〜20のものが好ましぐ 1 〜6が特に好ましぐ例えば、メチル基、ェチル基、ェチュル基、プロピル基、イソプロ ピル基、ブチル基、 s _ブチル基、 t _ブチル基、ブチリル基、シクロへキシル基、シク 口へキセニル基、などが挙げられる。前記置換基含有 2価ァリール基中のァリール置 換基としては、総炭素数 6〜20のものが好ましぐ 6〜： 14が特に好ましぐ例えば、フ ェニル基、ナフチル基、アントラセニル基、メトキシフエ二ル基、クロ口フエニル基、など 力 S挙げられる。前記置換基含有 2価ァリール基中のアルコキシ置換基としては、分岐 を有していてもよぐ総炭素数 1〜： 10のものが好ましぐ：!〜 5が特に好ましぐ例えば 、メトキシ基、エトキシ基、プロピルォキシ基、 2—メチルプロピルォキシ基、ブトキシ基 、などが挙げられる。  As the alkyl substituent in the substituent-containing divalent aryl group, one having a total carbon number of 1 to 20 which may have a branch, a double bond or a triple bond is preferable. 1 to 6 are particularly preferred, for example, methyl group, ethyl group, ethyl group, propyl group, isopropyl group, butyl group, s_butyl group, t_butyl group, butyryl group, cyclohexyl group, and cyclohexane A xenyl group, and the like. As the aryl substituent in the substituent-containing divalent aryl group, those having a total carbon number of 6 to 20 are preferable, and 6 to 14 is particularly preferable. For example, a phenyl group, a naphthyl group, an anthracenyl group, Methoxyphenyl group, black phenyl group, etc. As the alkoxy substituent in the substituent-containing divalent aryl group, those having a total carbon number of 1 to 10 which may have a branch are preferable:! To 5 are particularly preferable. For example, methoxy Group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
このような置換基含有 2価ァリール基としては、総炭素数 6〜40のものが好ましぐ 6 〜25力 S特に好ましく、例えば、ェチルフエニル、ビフエニル、ノニルフエニル、ォクチ ルフエニル、フルオロフヱニル、メトキシフエ二ル基、などが挙げられる。  As such a substituent-containing divalent aryl group, those having a total carbon number of 6 to 40 are preferred. 6 to 25 forces S are particularly preferred. For example, ethenylphenyl, biphenyl, nonylphenyl, octylphenyl, fluorophenyl, methoxyphenyl group. , Etc.
前記！^〜 11としては、単結合、二重結合、無置換 2価アルキル、ァリール基.アル ケニル基 ·アルコキシ基 .シァノ基 .ハロゲン原子で置換されており、酸素原子 ·硫黄 原子 ·カルボニル基 ·アミド基 ·ウレタン基 ·ウレァ基、エステル基の 2価の基を有してレヽ てもよい置換基含有 2価アルキル、無置換 2価ァリール、アルキル基 'ァリール基 'ァ ルケニル基 ·アルコキシ基 .シァノ基 .ハロゲン原子で置換されており、酸素原子 ·硫 黄原子 ·カルボニル基 ·アミド基 ·ウレタン基 ·ウレァ基、エステル基の 2価の基を有し てレ、てもよレ、置換基含有 2価ァリールのレ、ずれかを表す。 Said! ^ ~ 11 are single bond, double bond, unsubstituted divalent alkyl, aryl group, alkenyl group, alkoxy group, cyan group, substituted with halogen atom, oxygen atom, sulfur atom, carbonyl group, amide Substituent-containing divalent alkyl, unsubstituted divalent aryl, alkyl group 'aryl group', alkenyl group, alkoxy group, which may have a divalent group of a group, urethane group, urea group or ester group. Substituted by halogen atom, it has a divalent group of oxygen atom, sulfur atom, carbonyl group, amide group, urethane group, urea group, ester group, or may contain a substituent. Indicates whether the bivalent reel is misaligned.
前記無置換 2価アルキル基としては、分岐を有していてもよ 二重結合、三重結合 を有していてもよぐ総炭素数 1〜： 15のものが好まし 1〜： 10が特に好ましレ、。この ようなアルキル基としては、メチノレ基、ェチル基、ェチュル基、プロピル基、イソプロピ ル基、ブチル基、 s—ブチノレ基、 t _ブチル基、ブチリル基、シクロへキシル基、シクロ へキセニル基、などが挙げられる。 置換基含有 2価アルキル基中のァリール置換基としては、二重結合、三重結合を 有していてもよぐ総炭素数 6〜30のものが好ましぐ 6〜： 15が特に好ましぐ置換基 としては、例えば、フエニル基、ナフチル基、アントラセニル基、メトキシフエ二ル基、ク ロロフヱニル基、などが挙げられる。前記置換基含有 2価アルキル基中のアルケニル 置換基としては、総炭素数 2〜： 10のものが好ましぐ 2〜6が特に好ましぐ例えば、ェ チュル基、プロぺニル基、プチリル基、などが挙げられる。前記置換基含有 2価アル キル基中のアルコキシ置換基としては、分岐を有していてもよぐ総炭素数:!〜 10の ものが好ましく、：!〜 5が特に好ましぐ例えば、メトキシ基、エトキシ基、プロピルォキ シ基、 2—メチルプロピルォキシ基、ブトキシ基、などが挙げられる。 As the unsubstituted divalent alkyl group, those having a total number of carbon atoms of 1 to 15 which may have a branch or may have a double bond or a triple bond are preferred. I like it. Examples of such an alkyl group include a methinole group, an ethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butynole group, a t_butyl group, a butyryl group, a cyclohexyl group, a cyclohexenyl group, Etc. As the aryl substituent in the divalent alkyl group containing a substituent, those having a total carbon number of 6 to 30 which may have a double bond or a triple bond are preferred, and 6 to 15 is particularly preferred. Examples of the substituent include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like. As the alkenyl substituent in the above-mentioned divalent alkyl group containing a substituent, those having a total carbon number of 2 to 10 are preferable, and 2 to 6 are particularly preferable. For example, an ethyl group, a propenyl group, and a pentyl group. , Etc. The alkoxy substituent in the substituent-containing divalent alkyl group preferably has a total number of carbon atoms that may be branched:! To 10 and is particularly preferably: to 5; for example, methoxy Group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
このような置換基含有 2価アルキル基としては、分岐を有していてもよぐ二重結合、 三重結合を有していてもよぐ総炭素数 2〜40のものが好ましぐ 2〜25が特に好ま しい。このような置換基含有 2価アルキル基としては、例えば、 2—ェチルへキシル基 、クロロブチル基、ベンジル基、 2—ェチニルプロピル基、フエニルェチル基、シァノ プロピル基、メトキシェチル基、などが挙げられる。  As such a substituent-containing divalent alkyl group, a double bond which may have a branch or a group having 2 to 40 total carbon atoms which may have a triple bond is preferable. 25 is particularly preferred. Examples of such a substituent-containing divalent alkyl group include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethynylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group, and the like.
無置換 2価ァリール基としては、総炭素数 6〜30のものが好ましぐ 6〜20が特に好 ましい。このようなァリール基としては、例えば、フエニル基、ナフチル基、アントラセニ ル基、などが挙げられる。  As the unsubstituted divalent aryl group, those having a total carbon number of 6 to 30 are preferable, and 6 to 20 is particularly preferable. Examples of such aryl groups include a phenyl group, a naphthyl group, and an anthracenyl group.
置換基含有 2価ァリール基中のアルキル置換基としては、分岐を有していてもよぐ 二重結合、三重結合を有していてもよぐ総炭素数 1〜20のものが好ましぐ：!〜 6が 特に好ましぐ例えば、メチル基、ェチル基、ェチュル基、プロピル基、イソプロピノレ 基、ブチル基、 s—ブチノレ基、 t _ブチル基、ブチリル基、シクロへキシル基、シクロへ キセニル基、などが挙げられる。前記置換基含有 2価ァリール基中のァリール置換基 としては、総炭素数 6〜20のものが好ましぐ 6〜： 14が特に好ましぐ例えば、フエ二 ル基、ナフチル基、アントラセニル基、メトキシフヱニル基、クロロフヱニル基、などが 挙げられる。前記置換基含有 2価ァリール基中のアルコキシ置換基としては、分岐を 有していてもよぐ総炭素数 1〜： 10のものが好ましぐ：!〜 5が特に好ましぐ例えば、 メトキシ基、エトキシ基、プロピルォキシ基、 2 _メチルプロピルォキシ基、ブトキシ基、 などが挙げられる。 このような置換基含有 2価ァリール基としては、総炭素数 6〜40のものが好ましぐ 6 〜25力 S特に好ましく、例えば、ェチルフエニル、ビフエニル、ノユルフェニル、ォクチ ルフヱニル、フルオロフヱニル、メトキシフヱニル基、などが挙げられる。 As the alkyl substituent in the divalent aryl group containing a substituent, one having a total of 1 to 20 carbon atoms which may have a double bond or a triple bond is preferable. : ~ 6 are particularly preferred, for example, methyl group, ethyl group, ethyl group, propyl group, isopropylinole group, butyl group, s-butynole group, t-butyl group, butyryl group, cyclohexyl group, cyclohexyl A xenyl group, and the like. As the aryl substituent in the substituent-containing divalent aryl group, those having a total carbon number of 6 to 20 are preferable, and 6 to 14 is particularly preferable. For example, a phenyl group, a naphthyl group, an anthracenyl group, Examples thereof include a methoxyphenyl group and a chlorophenyl group. As the alkoxy substituent in the substituent-containing divalent aryl group, one having a total carbon number of 1 to 10 which may have a branch is preferable:! To 5 is particularly preferable. For example, methoxy Group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like. As such a substituent-containing divalent aryl group, those having a total carbon number of 6 to 40 are preferred. 6 to 25 forces S are particularly preferred, for example, ethenylphenyl, biphenyl, nourphenyl, octylphenyl, fluorophenyl, methoxyphenyl group, etc. Is mentioned.
このような 〜 11の中でも、単結合、二重結合、無置換 2価アルキル基、置換基含 有 2価アルキル基が好まし 単結合、二重結合が特に好ましい。 Among these to 11 , a single bond, a double bond, an unsubstituted divalent alkyl group, and a substituent-containing divalent alkyl group are preferable, and a single bond and a double bond are particularly preferable.
前記一般式（1)〜（6)で表される化合物の例としては、下記構造式（1)〜（33)で 表される化合物などが挙げられるが、これらの化合物に限定されるものではない。  Examples of the compounds represented by the general formulas (1) to (6) include compounds represented by the following structural formulas (1) to (33), but are not limited to these compounds. Absent.
[化 17] [Chemical 17]
Figure imgf000029_0001
Figure imgf000029_0001
構造式 （1 ) 構造式 （2) 構造式 （3) 構造式 （4)  Structural formula (1) Structural formula (2) Structural formula (3) Structural formula (4)
HOHO
Figure imgf000029_0002
L r\
Figure imgf000029_0002
L r \
O O O O O O O O
Figure imgf000029_0003
Figure imgf000029_0003
構造式 （9) 構造式 （ 1 0) 構造式 （1 1 ) 構造式 （1 2)  Structural formula (9) Structural formula (1 0) Structural formula (1 1) Structural formula (1 2)
Figure imgf000029_0004
Figure imgf000029_0004
構造式 （1 3) 構造式 （1 4) 構造式 （ 1 5) 構造式 （ 1 6) Structural formula (1 3) Structural formula (1 4) Structural formula (1 5) Structural formula (1 6)
HO N no -N HOィ NHO N no -N HO
D 0· ' π n o o O O 、 構造式 （1 7) 構造式 （1 8) 構造式 （1 9) 構造式 （20) D 0 · 'π n o o O O, structural formula (1 7) structural formula (1 8) structural formula (1 9) structural formula (20)
HO VN HOィ N
Figure imgf000029_0005
0 0 、 o o 構造式 （2 1 ) 構造式 （22) 構造式 （23) 構造式 （24)HO VN HO
Figure imgf000029_0005
0 0, oo Structural formula (2 1) Structural formula (22) Structural formula (23) Structural formula (24)
[化 18]
Figure imgf000030_0001
[Chemical 18]
Figure imgf000030_0001
構造式（25) 構造式（26) 構造式（27 ) 構造式（28)  Structural formula (25) Structural formula (26) Structural formula (27) Structural formula (28)
Figure imgf000030_0002
Figure imgf000030_0002
[0029] 本発明の硬化促進剤は、低温又は常温では反応を生じることがなぐ該硬化促進 剤及び該硬化促進剤を使用した化合物の優れた保存安定性が図れるとともに、加熱 処理時には、該熱処理温度で硬化促進剤兼熱硬化剤としての速やかな反応を示し て、表面硬度、及び耐アルカリ性などに優れる硬化物が得られる。このため、プリント 配線板（多層配線基板、ビルドアップ配線基板等）の保護膜、層間絶縁膜、及びソル ダーレジストパターン、カラーフィルタや柱材、リブ材、スぺーサ一、隔壁などのディス プレイ用部材、ホログラム、マイクロマシン、プルーフ、接着剤などの永久パターン形 成用として広く用いることができ、特に本発明の感光性組成物、感光性フィルム、並 びに永久パターン及びその形成方法に好適に用いることができる。  [0029] The curing accelerator of the present invention can achieve excellent storage stability of the curing accelerator and a compound using the curing accelerator that do not cause a reaction at a low temperature or normal temperature, and the heat treatment during the heat treatment. A cured product excellent in surface hardness, alkali resistance, etc. is obtained by showing a rapid reaction as a curing accelerator / thermosetting agent at a temperature. For this reason, displays such as protective films on printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be widely used for forming permanent patterns such as members, holograms, micromachines, proofs, adhesives, etc., and particularly suitable for the photosensitive composition, photosensitive film, permanent pattern and method for forming the same of the present invention. be able to.
[0030] (感光性組成物）  [0030] (Photosensitive composition)
本発明の感光性組成物は、 (A) 1分子中に 1個以上のカルボキシノレ基及びエステ ル基のいずれかを有する重合体と、（B)重合性化合物と、（C)光重合開始剤と、 (D) 前記本発明の硬化促進剤とを少なくとも含み、好ましくは (E)熱架橋剤を含み、更に 、必要に応じて、着色顔料、体質顔料、熱重合禁止剤、及び界面活性剤などのその 他の成分を含んでなる。  The photosensitive composition of the present invention comprises (A) a polymer having one or more carboxynole groups and ester groups in one molecule, (B) a polymerizable compound, and (C) photopolymerization initiation. And (D) the curing accelerator of the present invention, preferably (E) a thermal crosslinking agent, and further, if necessary, a coloring pigment, an extender pigment, a thermal polymerization inhibitor, and a surface active agent Other ingredients such as an agent.
[0031] 〔(A)バインダー（重合体)〕  [0031] [(A) Binder (Polymer)]
前記バインダーとしては、アルカリ性水溶液に対して膨潤性を示す化合物が好まし ぐアルカリ性水溶液に対して可溶性である化合物がより好ましレ、。 アルカリ性水溶液に対して膨潤性又は溶解性を示すバインダーとしては、例えば、 酸性基を有するものが好適に挙げられ、具体的には、エポキシ化合物にエチレン性 不飽和二重結合と酸性基とを導入した化合物（エポキシアタリレートイ匕合物）、側鎖に (メタ）アタリロイル基、及び酸性基を有するビュル共重合体、エポキシアタリレートイ匕 合物と、側鎖に (メタ）アタリロイル基、及び酸性基を有するビニル共重合体との混合 物、マレアミド酸系共重合体、などが好ましい。 The binder is preferably a compound that is soluble in an alkaline aqueous solution, and is preferably a compound that exhibits swelling properties in an alkaline aqueous solution. As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound. Compound (epoxy atalytoyl compound), a bur copolymer having a (meth) attalyloyl group and an acidic group in the side chain, an epoxy atalytoyl compound, and a (meth) attalyloyl group in the side chain, and A mixture with a vinyl copolymer having an acidic group, a maleamic acid copolymer, and the like are preferable.
前記酸性基としては、特に制限はなぐ 目的に応じて適宜選択することができ、例え ば、カルボキシル基、スルホン酸基、リン酸基、などが挙げられ、これらの中でも、原 料の入手性などの観点から、カルボキシル基が好ましく挙げられる。  The acidic group is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From this point of view, a carboxyl group is preferred.
[0032] くエポキシアタリレート化合物 > [0032] Kupo Epoxy Atarylate Compound>
前記エポキシ化合物にエチレン性不飽和二重結合と酸性基とを導入した化合物（ エポキシアタリレー H匕合物）としては、特に制限は無ぐ 目的に応じて適宜選択する ことができ、例えば、多官能エポキシ化合物とカルボキシル基含有モノマーとを反応 させ、更に多塩基酸無水物を付加させる方法などで得られる。  The compound in which an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound (epoxy atelier H compound) is not particularly limited and may be appropriately selected depending on the purpose. It can be obtained by reacting a functional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.
[0033] 前記多官能エポキシ化合物としては、例えば、ビキシレノール型もしくはビスフエノ ール型エポキシ樹脂（「YX4000；ジャパンエポキシレジン社製」等）又はこれらの混 合物、イソシァヌレート骨格等を有する複素環式エポキシ樹脂ひ TEPIC ;日産化学 工業社製」、「ァラルダイト PT810 ;チノく'スペシャルティ'ケミカルズ社製」等）、ビスフ ェノール Α型エポキシ樹脂、ビスフエノール F型エポキシ樹脂、水添ビスフエノール A 型エポキシ樹脂、ビスフエノール S型エポキシ樹脂、フエノールノボラック型エポキシ 樹脂、タレゾ一ルノボラック型エポキシ樹脂、ハロゲン化フエノールノボラック型ェポキ シ樹脂、グリシジルアミン型エポキシ樹脂（例えばテトラグリシジルジアミノジフヱニル メタン等）、ヒダントイン型エポキシ樹脂、脂環式エポキシ樹脂、トリヒドロキシフヱニル メタン型エポキシ樹脂、ビスフエノール Aノボラック型エポキシ樹脂、テトラフエ二ロー ルェタン型エポキシ樹脂、グリシジルフタレート樹脂、テトラグリシジルキシレノィルェ タン樹脂、ナフタレン基含有エポキシ樹脂（「ESN_ 190， ESN— 360 ;新日鉄化学 社製」、「HP— 4032， EXA-4750, EXA— 4700；大日本インキイ匕学工業社製」 等）、ジシクロペンタジェン骨格を有するエポキシ樹脂ひ HP— 7200, HP- 7200H ；大日本インキ化学工業社製」等）；フエノーノレ、 o_クレゾール、ナフトール等のフエノ ール化合物と、フエノール性水酸基を有する芳香族アルデヒド (例えば、 p ヒドロキ シベンズアルデヒド）との縮合反応により得られるポリフエノールイヒ合物とェピクロルヒ ドリンとの反応物；フエノール化合物とジビュルベンゼンゃジシクロペンタジェン等の ジォレフイン化合物との付加反応によって得られるポリフエノール化合物と、ェピクロ ノレヒドリンとの反応物； 4 -ビュルシクロへキセン一 1—オキサイドの開環重合物を過 酢酸等でエポキシ化したもの；トリグリシジルイソシァヌレート等の複素環を有するェポ キシ榭脂；グリシジルメタアタリレート共重合系エポキシ樹脂（「CP— 50S, CP— 50 M ;日本油脂社製」等）、シクロへキシルマレイミドとグリシジルメタアタリレートとの共 重合エポキシ樹脂などが挙げられる。これらは 1種単独で使用してもよいし、 2種以上 を併用してもよい。 [0033] Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin ("YX4000; manufactured by Japan Epoxy Resin Co., Ltd.") or a mixture thereof, a heterocyclic group having an isocyanurate skeleton, and the like. Epoxy resin TEPIC: Nissan Chemical Industry Co., Ltd., "Araldite PT810: Chinoku 'Specialty' Chemicals Co., Ltd."), Bisphenol Α type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin Bisphenol S type epoxy resin, phenol novolak type epoxy resin, tale novolol type epoxy resin, halogenated phenol novolak type epoxy resin, glycidylamine type epoxy resin (eg tetraglycidyl diaminodiphenyl methane, etc.), hydantoin type epoxy resin, Cyclic epoxy resin, trihydroxyphenyl methane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylylene ethane resin, naphthalene group containing epoxy resin ( "ESN_190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), epoxy resin having a dicyclopentagen skeleton HP — 7200, HP-7200H Obtained by Dainippon Ink Chemical Co., Ltd.); obtained by condensation reaction of phenolic compounds such as phenol, o_cresol, naphthol and aromatic aldehydes having phenolic hydroxyl groups (eg, p-hydroxybenzaldehyde). Reaction product of polyphenolic compound and epichlorohydrin; reaction product of polyphenol compound obtained by addition reaction of phenolic compound and diolefin compound such as dibutenebenzene dicyclopentagen and epichlorochlorohydrin; 4-Buylcyclo Hexene mono 1-oxide ring-opened polymer epoxidized with peracetic acid, etc .; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl meta-atalelate copolymer epoxy resin (“CP — 50S, CP— 50 M; manufactured by NOF Corporation, etc.), cyclohex Such as a copolymer epoxy resins of maleimide and glycidyl methacrylate Atari rate and the like. These may be used alone or in combination of two or more.
[0034] また、前記カルボキシル基含有モノマーの例としては、例えば（メタ）アクリル酸、ビ ニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、ィタコン酸 、クロトン酸、桂皮酸、ソルビン酸、 α—シァノ桂皮酸、アクリル酸ダイマー；この他、 2 ーヒドロキシェチル (メタ）アタリレート等の水酸基を有する単量体と無水マレイン酸、 無水フタル酸、シクロへキサンジカルボン酸無水物等の環状酸無水物との付加反応 物；ノ、ロゲン含有カルボン酸化合物との反応生成物、 ω カルボキシーポリ力プロラ タトンモノ (メタ）アタリレート、などが挙げられる。さらに、市販品としては、東亜合成化 学工業（株）製のァロニックス Μ— 5300、 Μ— 5400、 Μ— 5500および Μ— 5600、 新中村化学工業 (株)製の ΝΚエステル CB_ 1および CBX_ 1、共栄社油脂化学ェ 業 (株)製の HOA—MPおよび H〇A_MS、大阪有機化学工業 (株)製のビスコート # 2100などを用いることができる。これらは 1種単独で使用してもよいし、 2種以上を 併用してもよい。 [0034] Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and sorbic acid. Α-cyancinnamic acid, acrylic acid dimer; in addition to this, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, etc. And addition products with cyclic acid anhydrides; reaction products with rhogen-containing carboxylic acid compounds, ω- carboxy-polypropylene mono (meth) acrylate, and the like. In addition, commercially available products include ALONIX Μ-5300, Μ—5400, Μ—5500 and Μ—5600 manufactured by Toa Gosei Kagaku Kogyo Co., Ltd., ΝΚEster CB_1 and CBX_1 manufactured by Shin-Nakamura Chemical Co., Ltd. In addition, HOA-MP and H0_A_MS manufactured by Kyoeisha Yushi Chemical Co., Ltd., and Biscoat # 2100 manufactured by Osaka Organic Chemical Industry Co., Ltd. can be used. These may be used alone or in combination of two or more.
[0035] また、前記多塩基酸無水物としては、例えば、無水コハク酸、無水メチルコハク酸、 無水 2, 3_ジメチルコハク酸、無水 2， 2_ジメチルコハク酸、無水ェチルコハク酸、無 水ドデセニルコハク酸、無水ノネニルコハク酸、無水マレイン酸、無水メチルマレイン 酸、無水 2， 3—ジメチルマレイン酸、無水 2_クロロマレイン酸、無水 2， 3—ジクロ口 マレイン酸、無水ブロモマレイン酸、無水ィタコン酸、無水シトラコン酸、無水シスアコ ット酸、無水フタル酸、テトラヒドロ無水フタル酸、テトラクロ口無水フタル酸、テトラブロ モ無水フタル酸、へキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチル へキサヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、メチノレエンドメチ レンテトラヒドロ無水フタル酸、無水クロレンド酸および 5_ (2, 5—ジォキソテトラヒド 口フリル）一 3—メチノレ _ 3—シクロへキセン一 1 , 2—ジカルボン酸無水物などの二塩 基酸無水物、無水トリメリット酸、無水ピロメリット酸、 3, 3 ' , 4， 4' _ベンゾフヱノンテト ラカルボン酸等の多塩基酸無水物なども使用できる。これらは 1種単独で使用しても よいし、 2種以上を併用してもよい。 [0035] The polybasic acid anhydrides include, for example, succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, and anhydrous dodecenyl succinic acid. Nonenyl succinic anhydride, maleic anhydride, methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloro maleic acid, bromomaleic anhydride, itaconic anhydride, anhydrous Citraconic acid, anhydrous cis-aco Titanic acid, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride , Methinoredomethylenetetrahydrophthalic anhydride, chlorendic anhydride and 5_ (2,5-dioxotetrahydryl) furan) -1-methinole_3-cyclohexene mono-1,2-dicarboxylic anhydride, etc. Dibasic acid anhydrides, trimellitic anhydride, pyromellitic anhydride, polybasic acid anhydrides such as 3,3 ′, 4,4′_benzophenone tetracarboxylic acid, and the like can also be used. These may be used alone or in combination of two or more.
それぞれを順次反応させて、エポキシアタリレートを得る力 それらを反応させる比 率は、多官能エポキシィヒ合物のエポキシ基 1当量に対して、カルボキシル基含有モ ノマーの力ノレボキシノレ基 0. 8〜： 1. 2当量、好ましく ίま、 0. 9〜： 1. 1当量であり、多塩 基酸無水物 0. 1〜： 1. 0当量、好ましくは、 0. 3〜： 1. 0当量である。  The ability to react each in turn to obtain epoxy acrylates The ratio of reacting them is the ratio of the carboxyl group-containing monomer power to the carboxyoxy group 0.8 to 1 with respect to 1 equivalent of the epoxy group of the polyfunctional epoxy compound. 2 equivalents, preferably ί, 0.9 to: 1.1 equivalents, polybasic acid anhydrides 0.1 to 1.0 equivalents, preferably 0.3 to 1.0 equivalents .
[0036] また、特開平 5— 70528号公報記載のフルオレン骨格を有するエポキシアタリレー ト（カルボキシノレ基を有してはいない化合物）に前記多塩基酸無水物を付加させて得 られる化合物なども本発明のエポキシアタリレートとして利用できる。  [0036] Further, compounds obtained by adding the polybasic acid anhydride to an epoxy atalate having a fluorene skeleton (compound having no carboxynore group) described in JP-A-5-70528 are also included. It can be used as the epoxy acrylate of the present invention.
[0037] 前記エポキシ化合物にエチレン性不飽和二重結合と酸性基とを導入した化合物の 中でも、下記構造式 (III)及び (IV)で表されるエポキシアタリレートイ匕合物が好ましレ、  [0037] Among the compounds obtained by introducing an ethylenically unsaturated double bond and an acidic group into the epoxy compound, epoxy atalytotoy compounds represented by the following structural formulas (III) and (IV) are preferred. ,
[化 19]
Figure imgf000033_0001
構造式 （I I I ) [Chemical 19]
Figure imgf000033_0001
Structural formula (III)
ただし、前記構造式 (III)中、 Xは水素原子、及び少なくとも酸性基を含む置換基の いずれかを表し、 Yはメチレン基、イソプロピリデン基、及びスルホニル基のいずれか を表し、 nは、 1〜20の整数を表す。  However, in the structural formula (III), X represents any one of a hydrogen atom and a substituent containing at least an acidic group, Y represents any one of a methylene group, an isopropylidene group, and a sulfonyl group, and n represents Represents an integer of 1-20.
[0038] [化 20] = CH2 構造式 （I V)
Figure imgf000034_0001
[0038] [Chemical 20] = CH 2 structural formula (IV)
Figure imgf000034_0001
ただし、前記構造式 (IV)中、 nは、：!〜 20の整数を表す。  However, in said structural formula (IV), n represents the integer of:!-20.
また、前記構造式 (III)で表されるエポキシアタリレートイ匕合物としては、具体的には 、下記構造式 (V)で表されるビスフエノール F型エポキシアタリレートイ匕合物、及び下 記構造式 (VI)で表されるビスフエノール A型エポキシアタリレートイ匕合物がより好まし レ、。  In addition, as the epoxy ata relay toy compound represented by the structural formula (III), specifically, a bisphenol F type epoxy ata relay toy compound represented by the following structural formula (V), and A bisphenol A type epoxy atelar toy compound represented by the following structural formula (VI) is more preferred.
[化 21]  [Chemical 21]
Figure imgf000034_0002
構造式 （V )
Figure imgf000034_0002
Structural formula (V)
[化 22] [Chemical 22]
Figure imgf000034_0003
Figure imgf000034_0003
構造式 (VI ) 前記エポキシアタリレート化合物の分子量としては、 1， 000〜100, 000力好ましく 、 2, 000-50, 000がより好ましレ、。該分子量が 1， 000未満であると、感光層表面 のタック性が強くなることがあり、後述する感光層の硬化後において、膜質が脆くなる 、あるいは、表面硬度が劣化することがあり、 100， 000を超えると、現像性が劣化す ること力ある。また樹脂の合成も困難となる。 Structural Formula (VI) The molecular weight of the epoxy acrylate compound is preferably 1,000-100,000, more preferably 2,000-50,000. When the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may deteriorate. , Over 000, developability deteriorates There is power. Also, synthesis of the resin becomes difficult.
[0041] <側鎖に (メタ）アタリロイル基、及び酸性基を有するビュル共重合体 > [0041] <Bul copolymer having a (meth) attalyloyl group and an acidic group in the side chain>
前記側鎖に (メタ）アタリロイル基、及び酸性基を有するビニル共重合体としては、例 えば（1)酸性基を有するビニルモノマー、 （2)必要に応じて後述する高分子反応に 利用可能な官能基を有するビュルモノマー、及び（3)必要に応じてその他の共重合 可能なビニルモノマーのビニル (共)重合で得られた（共)重合体を合成し、更に (4) 該 (共)重合体中の酸性基、又は高分子反応に利用可能な官能基の少なくとも 1種に 対して反応性を有する官能基と (メタ）アタリロイル基を有する化合物とを高分子反応 させることによって得られる。  Examples of the vinyl copolymer having a (meth) atalyloyl group and an acidic group in the side chain include (1) a vinyl monomer having an acidic group, and (2) can be used for a polymer reaction described later if necessary. (4) The (co) polymer obtained by vinyl (co) polymerization of a butyl monomer having a functional group and (3) other copolymerizable vinyl monomer if necessary, and (4) the (co) polymer It is obtained by polymer-reacting a functional group having reactivity with at least one of an acidic group in a polymer or a functional group that can be used for polymer reaction and a compound having a (meth) atalyloyl group.
前記（1)酸性基を有するビュルモノマーの酸性基としては、特に制限はなぐ 目的 に応じて適宜選択することができ、例えば、カルボキシノレ基、スルホン酸基、リン酸基 などが挙げられ、これらの中でもカルボキシル基が好ましい。カルボキシル基を有す るビエルモノマーとしては、例えば、（メタ）アクリル酸、ビエル安息香酸、マレイン酸、 マレイン酸モノアルキルエステル、フマノレ酸、ィタコン酸、クロトン酸、桂皮酸、アタリノレ 酸ダイマー、水酸基を有する単量体（例えば、 2—ヒドロキシェチル (メタ）アタリレート 等）と環状無水物（例えば、無水マレイン酸や無水フタル酸、シクロへキサンジカルボ ン酸無水物）との付加反応物、 ω—カルボキシ一ポリ力プロラタトンモノ (メタ）アタリレ ートなどが挙げられる。これらの中でも、共重合性やコスト、溶解性などの観点から (メ タ）アクリル酸が特に好ましい。またこれらのモノマーは、 1種単独で使用してもよぐ 2 種以上を併用してもよい。  The acidic group of the (1) butyl monomer having an acidic group is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a carboxylate group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable. Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaroleic acid, itaconic acid, crotonic acid, cinnamic acid, attalinoleic acid dimer, and hydroxyl group. An addition reaction product of a monomer having a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic acid anhydride), Carboxy-poly-polypropylene mono (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. These monomers may be used alone or in combination of two or more.
また、カルボキシル基の前駆体として無水マレイン酸、無水ィタコン酸、無水シトラコ ン酸等の無水物を有するモノマーを用いてもょレ、。  In addition, monomers having anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as the precursor of the carboxyl group.
前記（2)の高分子反応に利用可能な官能基を有するビニルモノマーにおける、高 分子反応に利用可能な官能基としては水酸基、アミノ基、イソシァネート基、エポキシ 基、酸ハライド基、活性ハライド基、などが挙げられる。また前述（1)のカルボシキル 基や酸無水物基も利用可能な官能基として挙げられる。  In the vinyl monomer having a functional group that can be used for the polymer reaction of (2) above, the functional group that can be used for the high molecular reaction includes a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc. In addition, the above-mentioned (1) carboxyl group and acid anhydride group are also usable functional groups.
[0042] 前記水酸基を有するビニルモノマーとしては、例えば、下記構造式（34)〜（42)で 表される化合物が挙げられる。 [0043] [化 23] [0042] Examples of the vinyl monomer having a hydroxyl group include compounds represented by the following structural formulas (34) to (42). [0043] [Chemical 23]
構造式（34)
Figure imgf000036_0001
Structural formula (34)
Figure imgf000036_0001
o  o
[0044] [化 24]  [0044] [Chemical 24]
構造式（35)
Figure imgf000036_0002
Structural formula (35)
Figure imgf000036_0002
o  o
[0045] [化 25]  [0045] [Chemical 25]
H 構造式 (36)
Figure imgf000036_0003
H structural formula (36)
Figure imgf000036_0003
O  O
[0046] [化 26]  [0046] [Chemical 26]
構造式（37)
Figure imgf000036_0004
Structural formula (37)
Figure imgf000036_0004
[0047] [化 27] 構造式 (38)
Figure imgf000036_0005
[0047] [Chemical 27] Structural formula (38)
Figure imgf000036_0005
[0048] [化 28] 構造式（39)
Figure imgf000037_0001
[0048] [Chemical 28] Structural formula (39)
Figure imgf000037_0001
[0049] 構造式（40)
Figure imgf000037_0002
[0049] Structural formula (40)
Figure imgf000037_0002
[0050] [化 30] [0050] [Chemical 30]
構造式 (41 )Structural formula (41)
Figure imgf000037_0003
Figure imgf000037_0003
[0051] [化 31]  [0051] [Chemical 31]
構造式 (42)Structural formula (42)
Figure imgf000037_0004
H
Figure imgf000037_0004
H
[0052] 但し、前記構造式（34)〜（42)中、 R1は水素原子又はメチル基を表し、 n、 nl及び n2は 1以上の整数を表す。 In the structural formulas (34) to (42), R 1 represents a hydrogen atom or a methyl group, and n, nl, and n2 represent an integer of 1 or more.
[0053] 前記アミノ基を有するビエルモノマーとしては、例えば、ビエルベンジルァミン、アミ ノエチルメタタリレート、などが挙げられる。  [0053] Examples of the Biel monomer having an amino group include Bielbenzylamine, aminoethyl methacrylate, and the like.
[0054] 前記イソシァネート基を有するモノマーとしては、例えば、下記構造式 (43)〜（45) で表される化合物が挙げられる。  [0054] Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (43) to (45).
[0055] [化 32]  [0055] [Chemical 32]
H R1 HR 1
NCO  NCO
C=C一 C〇〇 構造式（43)  C = C One COO Structural formula (43)
H  H
[0056] [化 33] H R1 [0056] [Chemical 33] HR 1
C=C一 C〇一 NC〇 構造式 (44)  C = C 1 C 0 1 NC 0 Structural formula (44)
H  H
[化 34] 構造式（45) [Chemical Formula 34] Structural formula (45)
Figure imgf000038_0001
Figure imgf000038_0001
[0058] 但し、前記構造式 (43)〜（45)中、 R1は水素原子又はメチル基を表す。 However, in the structural formulas (43) to (45), R 1 represents a hydrogen atom or a methyl group.
[0059] 前記エポキシ基を有するビュルモノマーとしては、例えば、グリシジル（メタ）アタリレ ート、下記構造式 (46)で表される化合物などが挙げられる。 [0059] Examples of the butyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (46).
[0060] [化 35] [0060] [Chemical 35]
構造式 (46)Structural formula (46)
Figure imgf000038_0002
Figure imgf000038_0002
但し、前記構造式 (46)中、 Rは H及び Meのいずれかを表す。  However, in said structural formula (46), R represents either H or Me.
[0061] 前記酸ハライド基を有するビエルモノマーとしては、例えば、（メタ）アクリル酸クロリド 、などが挙げられる。 [0061] Examples of the Biel monomer having an acid halide group include (meth) acrylic acid chloride.
前記活性ハライド基を有するビエルモノマーとしては、例えば、クロロメチルスチレン 、などが挙げられる。  Examples of the Biel monomer having an active halide group include chloromethylstyrene.
これらの市販品としては、例えば、「カネカレジン AXE ;鐘淵化学工業 (株)製」、「サ イクロマー（CYCLOMER) A— 200 ;ダイセル化学工業（株）製」、「サイクロマー（ CYCLOMER) M— 200 ;ダイセル化学工業（株）製」、「SPCP1X、 SPCP2X、 S PCP3X;昭和高分子 (株)製」などを用いることができる。  Examples of these commercially available products include “Kaneka Resin AX; manufactured by Kaneka Chemical Industry Co., Ltd.”, “CYCLOMER A-200; manufactured by Daicel Chemical Industries, Ltd.”, “CYCLOMER M” 200; manufactured by Daicel Chemical Industries, Ltd. ”,“ SPCP1X, SPCP2X, S PCP3X; manufactured by Showa Polymer Co., Ltd. ”, and the like can be used.
また、前記各モノマーは、 1種単独で使用してもよぐ 2種以上を併用してもよい。  Each of the monomers may be used alone or in combination of two or more.
[0062] 前記（3)の必要に応じて用いられるその他の共重合可能なモノマーとしては、特に 制限はなぐ 目的に応じて適宜選択することができるが、例えば、（メタ）アクリル酸ェ ステル類、クロトン酸エステル類、ビュルエステル類、マレイン酸ジエステル類、フマ ル酸ジエステル類、ィタコン酸ジエステル類、（メタ）アクリルアミド類、ビュルエーテル 類、ビュルアルコールのエステル類、スチレン類（例えば、スチレン、スチレン誘導体 等）、 （メタ）アクリロニトリル、ビュル基が置換した複素環式基 (例えば、ビュルピリジン 、ビュルピロリドン、ビュル力ルバゾール等）、 N—ビュルホルムアミド、 N—ビュルァ セトアミド、 N—ビュルイミダゾール、ビュル力プロラタトン、 2_アクリルアミド一 2—メ チルプロパンスルホン酸、リン酸モノ（2—アタリロイルォキシェチルエステル）、リン酸 モノ（1—メチル _ 2—アタリロイルォキシェチルエステル）、官能基（例えば、ウレタン 基、ウレァ基、スルホンアミド基、イミド基）を有するビュルモノマーなどが挙げられる。 [0062] The other copolymerizable monomer used as necessary in the above (3) is not particularly limited and may be appropriately selected depending on the purpose. For example, (meth) acrylic acid esters , Crotonic acid esters, Bull esters, Maleic acid diesters, Fumaric acid diesters, Itaconic acid diesters, (Meth) acrylamides, Bull ether , Esters of butyl alcohol, styrenes (for example, styrene, styrene derivatives, etc.), (meth) acrylonitrile, heterocyclic groups substituted by bur groups (for example, burpyridine, bulurpyrrolidone, bulur rubazole, etc.), N —Burformamide, N-Burecetamide, N-Buylimidazole, Bulle Prolatatone, 2_Acrylamide-2-Methylpropanesulfonic acid, Monophosphate (2-Ataloyloxetyl ester), Monophosphate (1 -Methyl_2-attalylooxychetyl ester) and butyl monomer having a functional group (for example, urethane group, urea group, sulfonamide group, imide group).
[0063] 前記（メタ）アクリル酸エステル類としては、例えば、メチル (メタ）アタリレート、ェチル [0063] Examples of the (meth) acrylic acid esters include methyl (meth) acrylate and ethyl.
(メタ）アタリレート、 n—プロピル（メタ）アタリレート、イソプロピル（メタ）アタリレート、 n —ブチル (メタ）アタリレート、イソブチル (メタ）アタリレート、 t—ブチル (メタ）アタリレー ト、 n キシル（メタ）アタリレート、シクロへキシル（メタ）アタリレート、 tーブチルシク 口へキシル（メタ）アタリレート、 2—ェチルへキシル（メタ）アタリレート、 t—ォクチル（メ タ）アタリレート、ドデシル (メタ）アタリレート、ォクタデシル (メタ）アタリレート、ァセトキ シェチル (メタ）アタリレート、フエ二ノレ (メタ）アタリレート、 2—メトキシェチル (メタ）ァク リレート、 2—エトキシェチル (メタ）アタリレート、 2— (2—メトキシエトキシ）ェチル (メタ )アタリレート、ベンジル（メタ）アタリレート、ジエチレングリコールモノメチルエーテル（ メタ）アタリレート、ジエチレングリコールモノェチルエーテル（メタ）アタリレート、ジェ チレングリコーノレモノフエニノレエーテノレ（メタ）アタリレート、トリエチレングリコーノレモノ メチルエーテル（メタ）アタリレート、トリエチレングリコールモノェチルエーテル（メタ） アタリレート、ポリエチレングリコールモノメチルエーテル（メタ）アタリレート、ポリエチレ ングリコールモノェチルエーテル（メタ）アタリレート、 β—フエノキシエトキシェチルァ タリレート、ノユルフェノキシポリエチレングリコール（メタ）アタリレート、ジシクロペンタ ニル（メタ）アタリレート、ジシクロペンテュル（メタ）アタリレート、ジシクロペンテニルォ ノレ（メタ）アタリレート、パーフロロォクチルェチル（メタ）アタリレート、トリブロモフエニル (メタ）アタリレート、トリブロモフエニルォキシェチル (メタ）アタリレートなどが挙げられ る。  (Meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n — butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n xyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, tert-butyl hex Hexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) Atalylate, Octadecyl (meth) atylate, Acetoxy Shetyl (meth) Atalylate, Hueninore (meth) Atalylate, 2-Methoxyethyl (meth) acrylate, 2-Ethoxyethyl (meth) atarylate, 2— (2 —Methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethyl Glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monomono phenoleateolate (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, tri Ethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxy ethyl acrylate, nourphenoxy polyethylene Glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl nonole (meth) acrylate, Fluorochemicals O lipped Rue chill (meth) Atari rate, tribromo-phenylalanine (meth) Atari rate, tribromo-phenylalanine O key Chez chill (meth) Atari rate Ru mentioned.
[0064] 前記クロトン酸エステル類としては、例えば、クロトン酸ブチル、クロトン酸へキシル などが挙げられる。 [0064] Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid. Etc.
[0065] 前記ビュルエステル類としては、例えば、ビュルアセテート、ビュルプロピオネート、 ビュルブチレート、ビュルメトキシアセテート、安息香酸ビュルなどが挙げられる。  [0065] Examples of the bull esters include bull acetate, bull propionate, bull butyrate, bull methoxyacetate, and benzoic acid bull.
[0066] 前記マレイン酸ジエステル類としては、例えば、マレイン酸ジメチル、マレイン酸ジ ェチル、マレイン酸ジブチルなどが挙げられる。  [0066] Examples of the maleic diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
[0067] 前記フマル酸ジエステル類としては、例えば、フマル酸ジメチル、フマル酸ジェチ ノレ、フマル酸ジブチルなどが挙げられる。  [0067] Examples of the fumaric acid diesters include dimethyl fumarate, jetinole fumarate, and dibutyl fumarate.
[0068] 前記ィタコン酸ジエステル類としては、例えば、ィタコン酸ジメチル、ィタコン酸ジェ チル、ィタコン酸ジブチルなどが挙げられる。  [0068] Examples of the itaconic acid diesters include dimethyl itaconate, dimethyl itaconate, and dibutyl itaconate.
[0069] 前記（メタ）アクリルアミド類としては、例えば、 （メタ）アタリノレアミド、 N—メチル (メタ） アクリルアミド、 N—ェチル (メタ）アクリルアミド、 N—プロピル (メタ）アクリルアミド、 N —イソプロピル (メタ）アクリルアミド、 N—n—ブチルアクリル (メタ）アミド、 N— t—ブチ ル (メタ）アクリルアミド、 N—シクロへキシル (メタ）アクリルアミド、 N— (2—メトキシェ チル）（メタ）アクリルアミド、 N, N—ジメチル（メタ）アクリルアミド、 N, N—ジェチル（メ タ）アタリノレアミド、 N—フエニル (メタ）アクリルアミド、 N—ベンジル (メタ）アクリルアミド 、 （メタ）アタリロイルモルホリン、ジアセトンアクリルアミドなどが挙げられる。  [0069] Examples of the (meth) acrylamides include (meth) atalinoleamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) ) Acrylamide, N-n-butylacryl (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, Examples include N-dimethyl (meth) acrylamide, N, N-jetyl (meth) atalinoleamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) atalyloylmorpholine, diacetone acrylamide, etc. It is done.
[0070] 前記スチレン類としては、例えば、前記スチレン、前記スチレン誘導体（例えば、メ チノレスチレン、ジメチノレスチレン、トリメチノレスチレン、ェチノレスチレン、イソプロピノレス チレン、ブチノレスチレン、メトキシスチレン、ブトキシスチレン、ァセトキシスチレン、クロ ロスチレン、ジクロロスチレン、プロモスチレン、酸性物質により脱保護可能な基 (例え ば、 t— Boc等）で保護されたヒドロキシスチレン、ビュル安息香酸メチル、 a—メチノレ スチレン等）、などが挙げられる。  [0070] Examples of the styrene include, for example, the styrene, the styrene derivative (for example, methino styrene, dimethyl styrene, trimethyl styrene, ethino styrene, isopropyleno styrene, butino styrene, methoxy styrene, butoxy styrene, Cetoxystyrene, chlorostyrene, dichlorostyrene, promostyrene, hydroxystyrene protected with groups that can be deprotected by acidic substances (eg t-Boc), methyl butyl benzoate, a-methylol styrene, etc.), etc. Is mentioned.
[0071] 前記ビュルエーテル類としては、例えば、メチルビュルエーテル、ブチルビニルェ 一テル、へキシルビュルエーテル、メトキシェチルビニルエーテルなどが挙げられる。  [0071] Examples of the butyl ethers include methyl butyl ether, butyl vinyl ether, hexyl butyl ether, methoxyethyl vinyl ether, and the like.
[0072] 前記官能基としてウレタン基又はウレァ基を有するビュルモノマーの合成方法とし ては、例えば、イソシアナート基と水酸基又はアミノ基の付加反応が挙げられ、具体 的には、イソシアナ一ト基を有するモノマーと、水酸基を 1個含有する化合物又は 1級 若しくは 2級アミノ基を 1個有する化合物との付加反応、水酸基を有するモノマー又 は 1級若しくは 2級アミノ基を有するモノマーと、モノイソシァネートとの付カ卩反応が挙 げられる。 [0072] Examples of a method for synthesizing a bulu monomer having a urethane group or a urea group as the functional group include an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an isocyanate group is used. Addition reaction between a monomer having a hydroxyl group and a compound having one hydroxyl group or a compound having one primary or secondary amino group, a monomer having a hydroxyl group, In this case, an addition reaction between a monomer having a primary or secondary amino group and a monoisocyanate is mentioned.
[0073] 前記イソシアナ一ト基を有するモノマーとしては、例えば、前述の（2)に示したものと 同様に、前記構造式 (43)〜（45)で表される化合物が挙げられる。  [0073] Examples of the monomer having an isocyanato group include compounds represented by the structural formulas (43) to (45) in the same manner as described in (2) above.
前記モノイソシァネートとしては、例えば、シクロへキシルイソシァネート、 n_ブチル イソシァネート、トルイルイソシァネート、ベンジルイソシァネート、フエニルイソシァネ ート等が挙げられる。  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.
前記水酸基を有するモノマーとしては、例えば、前述の（2)に示したものと同様に、 前記構造式（34)〜（42)で表される化合物が挙げられる。  Examples of the monomer having a hydroxyl group include compounds represented by the structural formulas (34) to (42) as in the above-described (2).
[0074] 前記水酸基を 1個含有する化合物としては、例えば、アルコール類（例えば、メタノ ール、エタノール、 n プロパノール、 i プロパノール、 n—ブタノール、 sec ブタノ 一ノレ、 tーブタノ一ノレ、 n—へキサノーノレ、 2—ェチノレへキサノーノレ、 n—デカノーノレ、 n—ドデカノール、 n—ォクタデカノール、シクロペンタノール、シクロへキサノール、ベ ンジルアルコール、フエニルエチルアルコール等）、フエノール類（例えば、フエノー ル、クレゾール、ナフトール等）、更に置換基を含むものとして、フロロエタノール、トリ フロロエタノール、メトキシエタノール、フエノキシエタノール、クロ口フエノール、ジクロ 口フエノール、メトキシフエノーノレ、ァセトキシフエノール等が挙げられる。  [0074] Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butano-monore, t-butano-monore, n- Xananol, 2-ethynole hexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, Naphthol, etc.) and those further containing a substituent include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, black mouth phenol, dichloro mouth phenol, methoxy phenol and acetophenol.
[0075] 前記 1級又は 2級アミノ基を有するモノマーとしては、例えば、ビュルベンジルァミン などが挙げられる。  [0075] Examples of the monomer having a primary or secondary amino group include burbenzylamine.
[0076] 前記 1級又は 2級アミノ基を 1個含有する化合物としては、例えば、アルキルアミン（ メチノレァミン、ェチルァミン、 n—プロピルァミン、 i—プロピルァミン、 n—ブチルァミン 、 sec—ブチルァミン、 t—ブチルァミン、へキシルァミン、 2—ェチルへキシルァミン、 デシノレアミン、ドデシルァミン、ォクタデシルァミン、ジメチルァミン、ジェチルァミン、 ジブチルァミン、ジォクチルァミン）、環状アルキルアミン（シクロペンチルァミン、シク 口へキシルァミン等）、ァラルキルァミン（ベンジルァミン、フエネチルァミン等）、ァリー ルァミン（ァニリン、トノレイノレアミン、キシリルァミン、ナフチルァミン等）、更にこれらの 組合せ（N メチル—N—ベンジルァミン等）、更に置換基を含むアミン（トリフロロェ チルァミン、へキサフロロイソプロピルァミン、メトキシァニリン、メトキシプロピルァミン 等）などが挙げられる。 [0076] Examples of the compound containing one primary or secondary amino group include alkylamines (methinolamin, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, Xylamine, 2-ethylhexylamine, decynoleamine, dodecylamine, octadecylamine, dimethylamine, jetylamine, dibutylamine, dioctylamine), cyclic alkylamines (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.) Arylamines (aniline, tonorenoleamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and further amines containing substituents (trifluoroethylene) Amin, the hexa fluorosilicone isopropyl § Min, Metokishianirin, methoxypropyl § Min Etc.).
[0077] また、これらのモノマーは、 1種単独で使用してもよぐ 2種以上を併用してもよい。  [0077] These monomers may be used alone or in combination of two or more.
これらをビュル (共)重合させることにより酸性基、酸無水物基および必要に応じて 水酸基、アミノ基、イソシァネート基、エポキシ基、酸ハライド基、活性ハライド基など を含有する（共)重合体が得られる。前記ビュル (共)重合体は、それぞれ相当するモ ノマーを公知の方法により常法に従って共重合させることで調製することができる。例 えば、前記モノマーを適当な溶媒中に溶解し、ここにラジカル重合開始剤を添加して 溶液中で重合させる方法 (溶液重合法）を利用することにより調製することができる。 また、水性媒体中に前記モノマーを分散させた状態でいわゆる乳化重合等で重合を 禾 IJ用することにより調製すること力 Sできる。  These are (co) polymerized into a (co) polymer containing an acid group, an acid anhydride group and, if necessary, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. can get. The bull (co) polymer can be prepared by copolymerizing the corresponding monomers according to a conventional method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. In addition, it can be prepared by using IJ for polymerization by so-called emulsion polymerization or the like in a state where the monomer is dispersed in an aqueous medium.
このようにして得られた（共）重合体に対して、前記 (4)として、これらの共重合体中 の酸性基、および必要に応じて水酸基、アミノ基、イソシァネート基、グリシジル基、 酸ハライド基の少なくとも 1種に対して反応性を有する官能基と (メタ）アタリロイル基を 有する化合物とを高分子反応させることによって得られる。  With respect to the (co) polymer thus obtained, as the above (4), the acidic group in these copolymers and, if necessary, a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, an acid halide It can be obtained by polymer-reacting a functional group having reactivity with at least one of the groups and a compound having a (meth) atallyloyl group.
[0078] 前記該 (4)の（共)重合体中の酸性基、又は高分子反応に利用可能な官能基の少 なくとも 1種に対して反応性を有する官能基と (メタ）アタリロイル基を有する化合物と しては、前述の（2)に示した化合物などが利用できる。 [0078] A functional group having reactivity with at least one of an acidic group in the (co) polymer of the above (4) or a functional group that can be used in a polymer reaction, and a (meth) allyloyl group As the compound having the above, the compound shown in the above (2) can be used.
これらの高分子反応を行なう場合の官能基の組合せの例としては、例えば、酸性基 (カルボキシル基など）を有する共重合体とエポキシ基を有するビュルモノマーの組 合せ、アミノ基を有する共重合体とエポキシ基を有するビュルモノマーの組合せ、アミ ノ基を有する共重合体とイソシァネート基を有するビュルモノマーの組合せ、水酸基 を有する共重合体とイソシァネート基を有するビュルモノマーの組合せ、水酸基を有 する共重合体と酸ハライド基を有するビュルモノマーの組合せ、アミノ基を有する共 重合体と活性ハライド基を有するビニルモノマーの組合せ、酸無水物基を有する共 重合体と水酸基を有するビュルモノマーの組合せ、イソシァネート基を有する共重合 体とアミノ基を有するビュルモノマーの組合せ、イソシァネート基を有する共重合体と 水酸基を有するビュルモノマーの組合せ、活性ハライド基を有する共重合体とァミノ 基を有するビュルモノマーの組合せ、などが挙げられる。またこれらの組合せは 2種 以上を併用しても構わない。 Examples of combinations of functional groups for performing these polymer reactions include, for example, a copolymer having an acidic group (such as a carboxyl group) and a butyl monomer having an epoxy group, and a copolymer having an amino group. And a combination of a butyl monomer having an epoxy group, a combination of a copolymer having an amino group and a butyl monomer having an isocyanate group, a combination of a copolymer having a hydroxyl group and a butyl monomer having an isocyanate group, a copolymer having a hydroxyl group Combination of a butyl monomer having a polymer and an acid halide group, a combination of a copolymer having an amino group and a vinyl monomer having an active halide group, a combination of a copolymer having an acid anhydride group and a butyl monomer having a hydroxyl group, an isocyanate group A copolymer having an amino group and a butyl monomer having an amino group, isocyanate The combination of Bulle monomer having a copolymer and a hydroxyl group having a group, a combination of Bulle monomer having a copolymer and Amino group having an active halide groups, and the like. These combinations are 2 types You may use the above together.
[0079] <マレアミド酸系共重合体 >  [0079] <Maleamic acid copolymer>
前記マレアミド酸系共重合体は、無水マレイン酸共重合体の無水物基に対して 1級 ァミン化合物を 1種以上反応させて得られる共重合体である。該共重合体は下記構 造式 (VII)で表される、マレイン酸ハーフアミド構造を有するマレアミド酸ユニット Bと、 前記マレイン酸ハーフアミド構造を有しないユニット Aと、を少なくとも含むマレアミド 酸系共重合体であるのが好ましい。  The maleamic acid copolymer is a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer. The copolymer is a maleamic acid copolymer comprising at least a maleamic acid unit B having a maleic acid half amide structure and a unit A having no maleic acid half amide structure, represented by the following structural formula (VII). A polymer is preferred.
前記ユニット Aは 1種であってもよいし、 2種以上であってもよレ、。例えば、前記ュニ ット Bが 1種であるとすると、前記ユニット Aが 1種である場合には、前記マレアミド酸系 共重合体が 2元共重合体を意味することになり、前記ユニット Aが 2種である場合には 、前記マレアミド酸系共重合体が 3元共重合体を意味することになる。  The unit A may be one type or two or more types. For example, assuming that Unit B is one type, when Unit A is one type, the maleamic acid-based copolymer means a binary copolymer, and the unit When A is two kinds, the maleamic acid copolymer means a terpolymer.
前記ユニット Aとしては、置換基を有していてもよいァリール基と、後述するビニル単 量体であって、該ビニル単量体のホモポリマーのガラス転移温度（Tg)が 80°C未満 であるビュル単量体（c)との組合せが好適に挙げられる。  The unit A includes an aryl group which may have a substituent and a vinyl monomer which will be described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with a certain bull monomer (c) is preferred.
[0080] [化 36] [0080] [Chemical 36]
構造式 (V I I ) Structural formula (V I I)
Figure imgf000043_0001
Figure imgf000043_0001
A B  A B
ただし、前記構造式 (VII)中、 R3及び R4は水素原子及び低級アルキル基のいずれ かを表す。 X及び yは繰り返し単位のモル分率を表し、例えば、前記ユニット Aが 1種 の場合、 Xは 85〜50モノレ0 /0であり、 yは 15〜50モル0 /0である。 However, in the structural formula (VII), R 3 and R 4 represent either a hydrogen atom or a lower alkyl group. X and y represent mole fractions of the repeating units, for example, when the unit A is one, X is 85-50 Monore 0/0, y is 15 to 50 mole 0/0.
前記構造式 (VI)中、 R1としては、例えば、（― COOR10) (― CONRUR12)、置換 基を有していてもよいァリール基、（一〇C〇R13)、 (-OR14) , (— COR15)などの置 換基が挙げられる。ここで、前記 R1U〜R15は、水素原子（一 H)、置換基を有していて もよいアルキル基、ァリール基及びァラルキル基のいずれかを表す。該アルキル基、 ァリール基及びァラルキル基は、環状構造又は分岐構造を有してレ、てもよレ、。 In the structural formula (VI), as R 1 , for example, (—COOR 10 ) (—CONRUR 12 ), an aryl group optionally having a substituent, (10C0R 13 ), (—OR 14 ), (— COR 15 ) Examples include a substituent. Here, R 1U to R 15 each represents a hydrogen atom (1H), an optionally substituted alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
前記 R1()〜： R15としては、例えば、メチノレ、ェチル、 n—プロピル、 i—プロピル、 n—ブ チル、 i—ブチル、 sec—ブチル、 t—ブチル、ペンチル、ァリノレ、 n—へキシル、シクロ へキシル、 2—ェチルへキシル、ドデシノレ、メトキシェチル、フエニル、メチルフエニル 、メトキシフエニル、ベンジル、フエネチル、ナフチル、クロ口フエニルなどが挙げられ る。 R 1 () to R 15 may be, for example, methinole, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, aranole, n- Examples include xyl, cyclohexyl, 2-ethylhexyl, dodecinole, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, and black mouth phenyl.
前記 R1の具体例としては、例えば、フエニル、 a メチルフエニル、 2—メチルフエ ニル、 3 メチルフエニル、 4 メチルフエニル、 2, 4 ジメチルフエニル等のベンゼ ン誘導体； n—プロピルォキシカルボニル、 n—ブチルォキシカルボニル、ペンチルォ キシカノレボニノレ、へキシノレォキシカノレボニノレ、 n—ブチノレオキシカノレボニノレ、 n—へ キシルォキシカルボニル、 2—ェチルへキシルォキシカルボニル、メチルォキシカル ボニルなどが挙げられる。 Specific examples of R 1 include, for example, benzen derivatives such as phenyl, a methylphenyl, 2-methylphenyl, 3 methylphenyl, 4 methylphenyl, 2,4 dimethylphenyl; n-propyloxycarbonyl, n-butyloxy Examples thereof include xyloxycarbonyl, pentyloxycanenoboninole, hexinorexicanoreboninole, n-butynoleoxycanoleboninole, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.
前記 R2としては、置換基を有していてもよいアルキル基、ァリール基、ァラルキル基 などが挙げられる。これらは、環状構造又は分岐構造を有していてもよい。前記 の 具体例としては、例えば、ベンジル、フエネチル、 3—フエ二ルー 1—プロピル、 4—フ ェニル一1—ブチル、 5—フエニル一 1—ペンチル、 6—フエ二ノレ一 1—へキシル、 ひ —メチルベンジル、 2 _メチルベンジル、 3 _メチルベンジル、 4 _メチルベンジル、 2 _ (p—トリル）ェチル、 j3—メチルフエネチル、 1 _メチル _ 3 _フエニルプロピル、 2 —クロ口べンジノレ、 3 _クロ口べンジノレ、 4_クロ口べンジノレ、 2 _フロロべンジノレ、 3 _ フロロべンジノレ、 4—フロロべンジノレ、 4—ブロモフエネチノレ、 2— (2—クロ口フエ二ノレ） ェチル、 2 - (3—クロ口フエ二ノレ）ェチル、 2 _ (4—クロ口フエ二ノレ）ェチル、 2 _ (2 - フロロフエ二ノレ）ェチノレ、 2 _ (3 _フロロフエ二ノレ）ェチノレ、 2 _ (4 _フロロフエ二ノレ）ェ チル、 4—フロロ一ひ， a—ジメチルフエネチル、 2—メトキシベンジル、 3—メトキシべ ンジノレ、 4—メトキシベンジル、 2 _エトキシベンジル、 2—メトキシフエネチル、 3—メト キシフエネチル、 4—メトキシフエネチル、メチノレ、ェチル、プロピル、 i—プロピル、ブ チル、 tーブチル、 sec ブチノレ、ペンチノレ、へキシノレ、シクロへキシル、ヘプチノレ、ォ クチル、ラウリノレ、フエニル、 1 _ナフチル、メトキシメチノレ、 2—メトキシェチル、 2—ェ トキシェチル、 3 メトキシプロピル、 2 _ブトキシェチル、 2—シクロへキシルォキシェ チル、 3_エトキシプロピル、 3 _プロポキシプロピル、 3 _イソプロポキシプロピルアミ ンなどが挙げられる。 Examples of R 2 include an optionally substituted alkyl group, aryl group, aralkyl group, and the like. These may have a cyclic structure or a branched structure. Specific examples of the above include benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenol-1-hexyl, —-Methylbenzyl, 2_methylbenzyl, 3_methylbenzyl, 4_methylbenzyl, 2_ (p-tolyl) ethyl, j3-methylphenethyl, 1_methyl_3_phenylpropyl, 2—clobenbenole 3_Black-and-back Beninole, 4_Black-and-back Beninole, 2_Fluoro-Benzinore, 3_Fluoro-Benzinore, 4-Fluorobenzinole, 4-Bromofenetinore, 2— (2-Kuroguchi Fueninore) Ethyl, 2-(3-black mouth Fuenore) ethyl, 2 _ (4-black mouth Fuenore) ethyl, 2 _ (2-Fluoro Fuerinole) ethinore, 2 _ (3 _Floro Fuenorore) ethinore, 2 _ (4 _Florofenior) chill, 4— Roloichi, a-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzinole, 4-methoxybenzyl, 2_ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl , Methylol, ethyl, propyl, i-propyl, butyl, t-butyl, sec butinole, pentinole, hexinole, cyclohexyl, heptinole, o Cutyl, Laurinole, Phenyl, 1_Naphthyl, Methoxymethinole, 2-Methoxyethyl, 2-Equichetyl, 3Methoxypropyl, 2_Butoxytyl, 2-Cyclohexyloxychetyl, 3_Ethoxypropyl, 3_Propoxypropyl, 3_Isopropoxy And propylamine.
[0083] 前記バインダーは、特に、（a)無水マレイン酸と、（b)芳香族ビニル単量体と、（c)ビ 二ル単量体であって、該ビュル単量体のホモポリマーのガラス転移温度（Tg)が 80 °C未満であるビニル単量体と、力 なる共重合体の無水物基に対して 1級アミンィ匕合 物を反応させて得られる共重合体であるのが好ましい。該（a)成分と、該 (b)成分と、 力 なる共重合体では、後述する感光層の高い表面硬度を得ることはできるものの、 ラミネート性の確保が困難になることがある。また、該 (a)成分と、該 (c)成分と、から なる共重合体では、ラミネート性は確保することができるものの、前記表面硬度の確 保が困難になることがある。  [0083] The binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, which is a homopolymer of the bulle monomer. A copolymer obtained by reacting a primary amine compound with a vinyl monomer having a glass transition temperature (Tg) of less than 80 ° C and an anhydride group of a powerful copolymer is a copolymer. preferable. With the (a) component, the (b) component, and a powerful copolymer, it is possible to obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties. In addition, in the copolymer comprising the component (a) and the component (c), although the laminating property can be ensured, it may be difficult to ensure the surface hardness.
[0084] (b)芳香族ビュル単量体 [0084] (b) Aromatic Bull monomer
前記芳香族ビニル単量体としては、特に制限はなぐ 目的に応じて適宜選択するこ とができるが、本発明の感光性組成物を用いて形成される感光層の表面硬度を高く することができる点で、ホモポリマーのガラス転移温度 (Tg)が 80°C以上である化合 物が好ましぐ 100°C以上である化合物がより好ましい。  The aromatic vinyl monomer is not particularly limited and can be appropriately selected according to the purpose. However, the surface hardness of the photosensitive layer formed using the photosensitive composition of the present invention can be increased. In view of this, compounds having a glass transition temperature (Tg) of the homopolymer of 80 ° C or higher are preferred, and compounds having a temperature of 100 ° C or higher are more preferable.
前記芳香族ビュル単量体の具体例としては、例えば、スチレン（ホモポリマーの Tg = 100°C)、 ひ一メチルスチレン（ホモポリマーの Tg= 168。C)、 2—メチルスチレン（ ホモポリマーの Tg= 136。C)、 3 メチルスチレン（ホモポリマーの Tg = 97°C)、 4_ メチルスチレン（ホモポリマーの Tg = 93°C)、 2, 4_ジメチルスチレン（ホモポリマー の Tg = 112°C)などのスチレン誘導体が好適に挙げられる。これらは 1種単独で使用 してもょレ、し、 2種以上を併用してもよい。  Specific examples of the aromatic butyl monomer include, for example, styrene (homopolymer Tg = 100 ° C.), monomethylstyrene (homopolymer Tg = 168.C), 2-methylstyrene (homopolymer Tg = 136.C), 3 Methylstyrene (Homopolymer Tg = 97 ° C), 4_ Methylstyrene (Homopolymer Tg = 93 ° C), 2, 4_Dimethylstyrene (Homopolymer Tg = 112 ° C) Styrene derivatives such as) are preferred. These may be used alone or in combination of two or more.
[0085] - - (c)ビュル単量体— _ [0085]--(c) Bull monomer— _
前記ビュル単量体は、該ビュル単量体のホモポリマーのガラス転移温度 (Tg)が 80 °C未満であることが必要であり、 40°C以下が好ましぐ 0°C以下がより好ましい。  The bull monomer needs to have a glass transition temperature (Tg) of the homopolymer of the bull monomer of less than 80 ° C, preferably 40 ° C or less, more preferably 0 ° C or less. .
前記ビュル単量体としては、例えば、 n—プロピルアタリレート（ホモポリマーの Tg = — 37°C)、 n ブチルアタリレート（ホモポリマーの Tg=— 54°C)、ペンチルァクリレー ト、あるいはへキシルアタリレート（ホモポリマーの Tg= _ 57。C)、 n_ブチルメタクリレ ート（ホモポリマーの Tg= _ 24°C)、 n—へキシルメタタリレート（ホモポリマーの Tg = _ 5°C)などが挙げられる。これらは 1種単独で使用してもよいし、 2種以上を併用して ちょい。 Examples of the bull monomer include n-propyl acrylate (homopolymer Tg = -37 ° C), n-butyl acrylate (homopolymer Tg = -54 ° C), pentyl acrylate. Or hexyl acrylate (homopolymer Tg = _ 57.C), n_butyl methacrylate (homopolymer Tg = _ 24 ° C), n-hexyl methacrylate (Tg of homopolymer) = _ 5 ° C). These may be used alone or in combination of two or more.
[0086] 一 1級ァミン化合物一  [0086] One Primary Amamine Compound One
前記 1級ァミン化合物としては、例えば、ベンジルァミン、フヱネチルァミン、 3—フエ ニル— 1—プロピルァミン、 4—フエニル— 1—ブチルァミン、 5—フエニル— 1—ペン チルァミン、 6 フエ二ルー 1一へキシルァミン、 α メチルベンジルァミン、 2 メチ ルベンジルァミン、 3—メチルベンジルァミン、 4—メチルベンジルァミン、 2— (ρ トリ ル）ェチルァミン、 ；3—メチルフエネチルァミン、 1—メチル 3—フエニルプロピルァ ミン、 2 クロ口ベンジルァミン、 3 クロ口ベンジルァミン、 4—クロ口ベンジルァミン、 2 —フロロベンジルァミン、 3—フロロベンジルァミン、 4—フロロベンジルァミン、 4—ブ ロモフエネチルァミン、 2— (2 クロ口フエニル）ェチルァミン、 2— (3 クロ口フエニル )ェチルァミン、 2— (4—クロ口フエニル）ェチルァミン、 2— (2—フロロフエ二ノレ）ェチ ルァミン、 2— (3—フロロフエニル）ェチルァミン、 2— (4—フロロフエニル）ェチルアミ ン、 4 フロロ一 α , α—ジメチルフエネチルァミン、 2—メトキシベンジルァミン、 3— メトキシベンジルァミン、 4ーメトキシベンジルァミン、 2 エトキシベンジルァミン、 2— メトキシフエネチルァミン、 3—メトキシフエネチルァミン、 4—メトキシフエネチルァミン 、メチノレァミン、ェチルァミン、プロピルァミン、 1—プロピノレアミン、ブチルァミン、 t- ブチルァミン、 sec—ブチルァミン、ペンチルァミン、へキシルァミン、シクロへキシル ァミン、ヘプチルァミン、ォクチルァミン、ラウリルァミン、ァニリン、ォクチルァニリン、 ァニシジン、 4_クロノレア二リン、 1 _ナフチルァミン、メトキシメチルァミン、 2—メトキ シェチルァミン、 2 _エトキシェチルァミン、 3—メトキシプロピルァミン、 2 _ブトキシェ チルァミン、 2—シクロへキシルォキシェチルァミン、 3 _エトキシプロピルァミン、 3_ プロポキシプロピルアミン、 3 _イソプロポキシプロピルァミンなどが挙げられる。これら の中でも、ベンジルァミン、フエネチルァミンが特に好ましい。 Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6 phenyl 1-hexylamine, α Methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (ρ-tolyl) ethylamine,; 3-methylphenethylamine, 1-methyl-3-phenylpropylamine Minor, 2-Chlorobenzylamine, 3-Chlorobenzylamine, 4-Chlorobenzylamine, 2-Fluorobenzylamine, 3-Fluorobenzylamine, 4-Fluorobenzylamine, 4-Bromophenethylamine, 2- (2 Black mouth phenyl) ethylamine, 2— (3 Black mouth phenyl) ethylamine, 2— (4 Black mouth phenyl) ) Echiruamin, 2- (2-Furorofue two Honoré) E Ji Ruamin, 2- (3-Furorofueniru) Echiruamin, 2- (4-Furorofueniru) Echiruami down, 4 fluorosilicone one alpha, alpha - dimethyl Hue phenethyl Rua Min, 2- Methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2 ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methinoleamine , Ethylamine, propylamine, 1-propynoleamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, octylaniline, anisidine, 1 , Methoxymethylamine, 2-methoxy shetylamine, 2_ethoxyethylamine, 3-methoxypropylamine, 2_butoxy sheylamine, 2-cyclohexyloxychetilamine, 3_ethoxypropylamine 3_propoxypropylamine, 3_isopropoxypropylamine and the like. Of these, benzylamine and phenethylamine are particularly preferred.
前記 1級アミンィ匕合物は、 1種単独で使用してもよいし、 2種以上を併用してもよい。  The primary amine compounds may be used alone or in combination of two or more.
[0087] 前記 1級ァミン化合物の反応量としては、前記無水物基に対して 0. 1〜： 1. 2当量 であることが必要であり、 0. 1〜： 1. 0当量が好ましい。該反応量が 1. 2当量を超える と、前記 1級ァミン化合物を 1種以上反応させた場合に、溶解性が著しく悪化すること 力 sある。 [0087] The reaction amount of the primary amine compound is 0.1 to 1.2 equivalents relative to the anhydride group. And 0.1 to: 1.0 equivalent is preferable. When the reaction amount exceeds 1.2 equivalents, when the primary Amin compound was reacted for 1 or more, sometimes force s solubility is significantly deteriorated.
[0088] 前記（a)無水マレイン酸の前記バインダーにおける含有量は、 15〜50mol%が好 ましぐ 20〜45mol%がより好ましぐ 20〜40mol%が特に好ましレ、。該含有量が 15 mol%未満であると、アルカリ現像性の付与ができず、 50mol%を超えると、耐アル カリ性が劣化し、また、前記共重合体の合成が困難になり、正常な永久パターンの形 成を行うことができないことがある。また、この場合における、前記 (b)芳香族ビニル単 量体、及び（c)ホモポリマーのガラス転移温度（Tg)力 ¾0°C未満であるビニル単量体 の前記バインダーにおける含有量は、それぞれ 20〜60mol%、 15〜40mol%が好 ましい。該含有量が該数値範囲を満たす場合には、表面硬度及びラミネート性の両 立を図ることができる。  [0088] The content of (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol%. If the content is less than 15 mol%, alkali developability cannot be imparted, and if it exceeds 50 mol%, alkali resistance deteriorates, and the copolymer becomes difficult to synthesize. Permanent pattern formation may not be possible. In this case, the content of (b) the aromatic vinyl monomer and (c) the vinyl monomer having a glass transition temperature (Tg) power of less than 0 ° C. of the homopolymer in the binder is respectively 20-60 mol% and 15-40 mol% are preferred. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.
[0089] 前記マレアミド酸系共重合体の分子量は、 3, 000〜500, 000力 S好ましく、 8, 000 〜： 150, 000力 Sより好ましい。該分子量が 3, 000未満であると、後述する感光層の硬 化後において、膜質が脆くなり、表面硬度が劣化することがあり、 500， 000を超える と、前記感光性組成物の加熱積層時の流動性が低くなり、適切なラミネート性の確保 が困難になることがあり、また、現像性が悪化することがある。  The molecular weight of the maleamic acid copolymer is preferably 3,000 to 500,000 force S, more preferably 8,000 to: 150,000 force S. If the molecular weight is less than 3,000, the film quality becomes brittle and the surface hardness may deteriorate after curing of the photosensitive layer described later. If the molecular weight exceeds 500,000, the photosensitive composition is heated and laminated. The fluidity at the time may be low, and it may be difficult to ensure proper laminating properties, and the developability may deteriorate.
[0090] <その他のバインダー >  [0090] <Other binders>
前記その他バインダーとしては、特開平 11― 288087号公報記載のポリアミド (イミ ド)樹脂、特開平 11— 282155号公報記載のポリイミド前駆体などを用いることができ る。これらは 1種単独で使用してもよいし、 2種以上を混合して使用してもよい。  As the other binder, a polyamide (imide) resin described in JP-A-11-288087, a polyimide precursor described in JP-A-11-282155, or the like can be used. These may be used alone or as a mixture of two or more.
[0091] 前記ポリアミド（イミド）、あるいは、ポリイミド前駆体などのバインダーの分子量として ίま、 3, 000〜500， 000力好ましく、 5, 000〜100， 000カより好ましレヽ。該分子量 が 3, 000未満であると、感光層表面のタック性が強くなることがあり、後述する感光 層の硬化後において、膜質が脆くなる、あるいは、表面硬度が劣化することがあり、 5 00， 000を超えると、現像性が劣化することがある。  [0091] The molecular weight of the binder such as polyamide (imide) or polyimide precursor is preferably 3,000 to 500,000, more preferably 5,000 to 100,000. If the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may increase, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described below. If it exceeds 00,000, developability may deteriorate.
[0092] 前記バインダーの前記感光性組成物固形分中の固形分含有量は、 5〜70質量％ が好ましぐ 10〜50質量％がより好ましい。該固形分含有量が、 5質量％未満である と、後述する感光層の膜強度が弱くなりやすぐ該感光層の表面のタック性が悪化す ることがあり、 70質量％を超えると、露光感度が低下することがある。 [0092] The solid content in the photosensitive composition solid content of the binder is preferably 5 to 70 mass%, more preferably 10 to 50 mass%. The solid content is less than 5% by mass When the film strength of the photosensitive layer described later is weakened, the tackiness of the surface of the photosensitive layer may be deteriorated, and if it exceeds 70% by mass, the exposure sensitivity may be lowered.
[0093] 〔(B)重合性化合物〕 [(B) Polymerizable compound]
前記重合性化合物としては、特に制限はなぐ 目的に応じて適宜選択することがで きる力 分子中に少なくとも 1個の付加重合可能な基を有し、沸点が常圧で 100°C以 上である化合物が好まし 例えば、（メタ）アクリル基を有するモノマーから選択され る少なくとも 1種が好適に挙げられる。  The polymerizable compound is not particularly limited and can be appropriately selected according to the purpose. The polymerizable compound has at least one addition-polymerizable group in the molecule, and has a boiling point of 100 ° C. or higher at normal pressure. A certain compound is preferable. For example, at least one selected from monomers having a (meth) acryl group is preferable.
[0094] 前記 (メタ）アクリル基を有するモノマーとしては、特に制限はなぐ 目的に応じて適 宜選択することができ、例えば、ポリエチレングリコールモノ（メタ）アタリレート、ポリプ ロピレングリコールモノ（メタ）アタリレート、フエノキシェチル（メタ）アタリレート等の単 官能アタリレートや単官能メタタリレート；ポリエチレングリコールジ (メタ）アタリレート、 ポリプロピレングリコールジ（メタ）アタリレート、トリメチロールェタントリアタリレート、トリ メチロールプロパントリアタリレート、トリメチロールプロパンジアタリレート、ネオペンチ ルグリコールジ（メタ）アタリレート、ペンタエリスリトールテトラ（メタ）アタリレート、ペンタ エリスリトーノレトリ（メタ）アタリレート、ジペンタエリスリトールへキサ（メタ）アタリレート、 ジペンタエリスリトールペンタ（メタ）アタリレート、へキサンジオールジ（メタ）アタリレー ト、トリメチロールプロパントリ（アタリロイルォキシプロピル）エーテル、トリ（アタリロイル ォキシェチル）イソシァヌレート、トリ（アタリロイルォキシェチル）シァヌレート、グリセリ ントリ（メタ）アタリレート、トリメチロールプロパンやグリセリン、ビスフエノール等の多官 能アルコールに、エチレンオキサイドやプロピレンオキサイドを付カ卩反応した後で (メ タ）アタリレー卜ィ匕したもの、特公昭 48— 41708号、特公昭 50— 6034号、特開昭 51 — 37193号等の各公報に記載されているウレタンアタリレート類；特開昭 48— 6418 3号、特公昭 49 -43191号、特公昭 52— 30490号等の各公報に記載されているポ リエステルアタリレート類；エポキシ樹脂と（メタ）アクリル酸の反応生成物であるェポキ シアタリレート類等の多官能アタリレートやメタタリレートなどが挙げられる。これらの中 でも、トリメチロールプロパントリ（メタ）アタリレート、ペンタエリスリトールテトラ（メタ）ァ タリレート、ジペンタエリスリトールへキサ（メタ）アタリレート、ジペンタエリスリトールぺ ンタ (メタ）アタリレートが特に好ましい。 [0095] 前記重合性化合物の前記感光性組成物固形分中の固形分含有量は、 5〜50質 量％が好ましぐ 10〜40質量％がより好ましい。該固形分含有量が 5質量％未満で あると、現像性の悪化、露光感度の低下などの問題を生ずることがあり、 50質量％を 超えると、感光層の粘着性が強くなりすぎることがあり、好ましくない。 [0094] The monomer having the (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Monofunctional acrylates and monofunctional methallylates such as rate and phenoxychetyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate Rate, trimethylolpropane diatalylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta erythritol retri (meth) acrylate, dipentaerythritol Ruhexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylol propane tri (atallylooxypropyl) ether, tri (atallyloyloxychetyl) isocyanurate, tri (Methacryloyl oxychetyl) cyanurate, glycerin tri (meth) atallylate, trimethylolpropane, glycerin, bisphenol etc. ) Urethane acrylates described in publications such as JP-A-48-41708, JP-B-50-6034, JP-A-51-37193, etc .; JP-A-48-6418 3 No., JP-B 49-43191, JP-B 52-30490, etc. Polyester acrylates; polyfunctional acrylates such as epoxide acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and metatalates. Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol pent (meth) acrylate are particularly preferable. [0095] The solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
[0096] 〔(C)光重合開始剤〕  [0096] [(C) Photopolymerization initiator]
前記光重合開始剤としては、前記重合性化合物の重合を開始する能力を有する限 り、特に制限はなぐ公知の光重合開始剤の中から適宜選択することができるが、例 えば、紫外線領域から可視の光線に対して感光性を有するものが好ましぐ光励起さ れた增感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよぐ モノマーの種類に応じてカチオン重合を開始させるような開始剤であってもよい。 また、前記光重合開始剤は、約 300〜800nm (より好ましくは 330〜500nm)の範 圏内に少なくとも約 50の分子吸光係数を有する成分を少なくとも 1種含有しているこ とが好ましい。  The photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound. Those that have photosensitivity to visible light are preferred to photo-excited sensitizers and may act as active agents that generate active radicals. Cationic polymerization is performed depending on the type of monomer. It may be an initiator that initiates. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 in the range of about 300 to 800 nm (more preferably 330 to 500 nm).
[0097] 前記光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体 (例えば、トリアジ ン骨格を有するもの、ォキサジァゾール骨格を有するもの、など）、ホスフィンォキサイ ド、へキサァリールビイミダゾール、ォキシム誘導体、有機過酸化物、チォ化合物、ケ トン化合物、芳香族ォニゥム塩、メタセロン類、などが挙げられる。  [0097] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), phosphine oxides, hexarylbiimidazoles, oximes. Derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, metathelones, and the like.
[0098] 前記トリァジン骨格を有するハロゲン化炭化水素化合物としては、例えば、特開 20 05— 258431号公報の明細書の段落「0290」力 「0299」に記載されている前記ト リアジン骨格を有するハロゲン化炭化水素化合物などが挙げられる。  Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, a halogen having the triazine skeleton described in paragraphs “0290” and “0299” of the specification of JP-A No. 2005-258431. And hydrocarbon compounds.
[0099] 前記ホスフィンオキサイドとしては、例えば、ビス（2, 4, 6 _トリメチルベンゾィル）一 フエニルホスフィンオキサイド、ビス（2, 6—ジメトキシベンゾィル）_ 2， 4, 4一トリメチ ル一ペンチルフヱニルホスフィンオキサイド、 LucirinTPO,などが挙げられる。  [0099] Examples of the phosphine oxide include bis (2, 4, 6_trimethylbenzoyl) monophenylphosphine oxide and bis (2, 6-dimethoxybenzoyl) _2, 4, 4 monotrimethyl. Monopentylphenylphosphine oxide, LucirinTPO, and the like.
[0100] 前記へキサァリールビイミダゾールとしては、例えば、特開 2005— 258431号公報 の明細書の段落「0288」に記載されているへキサァリールビイミダゾールなどが挙げ られる。  [0100] Examples of the hexarylbiimidazole include hexarylbiimidazole described in paragraph "0288" of the specification of JP-A-2005-258431.
前記ビイミタ、、ゾーノレ類 ίま、 列え ίま、、 Bull. Chem. So Japan, 33， 565 (1960)、 及び J. Org. Chem, 36 (16) 2262 (1971)に開示されている方法により容易に合 成すること力 Sできる。 The method disclosed in the above-mentioned biimita, zonoles, arrangements, Bull. Chem. So Japan, 33, 565 (1960), and J. Org. Chem, 36 (16) 2262 (1971). More easily The ability to achieve S.
[0101] 本発明で好適に用いられる前記ォキシム誘導体としては、例えば、 3_ベンゾイロ キシイミノブタン一 2_オン、 3—ァセトキシィミノブタン一 2_オン、 3 _プロピオニル ォキシイミノブタン一 2_オン、 2—ァセトキシィミノペンタン一 3_オン、 2—ァセトキシ ィミノ _ 1 _フエ二ノレプロパン一 1 _オン、 2 _ベンゾイロキシィミノ一 1 _フエ二ノレプロ パン一 1 _オン、 3_ (4—トルエンスルホニルォキシ）イミノブタン一 2_オン、及び 2 —エトキシカルボニルォキシィミノ一 1 _フエニルプロパン一 1 _オンなどが挙げられ る。  [0101] Examples of the oxime derivative suitably used in the present invention include, for example, 3_benzoyloxyiminobutane 1_one, 3-acetoxyiminobutane 1_on, 3_propionyloxyiminobutane 1_on , 2-acetoximinopentane 1_one, 2-acetoximino 1_one, 2-vinylpropane 1_on, 2_benzoyloximino 1_phenolinopropane 1_on, 3_ (4 -Toluenesulfonyloxy) iminobutane-2-one and 2-ethoxycarbonyloxyimino-1- 1-phenylpropane-1-one.
[0102] 前記有機過酸化物としては、例えば、 3, 3 ' , 4, 4'—テトラ（t ブチルパーォキシ カルボニル）ベンゾフエノン、などが挙げられる。  [0102] Examples of the organic peroxide include 3, 3 ', 4, 4'-tetra (t-butylperoxycarbonyl) benzophenone.
前記チォ化合物としては、例えば、 2, 4—ジェチルチオキサントン、 2, 4—ジクロ口 チォキサントン、 1 クロロー 4 プロポキシチォキサントン、 2 べンゾィルメチレン 3—メチルナフトチアゾリン、などが挙げられる。  Examples of the thio compound include 2,4-jetylthioxanthone, 2,4-dichrothioxanthone, 1 chloro-4 propoxythioxanthone, 2 benzoylmethylene 3-methylnaphthothiazoline, and the like.
[0103] 前記ケトン化合物としては、例えば、ベンゾフヱノン、 2 メチルベンゾフエノン、 3— メチノレべンゾフエノン、 4ーメチノレべンゾフエノン、 4ーメトキシベンゾフエノン、 2—クロ 口べンゾフエノン、 4—クロ口べンゾフエノン、 4—ブロモベンゾフエノン、 2—カノレボキ シベンゾフエノン、 2—エトキシカルボニルベンゾルフェノン、ベンゾフエノンテトラカル ボン酸又はそのテトラメチルエステル、 4， 4'—ビス（ジアルキルァミノ）ベンゾフエノン 類（例えば、 4， 4，一ビス（ジメチルァミノ）ベンゾフエノン、 4, 4，一ビスジシクロへキシ ノレアミノ）ベンゾフエノン、 4, 4'—ビス（ジェチノレアミノ）ベンゾフエノン、 4， 4'—ビス（ ジヒドロキシェチルァミノ）ベンゾフエノン、 4—メトキシ一 4'—ジメチルァミノべンゾフエ ノン、 4， 4'—ジメトキシベンゾフエノン、 4—ジメチルァミノべンゾフエノン、 4_ジメチ ルアミノアセトフエノン、ベンジル、アントラキノン、 2— t—ブチルアントラキノン、 2—メ チルアントラキノン、フヱナントラキノン、キサントン、チォキサントン、 2_クロル一チォ キサントン、 2, 4_ジェチルチオキサントン、フルォレノン、 2_ベンジル一ジメチルァ ミノ一 1 _ (4—モルホリノフエ二ル）一 1—ブタノン、 2_メチル _ 1 _〔4_ (メチルチオ )フエニル〕一 2—モルホリノ一 1—プロパノン、 2—ヒドロキシ一 2—メチル一〔4— (1— メチルビニル）フエ二ノレ〕プロパノールオリゴマー、ベンゾイン、ベンゾインエーテル類 (例えば、ベンゾインメチルエーテル、ベンゾインェチルエーテル、ベンゾインプロピ ノレエーテノレ、ベンゾインイソプロピノレエーテノレ、ベンンインフエニノレエーテノレ、べンジ ルジメチルケタール）、アタリドン、クロロアタリドン、 N メチルアタリドン、 N ブチル アタリドン、 N ブチル一クロロアタリドンなどが挙げられる。 [0103] Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methenolebenzophenone, 4-methinolevenzophenone, 4-methoxybenzophenone, 2-clobenzobenzoneone, and 4-clobenzobenzoneone. 4-bromobenzophenone, 2-canoleboxibenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4,4′-bis (dialkylamino) benzophenones (for example, 4,4,1bis (dimethylamino) benzophenone, 4,4,1bisdicyclohexylenoleamino) benzophenone, 4,4'-bis (jetinoreamino) benzophenone, 4,4'-bis (dihydroxyethylamino) benzophenone, 4 —Methoxy-1 4′-dimethylaminoben Phenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4_dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone , Xanthone, thixanthone, 2_chlorothioxanthone, 2, 4_jetylthioxanthone, fluorenone, 2_benzyl monodimethylamino 1 _ (4-morpholinophenyl) 1 1-butanone, 2_methyl _ 1 _ [4_ (methylthio) phenyl] 1 2-morpholino 1-propanone, 2-hydroxy 1 2-methyl 1 [4- (1-methylvinyl) phenyl] propanol oligomers, benzoin, benzoin ethers (E.g., benzoin methyl ether, benzoin ethyl ether, benzoin propenoleatenore, benzoin isopropenoleatenore, benin phenenoleatenore, benzyl dimethyl ketal), attaridone, chloroataridon, N-methylataridon, N-butylataridon N-butyl monochloro attaridone and the like.
[0104] 前記芳香族ォニゥム塩としては、例えば、ジフエ二ルョードニゥムテトラフルォロボレ ート、ジフエニノレョードニゥムへキサフノレオ口ホスホネート、トリフエニノレスノレホニゥムテ トラフルォロボレート、トリフエニルスルホニゥムへキサフルォロホスホネート、テトラフエ ニルホスホニゥム一へキサフルォロホスフェート、などが挙げられる。  [0104] Examples of the aromatic onium salt include diphenyl rhodonitr tetrafluoroborate, diphenyleno melole phosphonate, triphenylenoles norehonumute traful. Examples include azoborate, triphenylsulfonium hexafluorophosphonate, tetraphenylphosphonium hexafluorophosphate, and the like.
前記メタ口セン類としては、例えば、ビス（ 7] 2, 4—シクロペンタジェン一 1—ィル )一ビス（2, 6 ジフロロー3—（1H—ピロ一ルー 1 ィル） フエニル）チタニウム、 7] 5—シクロペンタジェ二ノレ一 η 6—タメ二ノレ一アイアン（1 +)—へキサフロロホスフエ ート（1— )、などが挙げられる。 Examples of the metacathenes include bis (7) 2,4-cyclopentagen-1-yl) 1-bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, 7] 5 —Cyclopentadiniole η 6 —Tameninoleiron (1 +) — Hexafluorophosphate (1—), and the like.
[0105] また、上記以外の光重合開始剤として、 Ν フエニルダリシンなど、ポリハロゲン化 合物（例えば、四臭化炭素、フエニルトリブ口モメチルスルホン、フエニルトリクロロメチ ルケトンなど）、アミン類（例えば、 4ージメチルァミノ安息香酸ェチル、 4ージメチルァ ミノ安息香酸 η—ブチル、 4ージメチルァミノ安息香酸フエネチル、 4ージメチルァミノ 安息香酸 2—フタルイミドエチル、 4 ジメチルァミノ安息香酸 2—メタタリロイルォキシ ェチル、ペンタメチレンビス（4—ジメチルァミノべンゾエート）、 3—ジメチルァミノ安息 香酸のフエネチル、ペンタメチレンエステル、 4—ジメチルァミノべンズアルデヒド、 2 —クロル _ 4 _ジメチルァミノべンズアルデヒド、 4 -ジメチルァミノべンジルアルコ一 ノレ、ェチル（4—ジメチルァミノべンゾィル）アセテート、 4—ピベリジノアセトフヱノン、 4 —ジメチルァミノべンゾイン、 Ν, Ν—ジメチル _ 4—トルイジン、 Ν， Ν—ジェチル _ 3 —フエネチジン、トリベンジノレァミン、ジベンジルフエニルァミン、 Ν メチノレ一 Ν フ ェニルベンジルァミン、 4_ブロム _Ν，Ν_ジメチルァニリン、トリドデシノレァミン、タリ スタルバイオレツトラクトン、ロイコクリスタルバイオレットなど）、特開昭 53— 133428 号公報、特公昭 57— 1819号公報、同 57— 6096号公報、及び米国特許第 36154 55号明細書に記載された化合物などが挙げられる。  [0105] Further, as photopolymerization initiators other than those described above, polyhalogen compounds such as ダ phenyldaricin (for example, carbon tetrabromide, phenyl tribumomethylsulfone, phenyl trichloromethyl ketone, etc.), amines (for example, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid η-butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2-phthalimidoethyl, 4 dimethylaminobenzoic acid 2-metatalyloxyoxyethyl, pentamethylenebis (4-dimethylamino) Benzoate), 3-dimethylaminobenzoic acid phenethyl, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2 -chlor _ 4 _dimethylaminobenzaldehyde, 4-dimethylaminobenzil alcohol, ethyl (4-dimethyl) Aminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, Ν, Ν-dimethyl _ 4-toluidine, Ν, Ν-jetyl _ 3 —phenetidine, tribenzenoreamine, dibenzyl Phenylamine, Νmethylolene, phenylbenzylamine, 4_bromo_Ν, Ν_dimethylaniline, tridodecinoleamine, tarital biolactlactone, leucocrystal violet, etc.), JP-A 53- Examples thereof include compounds described in 133428, JP-B 57-1819, 57-6096, and US Pat. No. 3615455.
[0106] また、後述する感光層への露光における露光感度や感光波長を調整する目的で、 前記光重合開始剤に加えて、増感剤を添加することが可能である。 [0106] Further, for the purpose of adjusting the exposure sensitivity and photosensitive wavelength in exposure to the photosensitive layer described later, In addition to the photopolymerization initiator, a sensitizer can be added.
前記増感剤は、後述する光照射手段としての可視光線や紫外光及び可視光レー ザなどにより適宜選択することができる。  The sensitizer can be appropriately selected depending on visible light, ultraviolet light, visible light laser or the like as a light irradiation means described later.
前記増感剤は、活性エネルギー線により励起状態となり、他の物質 (例えば、ラジカ ル発生剤、酸発生剤等）と相互作用（例えば、エネルギー移動、電子移動等）するこ とにより、ラジカルや酸等の有用基を発生することが可能である。  The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby causing radicals and It is possible to generate useful groups such as acids.
尚、これらの化合物は、感光層の感度の向上を図るだけでなぐ光励起により前記 モノマーの重合を開始させるような光重合開始剤としての機能をも有している。  These compounds also have a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation only by improving the sensitivity of the photosensitive layer.
[0107] 前記増感剤としては、特に制限はなぐ公知の增感剤の中から適宜選択することが できるが、例えば、公知の多核芳香族類（例えば、ピレン、ペリレン、トリフエ二レン）、 キサンテン類（例えば、フルォレセイン、ェォシン、エリス口シン、ローダミン B、ローズ ベンガル）、シァニン類（例えば、インドカルボシァニン、チアカルボシァニン、ォキサ カルボシァニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、チア ジン類（例えば、チォニン、メチレンブルー、トルイジンブルー）、アタリジン類（例えば 、アタリジンオレンジ、クロロフラビン、ァクリフラビン）、アントラキノン類（例えば、アント ラキノン）、スクァリウム類 (例えば、スクァリウム）、などが挙げられる。  [0107] The sensitizer can be appropriately selected from known sensitizers that are not particularly limited. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), Xanthenes (for example, fluorescein, eosin, erythrosine synth, rhodamine B, rose bengal), cyanines (for example, indocarboyanine, thiacarboyanine, oxacarboyanine), merocyanines (for example, merocyanine, carbomerocyanine), Thiazines (for example, thionine, methylene blue, toluidine blue), atalidines (for example, atalidine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), etc. .
[0108] 前記増感剤としては、更に、ヘテロ縮環系化合物が好ましく挙げられる。前記へテ 口縮環系化合物とは、環の中にヘテロ元素を有する多環式化合物を意味し、前記環 の中に、窒素原子を含むのが好ましい。前記へテロ縮環系化合物としては、例えば、 ヘテロ縮環系ケトンィ匕合物、キノリンィ匕合物、アタリジン化合物が挙げられる。  [0108] Preferred examples of the sensitizer include hetero-fused compounds. The hetero-ring-ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound, a quinoline compound, and an atalidine compound.
前記へテロ縮環系ケトン化合物としては、具体的には、例えば、アタリドン、クロロア クリドン、 N メチルアタリドン、 N ブチルアタリドン、 N ブチル一クロロアタリドン、 などのアタリドン化合物；3— (2 ベンゾフロイル）_ 7—ジェチルァミノクマリン、 3 _ ( 2 _ベンゾフロイル）—Ί— ( 1—ピロリジニノレ）クマリン、 3 _ベンゾィル _ 7—ジェチル アミノクマリン、 3 - (2 メトキシベンゾィル） _ 7—ジェチルァミノクマリン、 3 _ (4—ジ メチルァミノベンゾィル）_ 7—ジェチルァミノクマリン、 3，3 ' _カルボ二ルビス（5, 7 —ジ一 n—プロポキシクマリン）、 3， 3，_カルボ二ルビス（7—ジェチルァミノクマリン） 、 3—ベンゾィル 7—メトキシクマリン、 3— (2—フロイル）一 7—ジェチルァミノタマリ ン、 3 _ (4—ジェチルァミノシンナモイル）一 7—ジェチルァミノクマリン、 7—メトキシ - 3 - (3—ピリジルカルボニル）クマリン、 3_ベンゾィル _ 5，7—ジプロポキシタマリ ン、 7_ベンゾトリアゾール _ 2_イルクマリン、 7—ジェチルァミノ一 4_メチルタマリ ン、また、特開平 5— 19475号、特開平 7— 271028号、特開 2002— 363206号、 特開 2002— 363207号、特開 2002— 363208号、特開 2002— 363209号公報等 に記載のクマリンィ匕合物、などのクマリン類；などが挙げられる。 Specific examples of the hetero-fused ketone compound include attaridone compounds such as attaridone, chloroacridone, N-methyl attaridone, N-butyl attalidone, N-butyl monochloro attaridone, etc .; 3- (2 benzofuroyl ) _ 7—Jetylaminocoumarin, 3 _ (2 _Benzofuroyl) —Ί— (1—Pyrrolidininole) coumarin, 3 _Benzyl _ 7—Jetyl aminocoumarin, 3-(2 methoxybenzoyl) _ 7—Jet Tyraminocoumarin, 3_ (4-Dimethylaminobenzoyl) _7-Jetylaminocoumarin, 3,3'_Carbonylbis (5,7-di-n-propoxycoumarin), 3, 3, _Carbonylbis (7-Jetylaminocoumarin), 3-Benzyl 7-methoxycoumarin, 3- (2-Furoyl) 1-Jetylaminominomari , 3 _ (4-Jetylaminocinnamoyl) -7-Jetylaminocoumarin, 7-Methoxy-3- (3-pyridylcarbonyl) coumarin, 3_Benzyl _ 5,7-dipropoxytamarin, 7_benzotriazole_2-ylcoumarin, 7-jetylamino 4-methyltamarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP And coumarins such as coumarin compounds described in JP-A-2002-363208 and JP-A-2002-363209.
[0109] 前記キノリンィ匕合物としては、具体的には、例えば、キノリン、 9—ヒドロキシ一1 , 2 ージヒドロキノリン 2 オン、 9 エトキシー 1 , 2 ジヒドロキノリン 2 オン、 9ージ ブチルアミノー 1 , 2 ジヒドロキノリンー2 オン、 8 ヒドロキシキノリン、 8 メルカプ トキノリン、キノリンー2—力ルボン酸、などが挙げられる。 [0109] Specific examples of the quinoline compound include, for example, quinoline, 9-hydroxy-1-1,2-dihydroquinoline 2-one, 9 ethoxy-1, 2-dihydroquinoline 2-one, 9-dibutylamino-1, 2 Dihydroquinoline-2-one, 8 hydroxyquinoline, 8 mercaptoquinoline, quinoline-2-powered rubonic acid, and the like.
前記アタリジン化合物としては、具体的には、例えば、 9—フエ二ルァクリジン、 1, 7 —ビス（9, 9，一アタリジニノレ）ヘプタン、アタリジンオレンジ、クロロフラビン、ァクリフラ ビン、などが挙げられる。これらへテロ縮環系化合物の中でも、環の中に窒素元素を 含有するものがより好ましい。前記環内に窒素元素を含有するものとしては、前記ァ クリジン化合物、アミノ基により置換されたクマリンィ匕合物、アタリドンィ匕合物、などが 好適に挙げられる。この中でも前記アタリドン、アミノ基により置換されたクマリン、 9 - フエ二ルァクリジン、などが更に好ましぐこれらの中でも、前記アタリドンが特に好まし レ、。  Specific examples of the atalidine compound include 9-phenacridine, 1,7-bis (9,9,1ataridininole) heptane, atalidine orange, chloroflavin, and acriflavine. Among these hetero-fused compounds, those containing a nitrogen element in the ring are more preferable. Preferred examples of the compound containing a nitrogen element in the ring include the acridine compound, a coumarin compound substituted with an amino group, and an attaridone compound. Among these, the talidone, the coumarin substituted with an amino group, 9-phenylacridine, and the like are more preferable, and the talidone is particularly preferable.
[0110] 前記光重合開始剤と前記増感剤との組合せとしては、例えば、特開 2001— 3057 34号公報に記載の電子移動型開始系 [ (1)電子供与型開始剤及び増感色素、（2) 電子受容型開始剤及び増感色素、（3)電子供与型開始剤、増感色素及び電子受容 型開始剤（三元開始系） ]などの組合せが挙げられる。  [0110] Examples of combinations of the photopolymerization initiator and the sensitizer include, for example, an electron transfer-type initiator system described in JP-A-2001-305734 [(1) an electron-donating initiator and a sensitizing dye , (2) electron accepting initiator and sensitizing dye, (3) electron donating initiator, sensitizing dye and electron accepting initiator (ternary initiation system)].
[0111] 前記増感剤の含有量としては、前記感光性組成物中の全成分に対し、 0. 05〜30 質量％が好ましぐ 0.：!〜 20質量％がより好ましぐ 0. 2〜： 10質量％が特に好ましい 。該含有量が、 0. 05質量％未満であると、活性エネルギー線への感度が低下し、露 光プロセスに時間がかかり、生産性が低下することがあり、 30質量％を超えると、保 存時に前記感光層から前記増感剤が析出することがある。  [0111] The content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0 to 20% by mass, based on all components in the photosensitive composition. 2 to 10% by mass is particularly preferable. If the content is less than 0.05% by mass, the sensitivity to active energy rays may be reduced, the exposure process may take time, and productivity may be reduced. When present, the sensitizer may precipitate from the photosensitive layer.
[0112] 前記光重合開始剤は、 1種単独で使用してもよぐ 2種以上を併用してもよい。 前記光重合開始剤の特に好ましい例としては、後述する露光において、波長が 40 5nmのレーザ光に対応可能である、前記ホスフィンオキサイド類、前記ひ —アミノア ルキルケトン類、前記トリァジン骨格を有するハロゲンィ匕炭化水素化合物とアミンィ匕 合物とを組合せた複合光開始剤、へキサァリールビイミダゾールイヒ合物、へキサァリ 一ルビイミダゾール化合物とヘテロ縮環系化合物、あるいは、メタ口セン類、などが挙 げられる。 [0112] The photopolymerization initiator may be used alone or in combination of two or more. As a particularly preferred example of the photopolymerization initiator, a halogenated carbon having the phosphine oxides, the triaminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the later-described exposure. Examples include composite photoinitiators that combine hydrogen compounds and amine compounds, hexaryl biimidazole compounds, hexyl biimidazole compounds and hetero-fused compounds, or meta-octenes. It is done.
更にこれらの開始剤とともに、連鎖移動剤（例えば、メルカプト化合物、より具体的 には、 2—メルカプトべンズイミダゾール、 2—メルカプトべンズォキサゾール、 2—メノレ カプトべンズチアゾール、など）を併用してもよい。  In addition to these initiators, chain transfer agents (for example, mercapto compounds, more specifically 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-menolecaptobenzthiazole, etc.) may be used in combination. Good.
[0113] 前記光重合開始剤の前記感光性組成物における含有量としては、 0.：!〜 30質量[0113] The content of the photopolymerization initiator in the photosensitive composition is from 0.:! To 30 masses.
%が好ましぐ 0. 5〜20質量％がより好ましぐ 0. 5〜： 15質量％が特に好ましい。 0.5 to 20% by mass is more preferable 0.5 to 15% by mass is particularly preferable.
[0114] 〔(D)硬化促進剤〕 [0114] [(D) Curing accelerator]
前記硬化促進剤は、前記 1分子中に 1個以上のカルボキシル基及びエステル基の レ、ずれかを有する重合体の熱硬化反応を促進するために添加される。  The curing accelerator is added to accelerate the thermosetting reaction of a polymer having one or more carboxyl groups and ester groups in one molecule.
前記硬化促進剤は、前記本発明の 1分子中に少なくとも 1個以上カルボキシル基 及びアミド基を共有する化合物からなるエポキシ樹脂用潜在硬化促進剤であり、前 記一般式（1)〜（6)のレ、ずれかで表される化合物であるのが好ましレ、。  The curing accelerator is a latent curing accelerator for epoxy resins composed of a compound sharing at least one carboxyl group and amide group in one molecule of the present invention, and the general formulas (1) to (6) It is preferable that the compound is represented by a deviation.
該硬化促進剤を感光性組成物、特に感光性フィルムとして製品化することにより、 保存時は反応を生じることがなぐ感光性組成物、或いは感光性フィルムの優れた保 存安定性が得られ、パターン形成のための加熱処理時には、速やかな反応を示して 化合物の硬化を促進し、形成される硬化膜の高い膜硬度、耐薬品性などが得られる 前記硬化促進剤の感光性組成物固形分中における固形分含有量としては、 0. 01 〜40質量％が好ましぐ 0. 01〜： 15質量％がより好まし 0. 05〜5質量％が特に 好ましレ、。前記含有量が 0. 01質量％未満であると、加熱処理時の反応が低下し、 硬化膜の膜強度の向上が図れないことがあり、 40質量％超であると、現像性、露光 感度の低下、及び硬化膜の膜硬度の低下を生ずることがある。  By commercializing the curing accelerator as a photosensitive composition, particularly a photosensitive film, it is possible to obtain a photosensitive composition that does not cause a reaction during storage, or an excellent storage stability of the photosensitive film. During the heat treatment for pattern formation, a rapid reaction is exhibited to accelerate the curing of the compound, and the cured film formed has high film hardness, chemical resistance, etc. The photosensitive composition solid content of the curing accelerator As a solid content in it, 0.01 to 40% by mass is preferable. 0.01 to: 15% by mass is more preferable, and 0.05 to 5% by mass is particularly preferable. When the content is less than 0.01% by mass, the reaction during the heat treatment is lowered, and the strength of the cured film may not be improved. When the content exceeds 40% by mass, the developability and exposure sensitivity are increased. And the hardness of the cured film may be lowered.
[0115] その他の熱硬化促進剤 前記エポキシ化合物の熱硬化を促進するため、本発明の硬化促進剤とは別個に、 従来公知の熱架橋剤などを、熱硬化促進剤として配合することができる。前記熱硬 化促進剤としては、例えば、ジシアンジアミド、ベンジルジメチルァミン、 4- (ジメチル ァミノ） _N, N—ジメチルベンジルァミン、 4—メトキシ一 N, N—ジメチルベンジルァ ミン、 4_メチル _N, N—ジメチルベンジルァミン等のアミン化合物；トリェチルベン ジルアンモニゥムクロリド等の 4級アンモニゥム塩化合物；ジメチルァミン等でブロック されたブロックイソシァネート化合物；イミダゾール、 2—メチルイミダゾール、 2—ェチ ルイミダゾール、 2—ェチルー 4ーメチルイミダゾール、 2—フエ二ルイミダゾール、 4 フエ二ルイミダゾール、 1ーシァノエチルー 2—フエ二ルイミダゾール、 1一（2—シァノ ェチル） 2—ェチルー 4ーメチルイミダゾール等のイミダゾール誘導体二環式アミジ ン化合物及びその塩；トリフエニルホスフィン等のリン化合物；メラミン、グアナミン、ァ セトグアナミン、ベンゾグアナミン等のグアナミン化合物； 2, 4 ジアミノー 6 メタタリ ロイルォキシェチル一 S トリァジン、 2 ビニル 2, 4 ジァミノ一 S トリアジン、 2 —ビニル一 4, 6 ジァミノ一 S トリァジン'イソシァヌル酸付加物、 2, 4 ジァミノ一 6—メタクリロイルォキシェチル一 S -トリァジン ·イソシァヌル酸付加物等の S—トリア ジン誘導体;などを用いることができる。これらは 1種単独で使用してもよぐ 2種以上 を併用してもよい。 [0115] Other thermosetting accelerators In order to accelerate the thermal curing of the epoxy compound, a conventionally known thermal crosslinking agent or the like can be blended as a thermal curing accelerator separately from the curing accelerator of the present invention. Examples of the thermosetting accelerator include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) _N, N-dimethylbenzylamine, 4-methoxy-1-N, N-dimethylbenzylamine, 4_methyl_N. , Amine compounds such as N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzil ammonium chloride; blocked isocyanate compounds blocked with dimethylamine; imidazole, 2-methylimidazole, 2-ethyl Imidazoles such as imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanethyl-2-phenylimidazole, 1- (2-cyanethyl) 2-ethyl-4-methylimidazole, etc. Derivative bicyclic amidin compounds and salts thereof; Phosphorus compounds such as sphin; Guanamine compounds such as melamine, guanamine, acetoguanamine, and benzoguanamine; 2,4 diamino-6 metathalyllooxychetyl 1 S triazine, 2 vinyl 2, 4 diamino 1 S triazine, 2 —vinyl 1 4 , 6 dianamino 1 S-triazine 'isocyanuric acid adduct, S-triazine derivatives such as 2, 4 dianamino 6-methacryloyloxychetyl 1 S-triazine isocyanuric acid adduct, and the like can be used. These may be used alone or in combination of two or more.
なお、前記その他の熱硬化促進剤としては、前記エポキシ化合物の熱硬化を促進 することができるものであれば、特に制限はなぐ上記以外の熱硬化を促進可能な化 合物を用いてもよい。  The other thermosetting accelerator is not particularly limited as long as it can accelerate the thermosetting of the epoxy compound, and other compounds that can accelerate the thermosetting may be used. .
[0116] 前記その他の熱硬化促進剤の前記感光性組成物固形分中の固形分含有量として は、 0. 01〜： 15質量％が好ましい。  [0116] The solid content of the other thermosetting accelerator in the solid content of the photosensitive composition is preferably 0.01 to 15% by mass.
[0117] 〔(E)熱架橋剤〕  [0117] [(E) Thermal crosslinking agent]
前記熱架橋剤としては、特に制限はなぐ 目的に応じて適宜選択することができ、 前記感光性組成物を用いて形成される感光層の硬化後の膜強度を改良するために 、現像性等などに悪影響を与えない範囲で、例えば、 1分子内に少なくとも 2つのォ キシラン基を有するエポキシ化合物、 1分子内に少なくとも 2つのォキセタニル基を有 するォキセタン化合物を用いることができる。 前記 1分子内に少なくとも 2つのォキシラン基を有するエポキシィ匕合物としては、例 えば、ビキシレノール型もしくはビフエノール型エポキシ樹脂（「YX4000；ジャパンェ ポキシレジン社製」等）又はこれらの混合物、イソシァヌレート骨格等を有する複素環 式エポキシ樹脂（「TEPIC ;日産化学工業社製」、「ァラルダイト PT810 ;チバ'スぺシ ャルティ'ケミカルズ社製」等）、ビスフエノール A型エポキシ樹脂、ノボラック型ェポキ シ樹脂、ビスフエノール F型エポキシ樹脂、水添ビスフエノール A型エポキシ樹脂、グ リシジノレアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、脂環式エポキシ樹脂、ト リヒドロキシフエニルメタン型エポキシ樹脂、ビスフエノール S型エポキシ樹脂、ビスフ ェノール Aノボラック型エポキシ樹脂、テトラフエ二ロールエタン型エポキシ樹脂、ダリ シジルフタレート樹脂、テトラグリシジノレキシレノィルェタン樹脂、ナフタレン基含有ェ ポキシ樹脂ひ ESN— 190, ESN— 360 ;新曰鉄ィ匕学社製」、「HP— 4032, EXA— 4750, EXA— 4700 ;大日本インキ化学工業社製」等）、ジシクロペンタジェン骨格 を有するエポキシ樹脂（「HP— 7200, HP - 7200H；大日本インキ化学工業社製」 等）、グリシジルメタアタリレート共重合系エポキシ樹脂ひ CP— 50S, CP- 50M ;日 本油脂社製」等）、シクロへキシルマレイミドとグリシジルメタアタリレートとの共重合ェ ポキシ樹脂などが挙げられる力 これらに限られるものではない。これらのエポキシ樹 脂は、 1種単独で使用してもよいし、 2種以上を併用してもよい。 The thermal crosslinking agent is not particularly limited and can be appropriately selected according to the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability, etc. For example, an epoxy compound having at least two oxsilane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used. Examples of the epoxy compound having at least two oxysilane groups in one molecule include, for example, bixylenol type or biphenol type epoxy resins (“YX4000; manufactured by Japan Epoxy Resin” etc.) or a mixture thereof, isocyanurate skeleton, etc. Heterocyclic epoxy resins (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba“ Specialty Chemicals ”, etc.), bisphenol A type epoxy resins, novolak type epoxy resins, bis Phenolic F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidinoleamine type epoxy resin, hydantoin type epoxy resin, cycloaliphatic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol Enol A novolac epoxy resin, Tet Phenylolethane type epoxy resin, Daricidyl phthalate resin, Tetraglycidino lexylylene ethane resin, Naphthalene group-containing epoxy resin ESN-190, ESN-360; — 4032, EXA— 4750, EXA— 4700; manufactured by Dainippon Ink Chemical Co., Ltd.), epoxy resin having a dicyclopentagen skeleton (“HP-7200, HP-7200H; manufactured by Dainippon Ink Chemical Co., Ltd.”), etc. ), Glycidyl metaatacrylate copolymer-based epoxy resin CP-50S, CP-50M; manufactured by Nippon Oil & Fats Co., Ltd.), cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin, etc. However, it is not limited to these. These epoxy resins may be used alone or in combination of two or more.
[0118] また、前記 1分子内に少なくとも 2つのォキシラン基を有する前記エポキシ化合物以 外に、 /3位にアルキル基を有するエポキシ基を少なくとも 1分子中に 2つ含むェポキ シィ匕合物を用いることができ、 β位がアルキル基で置換されたエポキシ基（より具体 的には、 β—アルキル置換グリシジノレ基など）を含む化合物が特に好ましい。 [0118] In addition to the epoxy compound having at least two oxysilane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the / 3-position in one molecule is used. A compound containing an epoxy group substituted at the β-position with an alkyl group (more specifically, a β-alkyl-substituted glycidinole group or the like) is particularly preferable.
前記 j3位にアルキル基を有するエポキシ基を少なくとも含むエポキシ化合物は、 1 分子中に含まれる 2個以上のエポキシ基のすべてが β—アルキル置換グリシジル基 であってもよく、少なくとも 1個のエポキシ基が j3 _アルキル置換グリシジル基であつ てもよい。  In the epoxy compound containing at least an epoxy group having an alkyl group at the j3 position, all of two or more epoxy groups contained in one molecule may be β-alkyl-substituted glycidyl groups, and at least one epoxy group May be a j3_alkyl-substituted glycidyl group.
[0119] 前記 β位にアルキル基を有するエポキシ基を含むエポキシ化合物は、室温におけ る保存安定性の観点から、前記感光性組成物中に含まれる前記エポキシ化合物全 量中における、全エポキシ基中の アルキル置換グリシジノレ基の割合力 70%以 上であることが好ましい。 [0119] From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is an all-epoxy group in the total amount of the epoxy compound contained in the photosensitive composition. Percentage of alkyl-substituted glycidinole group in 70% or more It is preferable that it is above.
前記 —アルキル置換グリシジノレ基としては、特に制限は無 目的に応じて適宜 選択することができ、例えば、 /3—メチルダリシジノレ基、 /3 —ェチルダリシジノレ基、 β —プロピルグリシジル基、 /3—ブチルダリシジル基、などが挙げられ、これらの中でも 、前記感光性樹脂組成物の保存安定性を向上させる観点、及び合成の容易性の観 点力ら、 /3—メチルダリシジノレ基が好ましい。  The —alkyl-substituted glycidinole group is not particularly limited and may be appropriately selected depending on the purpose. For example, / 3-methyldaricidinole group, / 3-ethylidylidinole group, β-propylglycidyl group , / 3-butyldaricidyl group, etc. Among these, from the viewpoint of improving the storage stability of the photosensitive resin composition and the viewpoint of ease of synthesis, / 3-methyldaricidinole group Is preferred.
[0120] 前記 β位にアルキル基を有するエポキシ基を含むエポキシ化合物としては、例え ば、多価フエノール化合物と —アルキルェピハロヒドリンとから誘導されたエポキシ 化合物が好ましい。 [0120] The epoxy compound containing an epoxy group having an alkyl group at the β-position is preferably, for example, an epoxy compound derived from a polyhydric phenol compound and an -alkylephalohydrin.
[0121] 前記 β—アルキルェピハロヒドリンとしては、特に制限はなぐ 目的に応じて適宜選 択することができ、例えば、 βーメチルェピクロロヒドリン、 β メチルェピブロモヒドリ ン、 βーメチルェピフロロヒドリン等の β メチルェピハロヒドリン； βーェチルェピクロ ロヒドリン、 ェチルェピブ口モヒドリン、 ーェチルェピフロロヒドリン等の —ェチ ルェピハロヒドリン； β プロピルェピクロロヒドリン、 β プロピルェピブ口モヒドリン、 β プロピルェピフロロヒドリン等の β プロピルェピハロヒドリン； β ブチルェピク ロロヒドリン、 β ブチルェピブ口モヒドリン、 βーブチルェピフロロヒドリン等の βーブ チルェピハロヒドリン；などが挙げられる。これらの中でも、前記多価フエノールとの反 応性及び流動性の観点から、 β—メチルェピハロヒドリンが好ましい。  [0121] The β-alkylepihalohydrin is not particularly limited and can be appropriately selected according to the purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepihalohydrin, such as β-methylepifluorohydrin; β-ethylepichlorohydrin, ethylepive mouth mohydrin, ethylepifluorohydrin, etc. —ethylepihalohydrin; β-propylepichloro Β-propylepihalohydrin, such as hydrin, β-propylepib mouth mohydrin, β-propylepifluorohydrin; β-butylepephalohydrin, β-butylepive mouth mohydrin, β-butylepifluorohydrin, etc. Halohydrin; and the like. Among these, β-methylepihalohydrin is preferable from the viewpoints of reactivity with the polyhydric phenol and fluidity.
[0122] 前記多価フエノール化合物としては、 1分子中に 2以上の芳香族性水酸基を含有 する化合物であれば、特に制限は無ぐ 目的に応じて適宜選択することができ、例え ば、ビスフエノーノレ Α、ビスフエノール F、ビスフエノール S等のビスフエノール化合物； ビフエノール、テトラメチルビフエノール等のビフエノール化合物；ジヒドロキシナフタレ ン、ビナフトール等のナフトール化合物；フエノール—ホルムアルデヒド重縮合物等の フエノールノボラック樹脂；タレゾール—ホルムアルデヒド重縮合物等の炭素数 1〜： 10 のモノアルキル置換フヱノール一ホルムアルデヒド重縮合物；キシレノール一ホルム アルデヒド重縮合物等の炭素数 1〜： 10のジアルキル置換フエノール—ホルムアルデ ヒド重縮合物；ビスフヱノール A ホルムアルデヒド重縮合物等のビスフヱノール化合 物 ホルムアルデヒド重縮合物；フエノールと炭素数 1〜 10のモノアルキル置換フエ ノールとホルムアルデヒドとの共重縮合物；フヱノール化合物とジビュルベンゼンの重 付加物；などが挙げられる。これらの中でも、例えば、流動性及び保存安定性を向上 させる目的で選択する場合には、前記ビスフエノール化合物が好ましい。 [0122] The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose, for example, bisphenol alcohol. Bisphenol compounds such as Α, bisphenol F and bisphenol S; biphenol compounds such as biphenol and tetramethylbiphenol; naphthol compounds such as dihydroxynaphthalene and binaphthol; phenol novolak resins such as phenol-formaldehyde polycondensates; A monoalkyl-substituted phenol monoformaldehyde polycondensate having 1 to 10 carbon atoms such as formaldehyde polycondensate; a dialkyl-substituted phenol having 1 to 10 carbon atoms such as xylenol monoform aldehyde polycondensate and a formaldehyde polycondensate; Bisphenol A A Holmoor Bisphenol compounds such as aldehyde polycondensates Formaldehyde polycondensates; phenols and monoalkyl-substituted phenols having 1 to 10 carbon atoms For example, a copolycondensate of diol and formaldehyde; a polyadduct of phenol compound and dibutenebenzene; Among these, for example, when selecting for the purpose of improving fluidity and storage stability, the bisphenol compound is preferable.
[0123] 前記 β位にアルキル基を有するエポキシ基を含むエポキシ化合物としては、例え ば、ビスフエノーノレ Αのジ一 β—アルキルグリシジルエーテル、ビスフエノール Fのジ - β—アルキルグリシジルエーテル、ビスフエノール Sのジ一 β—アルキルグリシジ ルエーテル等のビスフエノール化合物のジ— —アルキルグリシジルエーテル；ビフ ェノールのジー β アルキルグリシジルエーテル、テトラメチルビフエノールのジー β アルキルグリシジルエーテル等のビフエノール化合物のジー β アルキルグリシジ ルエーテル；ジヒドロキシナフタレンのジー β アルキルグリシジルエーテル、ビナフ トールのジー β アルキルグリシジルエーテル等のナフトール化合物の β アルキ ルグリシジルエーテル；フエノールーホルムアルデヒド重縮合物のポリ β アルキ ルグリシジルエーテル；クレゾ一ルーホルムアルデヒド重縮合物のポリ β アルキ ルグリシジルエーテル等の炭素数 1〜10のモノアルキル置換フエノールーホルムァ ルデヒド重縮合物のポリ β アルキルグリシジルエーテノレ；キシレノールーホルム アルデヒド重縮合物のポリ β アルキルグリシジルエーテル等の炭素数 1〜： 10の ジアルキル置換フエノールーホルムアルデヒド重縮合物のポリ β アルキルグリシ ジルエーテル；ビスフエノーノレ Α—ホルムアルデヒド重縮合物のポリ一 β—アルキル グリシジルエーテル等のビスフヱノール化合物—ホルムアルデヒド重縮合物のポリ— β—アルキルグリシジルエーテル；フヱノール化合物とジビュルベンゼンの重付加物 のポリ一 j3—アルキルグリシジルエーテル；などが挙げられる。 [0123] Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ethers of bisphenol or bisphenol F, di-β-alkyl glycidyl ethers of bisphenol F, and bisphenol S. Di-β-alkyl glycidyl ethers and other bisphenol compounds such as di-alkyl glycidyl ethers; Biphenol diols β alkyl glycidyl ethers and tetramethylbiphenol diols β alkyl glycidyl ethers and other biphenol compound diols β alkyl glycidyl Β ether glycidyl ethers of naphthol compounds such as dihydroxy naphthalene bis β alkyl glycidyl ether and binaphthol bis β alkyl glycidyl ether; phenol-formaldehyde polycondensate Poly β alkyl glycidyl ether; poly β alkyl glycidyl etherol of 1-10 carbon monoalkyl-substituted phenol-formaldehyde polycondensate such as poly β alkyl glycidyl ether of creso-ru formaldehyde polycondensate; xylenol -Formaldehyde aldehyde polycondensate poly β alkyl glycidyl ether, etc. C1-C10 dialkyl substituted phenol-formaldehyde polycondensate poly β alkyl glycidyl ether; bisphenolate Α-formaldehyde polycondensate poly β- Bisphenol compounds such as alkyl glycidyl ethers-polyformaldehyde polycondensate poly-beta-alkyl glycidyl ethers; polyadducts of phenol compounds and dibutenebenzene poly j3-alkyl glycidyl ethers, etc. That.
これらの中でも、ビスフエノール化合物、及びこれとェピクロロフドリンなどから得られ る重合体から誘導される /3 _アルキルグリシジルエーテル、及びフヱノール化合物— ホルムアルデヒド重縮合物のポリ— /3—アルキルグリシジルエーテルが好ましい。  Among these, / 3_alkyl glycidyl ethers derived from bisphenol compounds and polymers obtained from these and epic chlorohydrin, etc., and phenol compounds—polyformaldehyde polycondensate poly-3-alkyl glycidyl ethers Is preferred.
[0124] また、前記熱架橋剤は、一分子内に少なくとも 2つのォキシラン基を有するエポキシ 化合物であり、前記ォキシラン基が 2つの置換基を有している化合物であることが好 ましレ、。前記ォキシラン基における 2つの置換基のうち、 1つの置換基は、前記一分 子内に存在する 2つ以上のォキシラン基を連結するためのものであり、さらに、前記 ォキシラン基には、該置換基 (ォキシラン基を連結するためのもの）以外の置換基が 存在することが好ましい。 [0124] The thermal cross-linking agent is preferably an epoxy compound having at least two oxosilane groups in one molecule, and the oxysilane group is a compound having two substituents. Of the two substituents in the oxysilane group, one substituent is for linking two or more oxysilane groups present in the molecule, and It is preferable that a substituent other than the substituent (for linking the oxysilane group) is present in the oxysilane group.
このような熱架橋剤としては、下記一般式（7) （9)のいずれかで表される化合物 であることが好ましい。  Such a thermal crosslinking agent is preferably a compound represented by any one of the following general formulas (7) and (9).
[化 37] 一般式（7 ) [Chemical formula 37] General formula (7)
一般式（8) General formula (8)
Figure imgf000059_0001
Figure imgf000059_0001
ただし、前記一般式（7)、（8)、及び（9)中、 Pは、酸素原子、カルボニル基、アミド 基、ウレタン基、アルキレン基、及びァリーレン基のいずれかを表し、 Qは、ホウ素原 子、窒素原子、アルキレン基、及びァリーレン基のいずれかを表し、 Wは、 2つの X26 と結合を有するナフタレンを表し、 A21 A25は、単結合、アルキレン基、及びァリーレ ン基のいずれかを表し、 X21 X26は、 OCONH― NHCOO NHCO— 、及び CONH のいずれかを表す。 R21 R26は、水素原子、ハロゲン原子、アル キル基、及びァリール基のいずれかを表す。 However, in the general formulas (7), (8), and (9), P represents an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene group, or an arylene group, and Q represents boron. Represents an atom, a nitrogen atom, an alkylene group, or an arylene group, W represents naphthalene having a bond with two X 26 s , A 21 A 25 represents a single bond, an alkylene group, or an arylene group. X 21 X 26 represents any one of OCONH—NHCOO NHCO— and CONH. R 21 R 26 represents any one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
前記 Pにおけるアルキレン基としては、例えば、無置換アルキレン基、及びァリール 基 ·アルケニル基 ·ヒドロキシル基 ·アルコキシ基 ·シァノ基 'ハロゲン原子で置換され ている置換基含有アルキレン基、などが挙げられる。  Examples of the alkylene group in P include an unsubstituted alkylene group, an aryl group, an alkenyl group, a hydroxyl group, an alkoxy group, a cyan group, and a substituent-containing alkylene group substituted with a halogen atom.
前記無置換アルキレン基としては、分岐を有していてもよぐ二重結合、三重結合を 有していてもよい。  The unsubstituted alkylene group may have a double bond or a triple bond which may have a branch.
前記無置換アルキレン基の総炭素数としては、：!〜 20が好ましぐ：!〜 8が特に好ま しい。 前記無置換アルキレン基の具体例としては、例えば、エチレン、プロピレン、 i_プロ ピレン、ブチレン、 i—ブチレン、シクロへキシレン、などが挙げられる。 As the total number of carbon atoms of the unsubstituted alkylene group,:!-20 is preferable:!-8 is particularly preferable. Specific examples of the unsubstituted alkylene group include ethylene, propylene, i_propylene, butylene, i-butylene, cyclohexylene, and the like.
前記置換基含有アルキレン基中のァリール置換基としては、総炭素数 6〜30のも のが好ましぐ 6〜： 15が特に好ましい。前記ァリール置換基として、例えば、フエ二ノレ 基、ナフチル基、アントラセニル基、メトキシフヱニル基、クロロフヱニル基、などが挙 げられる。  As the aryl substituent in the substituent-containing alkylene group, those having a total carbon number of 6 to 30 are preferable, and 6 to 15 is particularly preferable. Examples of the aryl substituent include a phenylol group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
前記置換基含有アルキレン基中のアルケニル置換基としては、総炭素数 2〜： 10が 好ましぐ 2〜6が特に好ましい。前記アルケニル置換基として、例えば、ェチュル基 、プロぺニル基、プチリル基、などが挙げられる。  The alkenyl substituent in the substituent-containing alkylene group preferably has 2 to 6 carbon atoms, particularly preferably 2 to 6 carbon atoms. Examples of the alkenyl substituent include an ethur group, a propenyl group, a petityl group, and the like.
前記置換基含有アルキレン基中のアルコキシ置換基としては、分岐を有していても よぐ総炭素数:!〜 10が好ましぐ：!〜 5が特に好ましい。前記アルコキシ置換基とし て、例えば、メトキシ基、エトキシ基、プロピルォキシ基、 2—メチルプロピルォキシ基、 ブトキシ基、などが挙げられる。  The alkoxy substituent in the substituent-containing alkylene group preferably has a total carbon number of! To 10 which may have a branch:! To 5 is particularly preferable. Examples of the alkoxy substituent include a methoxy group, an ethoxy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.
前記置換基含有アルキレン基としては、分岐を有していてもよぐ二重結合、三重 結合を有していてもよい。  The substituent-containing alkylene group may have a double bond or a triple bond which may have a branch.
前記置換基含有アルキレン基の総炭素数としては、 2〜40力 S好ましく、 2〜25が特 に好ましい。  The total number of carbon atoms of the substituent-containing alkylene group is preferably 2 to 40 forces S, and particularly preferably 2 to 25.
前記置換含有アルキレン基の具体例としては、例えば、 2_ェチルへキシノレ基、ク ロロブチル基、ベンジル基、 2—ェチュルプロピル基、フエニルェチル基、シァノプロ ピル基、メトキシェチル基、などが挙げられる。  Specific examples of the substituent-containing alkylene group include 2_ethylhexenole group, chlorobutyl group, benzyl group, 2-ethylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group, and the like.
前記 Pのァリーレン基としては、後述する A21〜A25のァリーレン基と同義である。 前記 Qにおけるアルキレン基としては、例えば、前記 Pにおける無置換アルキレン 基が挙げられる。 The arylene group for P has the same meaning as the arylene group for A 21 to A 25 described later. Examples of the alkylene group for Q include an unsubstituted alkylene group for P.
前記無置換アルキレン基としては、例えば、分岐を有していてもよぐ二重結合、三 重結合を有していてもよい。  The unsubstituted alkylene group may have, for example, a double bond or a triple bond that may have a branch.
前記無置換アルキレン基の総炭素数としては、例えば、 2〜30が好ましい。  As a total carbon number of the said unsubstituted alkylene group, 2-30 are preferable, for example.
前記無置換アルキレン基の具体例としては、例えば、エチレン、プロピレン、 i_プロ ピレン、ブチレン、 iーブチレン、シクロへキシレン、などが挙げられる。 前記 Qのァリーレン基としては、後述する A21〜A25のァリーレン基と同義である。 Specific examples of the unsubstituted alkylene group include ethylene, propylene, i_propylene, butylene, i-butylene, cyclohexylene, and the like. The arylene group of Q has the same meaning as the arylene group of A 21 to A 25 described later.
[0127] 前記 Wのおける X部との結合部位としては、例えば、 1 , 2位、 1， 3位、 1 , 5位、 1， 6 位、 1， 7位、 1 , 8位、 2, 3位、 2, 4位、 2, 5位、 2, 7位力 S挙げられる。 [0127] Examples of the binding site with the X moiety in W include, for example, 1, 2 position, 1, 3 position, 1, 5 position, 1, 6 position, 1, 7 position, 1, 8 position, 2, 3rd, 2, 4th, 2, 5th, 2, 7th place S
前記 Wとしては、アルキル基、ァリーノレ基、アルコキシ基、及びハロゲン原子のいず れかで置換されてレ、てもよレ、。  The W may be an alkyl group, an aryleno group, an alkoxy group, or a halogen atom, which may be substituted.
[0128] 前記 A21〜A25におけるァリーレン基としては、例えば、ベンゼン環、及び、アルキル 基 ·ァリール基 ·アルケニル基 ·アルコキシ基 ·シァノ基 'ノ、ロゲン原子で置換されてレヽ る置換基含有ァリーレン基が挙げられる。 Examples of the arylene group in A 21 to A 25 include, for example, a benzene ring and an alkyl group, an aryl group, an alkenyl group, an alkoxy group, a cyan group, and a substituent that is substituted with a rogen atom. An arylene group.
前記置換基含有ァリーレン基中のアルキル置換基としては、分岐を有していてもよ ぐ二重結合、三重結合を有していてもよぐ総炭素数は 1〜20のものが好ましぐ 1 〜： 10が特に好ましい。前記アルキル置換基としては、メチル基、ェチル基、ェチニノレ 基、プロピル基、イソプロピル基、ブチル基、 s ブチル基、 t ブチル基、ブチリル基 、シクロへキシル基、シクロへキセニル基、などが挙げられる。  The alkyl substituent in the substituent-containing arylene group is preferably one having a total number of carbon atoms of 1 to 20 which may have a double bond or a triple bond which may have a branch. 1 to 10 is particularly preferable. Examples of the alkyl substituent include a methyl group, an ethyl group, an ethynino group, a propyl group, an isopropyl group, a butyl group, an sbutyl group, a tbutyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group. .
前記置換基含有ァリーレン基中のァリール置換基としては、総炭素数 6〜30のもの が好ましぐ 6〜： 15が特に好ましい。前記ァリール置換基としては、例えば、フエ二ノレ 基、ナフチル基、アントラセニル基、メトキシフヱニル基、クロロフヱニル基、などが挙 げられる。  As the aryl substituent in the substituent-containing arylene group, those having a total carbon number of 6 to 30 are preferable, and 6 to 15 is particularly preferable. Examples of the aryl substituent include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
前記置換基含有ァリーレン基中のアルケニル置換基としては、総炭素数 2〜： 10が 好ましぐ 2〜6が特に好ましい。前記アルケニル置換基としては、例えば、ェチュル 基、プロぺニル基、プチリル基、などが挙げられる。  The alkenyl substituent in the substituent-containing arylene group preferably has 2 to 6 carbon atoms, particularly preferably 2 to 6 carbon atoms. Examples of the alkenyl substituent include an ethur group, a propenyl group, a petityl group, and the like.
前記置換基含有ァリーレン基中のアルコキシ置換基としては、分岐を有していても よ 総炭素数:!〜 10が好まし ：!〜 5が特に好ましい。前記アルコキシ置換基とし ては、例えば、メトキシ基、エトキシ基、プロピルォキシ基、 2 _メチルプロピルォキシ 基、ブトキシ基、などが挙げられる。  The alkoxy substituent in the substituent-containing arylene group may have a branch, but preferably has a total carbon number:! To 10 and particularly preferably! To 5. Examples of the alkoxy substituent include a methoxy group, an ethoxy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.
前記置換基含有ァリーレン基としては、分岐を有していてもよぐ二重結合、三重結 合を有していてもよぐ総炭素数 2〜40が好ましぐ 2〜25が特に好ましい。  The substituent-containing arylene group is particularly preferably 2 to 25, preferably a total of 2 to 40 carbon atoms which may have a double bond or a triple bond.
前記置換基含有ァリーレン基の具体例としては、例えば、メチルフヱニル環、ジメチ ルフエ二ル環、ジブチルフエニル環、メトキシフエニル環、シクロへキシルフェニル環、 ビフエ二ル構造、ジクロロフヱニル環、トリブロモフエニル環、クロロシアノフヱニル環、 などが挙げられる。 Specific examples of the substituent-containing arylene group include, for example, a methyl phenyl ring, a dimethyl phenyl ring, a dibutyl phenyl ring, a methoxy phenyl ring, a cyclohexyl phenyl ring, And biphenyl structure, dichlorophenyl ring, tribromophenyl ring, chlorocyanophenyl ring, and the like.
前記 A21〜A25におけるアルキレン基は、前記 Pにおけるアルキレン基と同義である。 The alkylene group for A 21 to A 25 has the same meaning as the alkylene group for P.
[0129] 前記 X21〜X26は、前述のように、一〇C〇NH―、一 NHCOO 、一 NHCO 、及 び _C〇NH_のいずれかを表す。 [0129] As described above, X 21 to X 26 represent any one of 10C 0 NH-, 1 NHCOO, 1 NHCO, and _C 0 NH_.
[0130] 前記 R21〜R26におけるアルキル基としては、例えば、無置換アルキル基、及び、ァリ ール基 .アルケニル基 .ヒドロキシル基、アルコキシ基 .シァノ基 'ハロゲン原子で置換 されており、酸素原子 ·硫黄原子'カルボニル基 ·アミド基'ウレタン基'ウレァ基、エス テル基の 2価の基を有していてもよい置換基含有アルキル基が挙げられる。 [0130] Examples of the alkyl group in R 21 to R 26 include, for example, an unsubstituted alkyl group, and an aryl group, an alkenyl group, a hydroxyl group, an alkoxy group, a cyan group, and a halogen atom. Examples thereof include a substituent-containing alkyl group which may have a divalent group of oxygen atom, sulfur atom, carbonyl group, amide group, urethane group, urea group and ester group.
前記無置換アルキル基としては、分岐を有していてもよぐ二重結合、三重結合を 有していてもよぐ総炭素数は 1〜20のものが好ましぐ：!〜 10が特に好ましい。 前記無置換アルキル基としては、例えば、メチル基、ェチル基、ェチニル基、プロピ ル基、イソプロピル基、ブチル基、 s ブチル基、 t ブチル基、ブチリル基、シクロへ キシノレ基、シクロへキセニル基、などが挙げられる。  The unsubstituted alkyl group is preferably one having a total number of carbon atoms of 1 to 20 which may have a double bond or a triple bond which may have a branch: preferable. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, a sbutyl group, a tbutyl group, a butyryl group, a cyclohexynole group, a cyclohexenyl group, Etc.
前記置換基含有アルキル基中のァリール置換基としては、総炭素数 6〜30のもの が好ましぐ 6〜： 15が特に好ましい。前記ァリール置換基としては、例えば、フエ二ノレ 基、ナフチル基、アントラセニル基、メトキシフヱニル基、クロロフヱニル基、などが挙 げられる。  As the aryl substituent in the substituent-containing alkyl group, those having a total carbon number of 6 to 30 are preferable, and 6 to 15 is particularly preferable. Examples of the aryl substituent include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, a chlorophenyl group, and the like.
前記置換基含有アルキル基中のアルケニル置換基としては、総炭素数 2〜： 10が好 ましぐ 2〜6が特に好ましい。前記アルケニル置換基としては、例えば、ェチュル基、 プロぺニル基、ブチリル基、などが挙げられる。  The alkenyl substituent in the substituent-containing alkyl group preferably has a total carbon number of 2 to 10 and particularly preferably 2 to 6. Examples of the alkenyl substituent include an ethur group, a propenyl group, a butyryl group, and the like.
前記置換基含有アルキル基中のアルコキシ置換基としては、分岐を有していてもよ ぐ総炭素数 1〜： 10が好ましぐ：!〜 5が特に好ましい。前記アルコキシ置換基として は、例えば、メトキシ基、エトキシ基、プロピルォキシ基、 2 _メチルプロピルォキシ基 、ブトキシ基、などが挙げられる。  As the alkoxy substituent in the substituent-containing alkyl group, a total carbon number of 1 to 10 which may have a branch is preferable:! To 5 is particularly preferable. Examples of the alkoxy substituent include methoxy group, ethoxy group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
前記置換基含有アルキル基としては、分岐を有していてもよ 二重結合、三重結 合を有していてもよぐ総炭素数 2〜40が好ましぐ 2〜25が特に好ましい。  As the substituent-containing alkyl group, a total number of carbon atoms of 2 to 40, which may be branched or may have a double bond or a triple bond, is preferred, and 2 to 25 is particularly preferred.
前記置換含有アルキル基としては、例えば、 2—ェチルへキシル基、クロロブチル 基、ベンジル基、 2—ェチュルプロピル基、フエニルェチル基、シァノプロピル基、メト キシェチル基、などが挙げられる。 Examples of the substituted alkyl group include 2-ethylhexyl group, chlorobutyl Group, benzyl group, 2-ethylpropyl group, phenylethyl group, cyanopropyl group, methoxetyl group, and the like.
前記一般式（7)〜（9)のいずれかで表される化合物としては、例えば、下記式で表 される化合物などが挙げられる。  Examples of the compound represented by any one of the general formulas (7) to (9) include a compound represented by the following formula.
[化 38] [Chemical 38]
Figure imgf000064_0001
化合物例 6 化合物例 7 化合物例 8 ίヒ合物例 9 化合物例 1G
Figure imgf000064_0002
Figure imgf000064_0001
Compound Example 6 Compound Example 7 Compound Example 8 ίH Compound Example 9 Compound Example 1G
Figure imgf000064_0002
化合物例 11 化合物例 12 化合物例 13 化合物例 14 化合物例 1'  Compound Example 11 Compound Example 12 Compound Example 13 Compound Example 14 Compound Example 1 '
Figure imgf000064_0003
Figure imgf000064_0003
化台物例 16 化台物例 17 化合物例 18 iL^ff'Jl9 it^ iO Chemical table example 16 Chemical table example 17 Compound example 18 iL ^ ff'Jl9 it ^ iO
[0132] 前記ォキセタン化合物としては、例えば、ビス [ (3—メチル _ 3—ォキセタニルメトキ シ）メチル]エーテル、ビス [ (3 _ェチル _ 3—ォキセタニルメトキシ）メチル]エーテル 、 1， 4_ビス [ (3—メチル _ 3—ォキセタニルメトキシ）メチル]ベンゼン、 1， 4_ビス [ (3 _ェチル _ 3—ォキセタニルメトキシ）メチル]ベンゼン、 （3 _メチル _ 3 _ォキセ タニル）メチルアタリレート、 —ェチル _ 3—ォキセタニル）メチルアタリレート、 (3- メチル _ 3—ォキセタニノレ）メチルメタタリレート、 (3-ェチル _ 3—ォキセタニノレ）メチ ルメタタリレート又はこれらのオリゴマーあるいは共重合体等の多官能ォキセタン類の 他、ォキセタン基と、ノボラック樹脂、ポリ（p—ヒドロキシスチレン）、力ルド型ビスフエノ ール類、カリックスァレーン類、力リックスレゾルシンアレーン類、シルセスキォキサン 等の水酸基を有する樹脂など、とのエーテルィ匕合物が挙げられ、この他、ォキセタン 環を有する不飽和モノマーとアルキル (メタ）アタリレートとの共重合体なども挙げられ る。 [0132] Examples of the oxetane compound include bis [(3-methyl_3-oxetanylmethoxy) methyl] ether, bis [(3_ethyl_3-oxetanylmethoxy) methyl] ether, 4_bis [(3-methyl_3-oxetanylmethoxy) methyl] benzene, 1,4_bis [(3_ethyl_3-oxetanylmethoxy) methyl] benzene, (3_methyl_3_oxe Tanyl) methyl atallylate, —ethyl _ 3—oxetanyl) methyl atylate, (3-methyl _3-oxetaninole) methyl metatalylate, (3-ethyl _3-oxetaninole) methyl metatalylate or oligomers or co-polymers thereof In addition to polyfunctional oxetanes such as polymers, oxetane groups, novolac resins, poly (p-hydroxystyrene), force-type bisphenols, calixarenes, strength Examples include etheric compounds such as lyxresorcinarenes and resins having a hydroxyl group such as silsesquioxane, as well as a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. Also mentioned.
[0133] また、前記熱架橋剤として、メラミン誘導体を用いることができる。該メラミン誘導体と しては、例えば、メチロールメラミン、アルキル化メチロールメラミン（メチロール基を、 メチル、ェチル、ブチルなどでエーテル化した化合物）などが挙げられる。これらは 1 種単独で使用してもよいし、 2種以上を併用してもよい。これらの中でも、保存安定性 が良好で、感光層の表面硬度あるいは硬化膜の膜強度自体の向上に有効である点 で、アルキル化メチロールメラミンが好まし へキサメチル化メチロールメラミンが特 に好ましい。  [0133] As the thermal crosslinking agent, a melamine derivative can be used. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, etc.). These may be used alone or in combination of two or more. Of these, alkylated methylol melamine is preferred and hexamethylated methylol melamine is particularly preferred because of its good storage stability and effectiveness in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.
[0134] また、前記熱架橋剤として、下記構造式 (I)及び (II)のいずれかで表される化合物 を用いることができる。  [0134] As the thermal crosslinking agent, a compound represented by any one of the following structural formulas (I) and (II) can be used.
[化 39]
Figure imgf000065_0001
構造式 (I)[Chemical 39]
Figure imgf000065_0001
Structural formula (I)
[化 40] 構造式 （Π )[Chemical 40] Structural formula (Π)
Figure imgf000066_0001
Figure imgf000066_0001
ただし、前記構造式 (I)及び (II)中、 Rは水素原子及び炭素数:!〜 6のアルキル基 のいずれかを表し、 nは 0〜20の整数を表す。  In the structural formulas (I) and (II), R represents either a hydrogen atom or an alkyl group having from 6 to 6 carbon atoms, and n represents an integer of 0 to 20.
[0135] 前記熱架橋剤の前記感光性組成物固形分中の固形分含有量は、：!〜 50質量％ が好ましぐ 3〜30質量％がより好ましい。該固形分含有量が 1質量％未満であると、 硬化膜の膜強度の向上が認められず、 50質量％を超えると、現像性の低下や露光 感度の低下を生ずることがある。 [0135] The solid content in the solid content of the photosensitive composition of the thermal crosslinking agent is preferably 3 to 30% by mass, preferably:! When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not observed, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.
[0136] 〔その他の成分〕 [0136] [Other ingredients]
前記その他の成分としては、例えば、熱重合禁止剤、可塑剤、着色剤（着色顔料あ るいは染料）、体質顔料、などが挙げられ、更に基材表面への密着促進剤及びその 他の助剤類 (例えば、導電性粒子、充填剤、消泡剤、難燃剤、レべリング剤、剥離促 進剤、酸化防止剤、香料、表面張力調整剤、連鎖移動剤など)を併用してもよい。こ れらの成分を適宜含有させることにより、 目的とする感光性組成物あるいは感光性フ イルムの安定性、写真性、膜物性などの性質を調整することができる。  Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and further, adhesion promoters to the substrate surface and other assistants. Agents (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination. Good. By appropriately containing these components, it is possible to adjust properties such as the stability, photographic properties, and film properties of the target photosensitive composition or photosensitive film.
[0137] 熱重合禁止剤 [0137] Thermal polymerization inhibitor
前記熱重合禁止剤は、前記重合性化合物の熱的な重合又は経時的な重合を防止 するために添カ卩してもよい。  The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
前記熱重合禁止剤としては、例えば、 4ーメトキシフエノール、ハイドロキノン、アル キルまたはァリール置換ハイドロキノン、 t—ブチルカテコール、ピロガロール、 2—ヒド ロキシベンゾフエノン、 4 メトキシ一 2 ヒドロキシベンゾフエノン、塩化第一銅、フエ ノチアジン、クロラエル、ナフチルァミン、 β—ナフトール、 2, 6—ジ _t_ブチル _4 —タレゾール、 2， 2 '—メチレンビス（4 メチル _ 6 _t_ブチルフエノール）、ピリジン 、ニトロベンゼン、ジニトロベンゼン、ピクリン酸、 4—トルイジン、メチレンブルー、銅と 有機キレート剤反応物、サリチル酸メチル、及びフエノチアジン、ニトロソ化合物、ニト ロソ化合物と Alとのキレート等が挙げられる。 Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4 methoxy-2-hydroxybenzophenone, Cuprous, phenothiazine, chlorael, naphthylamine, β-naphthol, 2, 6-di_t_butyl _4 —taresol, 2, 2'-methylenebis (4 methyl _6 _t_butylphenol), pyridine, nitrobenzene, dinitrobenzene, Picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nito Examples include chelates of losso compounds and Al.
[0138] 前記熱重合禁止剤の含有量としては、前記重合性化合物に対して 0. 00：!〜 5質 量％が好ましぐ 0. 005〜2質量％力 Sより好ましく、 0. 01〜：!質量％が特に好ましい 。該含有量が、 0. 001質量％未満であると、保存時の安定性が低下することがあり、 5質量％を超えると、活性エネルギー線に対する感度が低下することがある。  [0138] The content of the thermal polymerization inhibitor is preferably from 0.00:! To 5 mass% relative to the polymerizable compound, more preferably from 0.005 to 2 mass% force S, and 0.01. ~:!% By mass is particularly preferred. If the content is less than 0.001% by mass, the stability during storage may be reduced, and if it exceeds 5% by mass, the sensitivity to active energy rays may be reduced.
[0139] 一着色顔料一  [0139] One colored pigment
前記着色顔料としては、特に制限はなぐ 目的に応じて適宜選択することができ、 例えば、ビクトリア 'ピュア一ブルー BO (C. I. 42595)、オーラミン（C. I. 41000)、 フアット'ブラック HB (C. I. 26150)、モノライト'イェロー GT (C. I.ピグメント.イエロ 一 12)、 パーマネント 'イェロー GR (C. I. ピグメント.イェロー 17)、 パーマネント 'イエ ロー HR (C. I. ビグメント 'イェロー 83)、パーマネント 'カーミン FBB (C. I.ビグメント 'レッド 146)、ホスターバームレッド ESB (C. I.ビグメント 'バイオレット 19)、パーマネ ント'ルビー FBH (C. I.ビグメント 'レッド 11)、フアステル 'ピンク Bスプラ（C. I. ピグメ ント'レッド 81)モナストラル.ファースト 'ブルー（C. I.ビグメント 'ブルー 15)、モノライ ト 'ファースト 'ブラック B (C. I.ビグメント 'ブラック 1)、カーボン、 C. I.ビグメント 'レツ ド 97、 C. I. ピク、メント 'レッド 122、 C. I. ピク、メント 'レッド 149、 C. I. ピク、メント 'レッド 168、 C. I.ビグメント 'レッド 177、 C. I.ビグメント 'レッド 180、 C. I.ビグメント 'レッド 192、 C. I.ピグメント ·レッド 215、 C. I.ピグメント ·グリーン 7、 C. I.ピグメント 'グリー ン 36、 C. I.ピグメント 'ブノレ一 15 : 1、 C. I.ピグメント 'ブノレ一 15 : 4、 C. I. ビグメント 'ブノレ一 15 : 6、 C. I. ビグメント 'ブノレ一 22、 C. I.ピグメント 'ブノレ一 60、 C. I.ピグメ ント 'ブルー 64などが挙げられる。これらは 1種単独で用いてもよいし、 2種以上を併 用してもよい。  The coloring pigment is not particularly limited and can be appropriately selected according to the purpose. For example, Victoria 'Pure One Blue BO (CI 42595), Auramin (CI 41000), Fat' Black HB (CI 26150), Mono Light Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment 'Violet 19), Permanent' Ruby FBH (CI Pigment 'Red 11), Huster's' Pink B Supra (CI Pigment' Red 81) Monastral First 'Blue (CI Pigment' Blue 15) , Monolite 'First' Black B (CI Pigment 'Black 1), Carbon, CI Pigment 'Let 97, CI Pic, Men' Red 122, CI Pic, Men 'Red 149, CI Pic, Men' Red 168, CI Pigment 'Red 177, CI Pigment' Red 180, CI Pigment 'Red 192, CI Pigment · Red 215, CI Pigment · Green 7, CI Pigment 'Green 36, CI Pigment' Bonore 1 15: 1, CI Pigment 'Bonore 1 15: 4, CI Pigment' Bonore 1 15: 6, CI Pigment 'Bonore 1 22 CI Pigment 'Bonole 1 60, CI Pigment' Blue 64, etc. These may be used alone or in combination of two or more.
[0140] 前記着色顔料の前記感光性組成物固形分中の固形分含有量は、永久パターン形 成の際の感光層の露光感度、解像性などを考慮して決めることができ、前記着色顔 料の種類により異なる力 一般的には 0. 01〜： 10質量％が好まし 0. 05〜5質量 %がより好ましい。  [0140] The solid content in the solid content of the photosensitive composition of the coloring pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during the formation of a permanent pattern. Different forces depending on the type of facial material Generally 0.01 to 10% by mass is preferred, and 0.05 to 5% by mass is more preferred.
[0141] 一体質顔料一  [0141] One-piece pigment
前記感光性組成物には、必要に応じて、永久パターンの表面硬度の向上、あるレ、 は線膨張係数を低く抑えること、あるいは、硬化膜自体の誘電率や誘電正接を低く 抑えることを目的として、無機顔料や有機微粒子を添加することができる。 In the photosensitive composition, if necessary, improvement of the surface hardness of the permanent pattern, Inorganic pigments and organic fine particles can be added for the purpose of keeping the linear expansion coefficient low or keeping the dielectric constant and dielectric loss tangent of the cured film itself low.
前記無機顔料としては、特に制限はなぐ公知のものの中から適宜選択することが でき、例えば、カオリン、硫酸バリウム、チタン酸ノ リウム、酸化ケィ素粉、微粉状酸化 ケィ素、気相法シリカ、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、タノレク、 クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、 マイ力などが挙げられる。  The inorganic pigment can be appropriately selected from known ones that are not particularly limited, and examples thereof include kaolin, barium sulfate, noble titanate, key oxide powder, fine powder oxide oxide, vapor phase method silica, Amorphous silica, crystalline silica, fused silica, spherical silica, Tanolec, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, My strength, and the like can be mentioned.
前記無機顔料の平均粒径は、 10 μ ΐη未満が好ましぐ 3 μ ΐη以下がより好ましい。 該平均粒径が 10 μ m以上であると、光錯乱により解像度が劣化することがある。 前記有機微粒子としては、特に制限はなぐ 目的に応じて適宜選択することができ 、例えば、メラミン樹脂、ベンゾグアナミン樹脂、架橋ポリスチレン樹脂などが挙げられ る。また、平均粒径 l〜5 /i m、吸油量 100〜200m2/g程度のシリカ、架橋樹脂から なる球状多孔質微粒子などを用いることができる。 The average particle size of the inorganic pigment is preferably 3 μΐη or less, preferably less than 10 μΐη. If the average particle size is 10 μm or more, resolution may deteriorate due to light scattering. The organic fine particles are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. In addition, silica having an average particle diameter of 1 to 5 / im, an oil absorption of about 100 to 200 m 2 / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.
[0142] 前記体質顔料の添加量は、 5〜60質量％が好ましい。該添加量が 5質量％未満で あると、十分に線膨張係数を低下させることができないことがあり、 60質量％を超える と、感光層表面に硬化膜を形成した場合に、該硬化膜の膜質が脆くなり、永久パタ ーンを用いて配線を形成する場合において、配線の保護膜としての機能が損なわれ ることがある。  [0142] The amount of the extender pigment added is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function as a wiring protective film may be impaired.
[0143] 一密着促進剤一  [0143] One adhesion promoter
各層間の密着性、又は感光層と基材との密着性を向上させるために、各層に公知 のレ、わゆる密着促進剤を用いることができる。  In order to improve the adhesion between the layers or between the photosensitive layer and the substrate, a known adhesion promoter or a so-called adhesion promoter can be used for each layer.
[0144] 前記密着促進剤としては、例えば、特開平 5— 11439号公報、特開平 5— 34153 2号公報、及び特開平 6— 43638号公報などに記載の密着促進剤が好適挙げられ る。具体的には、ベンズイミダゾール、ベンズォキサゾール、ベンズチアゾール、 2- メルカプトべンズイミダゾール、 2 _メルカプトべンズォキサゾール、 2 _メルカプトベン ズチアゾール、 3_モルホリノメチル _ 1 _フエ二ルートリアゾール _ 2—チオン、 3 _ モルホリノメチノレ _ 5 _フエ二ノレ一ォキサジァゾール - 2-チオン、 5—ァミノ _ 3—モ ルホリノメチルーチアジアゾールー 2 チオン、及び 2 メルカプト 5 メチルチオ —チアジアゾール、トリァゾーノレ、テトラゾール、ベンゾトリァゾール、カルボキシベン ゾトリァゾール、アミノ基含有べンゾトリァゾール、シランカップリング剤などが挙げられ る。 [0144] Preferable examples of the adhesion promoter include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzoximidazole, 2_mercaptobenzoxazole, 2_mercaptobenzthiazole, 3_morpholinomethyl _ 1 _phenol ritriazole _ 2-thione , 3 _ morpholino methinore _ 5 _ phenyloloxadiazole-2-thione, 5-amino _ 3-morpholinomethyl-thiadiazole-2 thione, and 2 mercapto-5 methylthio —Thiadiazole, triazolole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.
[0145] 前記密着促進剤の含有量としては、前記感光性組成物中の全成分に対して 0. 00 1質量％〜20質量％が好ましぐ 0. 01〜： 10質量％がより好まし 0. 1質量％〜5 質量％が特に好ましい。  [0145] The content of the adhesion promoter is preferably 0.001% by mass to 20% by mass with respect to all components in the photosensitive composition, and more preferably 0.01% to 10% by mass. More preferably, 1% by mass to 5% by mass is particularly preferable.
[0146] 本発明の感光性組成物は、 UV露光により画像形成可能で、表面のタック性が小さ ぐラミネート性及び取扱い性が良好で、保存安定性に優れ、高感度で現像性にも優 れ、現像後に優れた耐薬品性、表面硬度、耐熱性、誘電特性、電気絶縁性などを発 現する。このため、プリント配線板（多層配線基板、ビルドアップ配線基板等）の保護 膜、層間絶縁膜、及びソルダーレジストパターン、カラーフィルタや柱材、リブ材、ス ぺーサ一、隔壁などのディスプレイ用部材、ホログラム、マイクロマシン、プルーフな どの永久パターン形成用として広く用いることができ、特に本発明の感光性フィルム、 永久パターン及びその形成方法に好適に用いることができる。 [0146] The photosensitive composition of the present invention can form an image by UV exposure, has low surface tackiness, good laminating properties and handling properties, excellent storage stability, high sensitivity, and excellent developability. It exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, etc. after development. For this reason, protective materials for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, color filters, pillar materials, rib materials, spacers, partition walls, and other display members It can be widely used for forming permanent patterns such as holograms, micromachines, and proofs, and can be particularly suitably used for the photosensitive film, permanent pattern, and method for forming the same of the present invention.
また、感光性組成物に含まれる前記本発明の硬化促進剤が、熱架橋剤として機能 することにより、別個に熱架橋剤を添加しなくても、硬化膜の優れた膜硬度が得られ る。特に、アミン系熱硬化剤を用いない場合は、特に高感度な感光性組成物が得ら れ、前記永久パターン形成用として広く用いることができ、本発明の感光性フィルム、 永久パターン及びその形成方法に特に好適に用いることができる。  Further, since the curing accelerator of the present invention contained in the photosensitive composition functions as a thermal crosslinking agent, excellent film hardness of the cured film can be obtained without adding a thermal crosslinking agent separately. . In particular, when an amine-based thermosetting agent is not used, a particularly sensitive photosensitive composition can be obtained and widely used for forming the permanent pattern. The photosensitive film of the present invention, the permanent pattern and the formation thereof It can be particularly preferably used in the method.
[0147] (熱硬化性樹脂組成物） [0147] (Thermosetting resin composition)
本発明の熱硬化性樹脂組成物は、エポキシ樹脂化合物と、前記本発明の硬化促 進剤と、を少なくとも含み、さらに必要に応じて、硬化剤を含んでいてもよい。  The thermosetting resin composition of the present invention includes at least an epoxy resin compound and the curing accelerator of the present invention, and may further include a curing agent as necessary.
前記硬化促進剤の含有量としては、エポキシ樹脂化合物の含有量に対して、 0. 0 ：!〜 50質量％が好ましぐ 0. 01〜40質量％がより好ましい。  The content of the curing accelerator is preferably 0.0 :! to 50% by mass, more preferably 0.01 to 40% by mass with respect to the content of the epoxy resin compound.
前記含有量が、 0. 01質量％未満であると、加熱処理時の反応性が低下し、硬化 膜の膜強度の向上が図れないことがあり、 50質量％超であると、現像性、露光感度 の低下、及び硬化膜の膜硬度の低下を生じることがある。  When the content is less than 0.01% by mass, the reactivity during the heat treatment may decrease, and the strength of the cured film may not be improved. When the content exceeds 50% by mass, developability, It may cause a decrease in exposure sensitivity and a decrease in film hardness of the cured film.
前記エポキシ樹脂化合物としては、前記本発明の感光性組成物で使用したものと 同様のエポキシ樹脂化合物を使用することができる。 Examples of the epoxy resin compound include those used in the photosensitive composition of the present invention. Similar epoxy resin compounds can be used.
前記硬化剤としては、特に制限はなぐ前記エポキシ樹脂と反応し得るものであれ ば、公知の硬化剤の中から適宜選択することができ、例えば、フエノール系樹脂、アミ ン系化合物、酸無水物、活性エステル、カルボン酸系化合物、スルホン酸系化合物 などが好適に挙げられる。これらの中でも、 1分子内に 2個以上のフエノール性水酸 基を有する化合物や、アミン系硬化剤が特に好ましぐ具体的には、前者ではフエノ 一ルノボラック樹脂、クレゾ一ルノボラック樹脂、アルキル変性ノボラック樹脂、フエノ ールァラルキル樹脂、ナフトール類とフエノール類をカルボニル基含有化合物と共縮 合した樹脂、ジシクロペンタジェンとフヱノール類の共縮合物などが好適に挙げられ る。また、後者のアミン系硬化剤としては、ジアミノジフエノルメタンなどの芳香族ジアミ ン、ァニリン樹脂、ジシアンジアミド、グァニジンやその誘導体などが好適に挙げられ る。なお、前記硬化剤は、上記例示に限られるものではない。  The curing agent is not particularly limited as long as it can react with the epoxy resin without limitation, and can be appropriately selected from known curing agents. For example, phenolic resins, amine compounds, acid anhydrides. , Active esters, carboxylic acid compounds, sulfonic acid compounds, and the like. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine-based curing agents are particularly preferred. Specifically, in the former case, the phenolic novolac resin, the cresolone novolak resin, and the alkyl-modified are used. Preferable examples include novolak resins, phenol aralkyl resins, resins obtained by co-condensation of naphthols and phenols with a carbonyl group-containing compound, and co-condensates of dicyclopentagen and phenols. As the latter amine-based curing agent, aromatic diamines such as diaminodiphenol, aniline resins, dicyandiamide, guanidine and derivatives thereof are preferably exemplified. In addition, the said hardening | curing agent is not restricted to the said illustration.
前記硬化剤の含有量としては、エポキシ基 1当量に対して 0. 3〜3. 0当量が好まし く、 0. 5〜2. 5当量がより好ましく、 0. 8〜2. 0当量が特に好ましい。  The content of the curing agent is preferably from 0.3 to 3.0 equivalents, more preferably from 0.5 to 2.5 equivalents, and from 0.8 to 2.0 equivalents per 1 equivalent of epoxy group. Particularly preferred.
本発明の熱硬化性樹脂組成物は、保存時の常温では硬化反応を生じることがなく 、加熱によって硬化可能で保存安定性に優れ、硬化後は優れた耐薬品性、硬度、耐 熱性、誘電特性、電気絶縁性などを発現できるので、接着剤などに好適に用いること ができる。  The thermosetting resin composition of the present invention does not cause a curing reaction at room temperature during storage, can be cured by heating, has excellent storage stability, and has excellent chemical resistance, hardness, heat resistance, dielectric after curing. Since characteristics, electrical insulation, etc. can be expressed, it can be suitably used for adhesives and the like.
[0148] (感光性フィルム）  [0148] (Photosensitive film)
本発明の感光性フィルムは、少なくとも支持体と、感光層とを有してなり、好ましくは 保護フィルムを有してなり、更に必要に応じて、クッション層、酸素遮断層（PC層）な どのその他の層を有してなる。  The photosensitive film of the present invention includes at least a support and a photosensitive layer, preferably includes a protective film, and further includes a cushion layer, an oxygen barrier layer (PC layer) and the like as necessary. It has other layers.
[0149] 前記感光性フィルムの形態としては、特に制限はなぐ 目的に応じて適宜選択する ことができ、例えば、前記支持体上に、前記感光層、前記保護膜フィルムをこの順に 有してなる形態、前記支持体上に、前記 PC層、前記感光層、前記保護フィルムをこ の順に有してなる形態、前記支持体上に、前記クッション層、前記 PC層、前記感光 層、前記保護フィルムをこの順に有してなる形態などが挙げられる。なお、前記感光 層は、単層であってもよいし、複数層であってもよい。 [0150] 〔感光層〕 [0149] The form of the photosensitive film is not particularly limited and may be appropriately selected depending on the purpose. For example, the photosensitive film and the protective film are provided on the support in this order. Form: Form in which the PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film on the support. In this order. The photosensitive layer may be a single layer or a plurality of layers. [Photosensitive layer]
前記感光層は、本発明の前記感光性組成物により形成される。  The photosensitive layer is formed by the photosensitive composition of the present invention.
前記感光層の前記感光性フィルムにおいて設けられる箇所としては、特に制限は なぐ 目的に応じて適宜選択することができるが、通常、前記支持体上に積層される 前記感光層は、後述する露光工程において、光照射手段からの光を受光し出射す る描素部を n個有する光変調手段により、前記光照射手段からの光を変調させた後、 前記描素部における出射面の歪みによる収差を補正可能な非球面を有するマイクロ レンズを配列したマイクロレンズアレイを通した光で、露光されるのが好ましレ、。  The portion of the photosensitive layer provided in the photosensitive film is not particularly limited, and can be appropriately selected according to the purpose. Usually, the photosensitive layer laminated on the support is an exposure step described later. In this embodiment, after the light from the light irradiating means is modulated by the light modulating means having n number of picture elements for receiving and emitting the light from the light irradiating means, the aberration due to the distortion of the emission surface in the picture element It is preferable to be exposed to light through a microlens array in which microlenses having an aspheric surface capable of correcting are arranged.
[0151] 前記感光層を露光し現像する場合において、該感光層の露光する部分の厚みを 該露光及び現像後において変化させない前記露光に用いる光の最小エネルギーは 、 0. 1〜： 100 (mj/cm2)であることが好ましぐ：!〜 80mj/cm2であることがより好ま しレ、。前記露光に用いる光の最小エネルギー力 0. lmj/cm2未満であると、加工 マージンが狭くなることがあり、 100mj/cm2を超えると、タクト時間が長くなるため好 ましくない。 [0151] In the case where the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 100 (mj / cm 2 ) is preferred:! ~ 80 mj / cm 2 is more preferred. If the minimum energy force of light used for the exposure is less than 0.1 lmj / cm 2 , the processing margin may be narrowed, and if it exceeds 100 mj / cm 2 , the tact time becomes long, which is not preferable.
[0152] ここで、「該感光層の露光する部分の厚みを該露光及び現像後において変化させ ない前記露光に用いる光の最小エネルギー」とは、いわゆる現像感度であり、例えば 、前記感光層を露光したときの前記露光に用いた光のエネルギー量 (露光量）と、前 記露光に続く前記現像処理により生成した前記硬化層の厚みとの関係を示すグラフ (感度曲線)から求めることができる。  [0152] Here, "the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development" is so-called development sensitivity. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure when exposed and the thickness of the cured layer generated by the development process following the exposure. .
前記硬化層の厚みは、前記露光量が増えるに従い増加していき、その後、前記露 光前の前記感光層の厚みと略同一かつ略一定となる。前記現像感度は、前記硬化 層の厚みが略一定となったときの最小露光量を読み取ることにより求められる値であ る。  The thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
ここで、前記硬化層の厚みと前記露光前の前記感光層の厚みとの差が ± l x m以 内であるとき、前記硬化層の厚みが露光及び現像により変化していないとみなす。 前記硬化層及び前記露光前の前記感光層の厚みの測定方法としては、特に制限 はなく、 目的に応じて適宜選択することができるが、膜厚測定装置、表面粗さ測定機 (例えば、サーフコム 1400D (東京精密社製)）などを用いて測定する方法が挙げら れる。 Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± lxm, it is considered that the thickness of the cured layer is not changed by exposure and development. A method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the intended purpose. (For example, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) can be used.
[0153] 前記感光層の厚みとしては、特に制限はな 目的に応じて適宜選択することがで きる力 例えば、 3〜： 100 μ mが好ましぐ 5 70 μ mがより好ましい。  The thickness of the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose. For example, 3 to: 100 μm is preferable, and 570 μm is more preferable.
[0154] 前記感光層の形成方法としては、前記支持体の上に、本発明の前記感光性組成 物を、水又は溶剤に溶解、乳化又は分散させて感光性組成物溶液を調製し、該溶 液を直接塗布し、乾燥させることにより積層する方法が挙げられる。  [0154] As the method for forming the photosensitive layer, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support. The method of laminating | stacking by apply | coating a solution directly and drying is mentioned.
[0155] 前記感光性組成物溶液の溶剤としては、特に制限はなぐ 目的に応じて適宜選択 することができ、例えば、メタノーノレ、エタノール、 n—プロパノール、イソプロパノール n—ブタノール、 sec ブタノール、 n キサノール等のアルコール類；アセトン、メ チルェチルケトン、メチルイソブチルケトン、シクロへキサノン、ジイソプチルケトンなど のケトン類；酢酸ェチル、酢酸ブチル、酢酸 n ァミル、硫酸メチル、プロピオン酸 ェチル、フタル酸ジメチル、安息香酸ェチル、及びメトキシプロピルアセテートなどの エステル類；トルエン、キシレン、ベンゼン、ェチルベンゼンなどの芳香族炭化水素類 ；四塩化炭素、トリクロロエチレン、クロ口ホルム、 1 , 1 , 1—トリクロロェタン、塩化メチ レン、モノクロ口ベンゼンなどのハロゲン化炭化水素類；テトラヒドロフラン、ジェチル エーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノェチルェ 一テル、 1—メトキシ _ 2_プロパノールなどのエーテル類；ジメチルホルムアミド、ジメ チルァセトアミド、ジメチルスルホオキサイド、スルホランなどが挙げられる。これらは、 1種単独で使用してもよぐ 2種以上を併用してもよい。また、公知の界面活性剤を添 加してもよい。  [0155] The solvent of the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol, n-propanol, isopropanol n-butanol, sec butanol, and n-xanol. Alcohols: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone, etc. ketones: ethyl acetate, butyl acetate, namyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate And esters such as methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methyl chloride, monochrome Halogens such as mouth benzene Hydrocarbons such as tetrahydrofuran, jetyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy_2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. Can be mentioned. These may be used alone or in combination of two or more. In addition, a known surfactant may be added.
[0156] 前記塗布の方法としては、特に制限はな 目的に応じて適宜選択することができ 、例えば、スピンコーター、スリットスピンコーター、ローノレコーター、ダイコーター、力 一テンコーターなどを用いて、前記支持体に直接塗布する方法が挙げられる。  [0156] The coating method can be appropriately selected depending on the purpose without any particular limitation. For example, the spin coater, slit spin coater, Rohno coater, die coater, force ten coater, etc. The method of apply | coating directly to a support body is mentioned.
前記乾燥の条件としては、各成分、溶媒の種類、使用割合等によっても異なるが、 通常 60 110°Cの温度で 30秒間〜 15分間程度である。  The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.
[0157] 〔支持体〕  [Support]
前記支持体としては、特に制限はなぐ 目的に応じて適宜選択することができる力 S 前記感光層を剥離可能であり、かつ光の透過性が良好であるのが好ましぐ更に表 面の平滑性が良好であるのがより好ましい。 The support is not particularly limited and can be appropriately selected according to the purpose. It is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and it is more preferable that the surface smoothness is good.
[0158] 前記支持体は、合成樹脂製で、かつ透明であるものが好ましぐ例えば、ポリエチレ ンテレフタレート、ポリエチレンナフタレート、ポリプロピレン、ポリエチレン、三酢酸セ ノレロース、二酢酸セルロース、ポリ（メタ）アクリル酸アルキルエステル、ポリ（メタ）アタリ ル酸エステル共重合体、ポリ塩化ビュル、ポリビュルアルコール、ポリカーボネート、 ポリスチレン、セロファン、ポリ塩化ビニリデン共重合体、ポリアミド、ポリイミド、塩ィ匕ビ ニル.酢酸ビュル共重合体、ポリテトラフロロエチレン、ポリトリフロロエチレン、セル口 ース系フィルム、ナイロンフィルム等の各種のプラスチックフィルムが挙げられ、これら の中でも、ポリエチレンテレフタレートが特に好ましい。これらは、 1種単独で使用して もよぐ 2種以上を併用してもよい。 [0158] The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic. Alkyl ester, poly (meth) acrylate ester copolymer, polychlorinated butyl, polybutyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride. Butyl acetate Various plastic films such as polymers, polytetrafluoroethylene, polytrifluoroethylene, cellulose-based films, nylon films and the like can be mentioned. Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
なお、前記支持体としては、例えば、特開平 4 208940号公報、特開平 5— 8050 Examples of the support include, for example, JP-A-4 208940 and JP-A-5-8050.
3号公報、特開平 5— 173320号公報、特開平 5— 72724号公報などに記載の支持 体を用レ、ることもできる。 It is also possible to use the support described in JP-A No. 3, JP-A-5-173320, JP-A-5-72724 and the like.
[0159] 前記支持体の厚みとしては、特に制限はなぐ 目的に応じて適宜選択することがで きる力 例えば、 4〜300 μ mが好ましぐ 5〜： 175 μ mがより好ましい。 [0159] The thickness of the support is not particularly limited, and can be appropriately selected according to the purpose. For example, 4 to 300 µm is preferable, and 5 to 175 µm is more preferable.
[0160] 前記支持体の形状としては、特に制限はなぐ 目的に応じて適宜選択することがで きる力 長尺状が好ましい。前記長尺状の支持体の長さとしては、特に制限はなぐ 例えば、 10m〜20， 000mの長さのものが挙げられる。 [0160] The shape of the support is not particularly limited, and is preferably a long and long force that can be appropriately selected according to the purpose. The length of the long support is not particularly limited. For example, the length of the long support is 10 m to 20,000 m.
[0161] 〔保護フィルム〕 [0161] [Protective film]
前記保護フィルムは、前記感光層の汚れや損傷を防止し、保護する機能を有する 前記保護フィルムの前記感光性フィルムにおいて設けられる箇所としては、特に制 限はなぐ 目的に応じて適宜選択することができるが、通常、前記感光層上に設けら れる。  The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged. The portion of the protective film provided in the photosensitive film is not particularly limited and may be appropriately selected according to the purpose. Usually, it is provided on the photosensitive layer.
前記保護フィルムとしては、例えば、前記支持体に使用されるもの、シリコーン紙、 ポリエチレン、ポリプロピレンがラミネートされた紙、ポリオレフイン又はポリテトラフルォ ルエチレンシート、などが挙げられ、これらの中でも、ポリエチレンフィルム、ポリプロピ レンフイノレムが好ましい。 Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film, polypropylene, etc. Renfinorem is preferred.
前記保護フィルムの厚みとしては、特に制限はなぐ 目的に応じて適宜選択するこ とができるが、例えば、 5〜： 100 z m力好ましく、 8〜30 z mがより好ましい。  The thickness of the protective film is not particularly limited and may be appropriately selected depending on the purpose. For example, 5 to 100 zm force is preferable, and 8 to 30 zm is more preferable.
前記保護フィルムを用いる場合、前記感光層及び前記支持体の接着力 Aと、前記 感光層及び保護フィルムの接着力 Bとが、接着力 A>接着力 Bの関係であることが好 ましい。  When the protective film is used, it is preferable that the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
前記支持体と保護フィルムとの組合せ（支持体/保護フィルム）としては、例えば、 ポリエチレンテレフタレート/ポリプロピレン、ポリエチレンテレフタレート/ポリェチレ ン、ポリ塩化ビニル /セロファン、ポリイミド/ポリプロピレン、ポリエチレンテレフタレ ート/ポリエチレンテレフタレートなどが挙げられる。また、支持体及び保護フィルム の少なくともいずれかを表面処理することにより、上述のような接着力の関係を満たす こと力 Sできる。前記支持体の表面処理は、前記感光層との接着力を高めるために施 されてもよぐ例えば、下塗層の塗設、コロナ放電処理、火炎処理、紫外線照射処理 、高周波照射処理、グロ一放電照射処理、活性プラズマ照射処理、レーザ光線照射 処理などを挙げることができる。  Examples of the combination of the support and the protective film (support / protective film) include, for example, polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate. Etc. In addition, by applying a surface treatment to at least one of the support and the protective film, it is possible to satisfy the adhesive force relationship as described above. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glossy treatment, One discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like can be mentioned.
[0162] また、前記支持体と前記保護フィルムとの静摩擦係数としては、 0. 3〜： 1. 4が好ま しぐ 0. 5〜： 1. 2がより好ましい。 [0162] Further, the coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2.
前記静摩擦係数が、 0. 3未満であると、滑り過ぎるため、ロール状にした場合に卷 ズレが発生することがあり、 1. 4を超えると、良好なロール状に卷くことが困難となるこ とがある。  If the coefficient of static friction is less than 0.3, slipping may occur excessively, so that deviation may occur when the roll is formed.If it exceeds 1.4, it is difficult to form a good roll. There is a thing.
[0163] 前記感光性フィルムは、例えば、円筒状の卷芯に巻き取って、長尺状でロール状 に卷かれて保管されるのが好ましい。前記長尺状の感光性フィルムの長さとしては、 特に制限はなぐ例えば、 10m〜20, 000mの範囲から適宜選択することができる。 また、ユーザーが使いやすいようにスリット加工し、 100m〜l , 000mの範囲の長尺 体をロール状にしてもよい。なお、この場合には、前記支持体が一番外側になるよう に卷き取られるのが好ましい。また、前記ロール状の感光性フィルムをシート状にスリ ットしてもよい。保管の際、端面の保護、エッジフュージョンを防止する観点から、端 面にはセパレーター（特に防湿性のもの、乾燥剤入りのもの）を設置するのが好ましく 、また梱包も透湿性の低レ、素材を用レ、るのが好ましレ、。 [0163] The photosensitive film is preferably wound and stored in a long roll shape, for example, wound around a cylindrical core. The length of the long photosensitive film is not particularly limited, and can be appropriately selected from a range of 10 m to 20,000 m, for example. In addition, slitting may be performed so that it is easy for the user to use, and a long body in the range of 100 m to l, 000 m may be rolled. In this case, it is preferable that the support is scraped off so as to be the outermost side. The roll-shaped photosensitive film may be slit into a sheet. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and with desiccant) on the end face. Also, the packaging is low in moisture permeability, and it is preferable to use materials.
[0164] 前記保護フィルムは、前記保護フィルムと前記感光層との接着性を調整するために 表面処理してもよい。前記表面処理は、例えば、前記保護フィルムの表面に、ポリオ ルガノシロキサン、弗素化ポリオレフイン、ポリフルォロエチレン、ポリビュルアルコー ル等のポリマーからなる下塗層を形成させる。該下塗層の形成は、前記ポリマーの塗 布液を前記保護フィルムの表面に塗布した後、 30〜： 150°C (特に 50〜： 120°C)で 1 〜30分間乾燥させることにより形成させることができる。 [0164] The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polybutyl alcohol is formed on the surface of the protective film. The undercoat layer is formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C (especially 50 to 120 ° C) for 1 to 30 minutes. Can be made.
また、前記感光層、前記支持体、前記保護フィルムの他に、クッション層、酸素遮断 層（PC層）、剥離層、接着層、光吸収層、表面保護層などの層を有してもよい。  In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included. .
前記クッション層は、常温ではタック性が無ぐ真空及び加熱条件で積層した場合 に溶融し、流動する層である。  The cushion layer is a layer that melts and flows when laminated under vacuum and heating conditions that have no tackiness at room temperature.
前記 PC層は、通常ポリビニルアルコールを主成分として形成された 0. 5〜5 /i m程 度の被膜である。  The PC layer is usually a film of about 0.5 to 5 / im formed with polyvinyl alcohol as a main component.
[0165] 本発明の感光性フィルムは、表面のタック性が小さぐラミネート性及び取扱い性が 良好で、保存安定性に優れ、高感度で現像性にも優れ、現像後に優れた耐薬品性 、表面硬度、耐熱性、誘電特性などを発現する感光性組成物が積層された感光層を 有してなる。このため、プリント配線板、カラーフィルタや柱材、リブ材、スぺーサ一、 隔壁などのディスプレイ用部材、ホログラム、マイクロマシン、プルーフなどの永久パ ターン形成用として広く用いることができ、本発明の永久パターン及びその形成方法 に好適に用いることができる。また、アミン系熱硬化剤を用いない場合は、特に高感 度な感光性フィルムが得られ、前記用途に特に好適に用いることができる。  [0165] The photosensitive film of the present invention has low surface tackiness, good laminating properties and handleability, excellent storage stability, high sensitivity and excellent developability, and excellent chemical resistance after development. It has a photosensitive layer on which a photosensitive composition exhibiting surface hardness, heat resistance, dielectric properties and the like is laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for a permanent pattern and a method for forming the permanent pattern. Further, when no amine thermosetting agent is used, a photosensitive film having particularly high sensitivity can be obtained, and can be particularly suitably used for the above-mentioned use.
特に、本発明の感光性フィルムは、該フィルムの厚みが均一であるため、永久パタ ーンの形成に際し、基材への積層がより精細に行われる。  In particular, since the photosensitive film of the present invention has a uniform thickness, the film is more precisely laminated on the substrate when the permanent pattern is formed.
[0166] (永久パターン及び永久パターン形成方法） [0166] (Permanent pattern and permanent pattern forming method)
本発明の永久パターンは、本発明の永久パターン形成方法により得られる。  The permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
本発明の永久パターン形成方法は、第 1の態様として、本発明の感光性組成物を、 基材の表面に塗布し、乾燥して感光層を形成した後、露光し、現像する。  In the method for forming a permanent pattern of the present invention, as a first embodiment, the photosensitive composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed and developed.
また、本発明の永久パターン形成方法は、第 2の態様として、本発明の感光性フィ ルムを、加熱及び加圧の少なくともいずれかの下において基材の表面に積層した後 、露光し、現像する。 The method for forming a permanent pattern of the present invention includes, as a second aspect, the photosensitive film of the present invention. The film is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed.
以下、本発明の永久パターン形成方法の説明を通じて、本発明の永久パターンの 詳細も明らかにする。  Hereinafter, the details of the permanent pattern of the present invention will be clarified through the description of the method for forming a permanent pattern of the present invention.
[0167] 〔基材〕 [Base material]
前記基材としては、特に制限はなぐ公知の材料の中から表面平滑性の高いもの 力も凸凹のある表面を有するものまで適宜選択することができ、板状の基材 (基板）が 好ましぐ具体的には、公知のプリント配線板形成用基板 (例えば、銅張積層板）、ガ ラス板（例えば、ソーダガラス板等）、合成樹脂性のフィルム、紙、金属板などが挙げ られる力 これらの中でも、プリント配線板形成用基板が好ましぐ多層配線基板ゃビ ルドアップ配線基板などへの半導体等の高密度実装化が可能となる点で、該プリント 配線板形成用基板が配線形成済みであるのが特に好ましレ、。  The base material can be appropriately selected from publicly known materials that are not particularly limited to those having a high surface smoothness and a surface having a rough surface, and a plate-like base material (substrate) is preferred. Specific examples include known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic resin films, paper, metal plates, etc. Among them, the printed wiring board forming substrate has already been formed in that it can be mounted on a multilayer wiring board where a printed wiring board forming substrate is preferred, such as a semiconductor on a built-up wiring substrate. It is especially preferred to have it.
[0168] 前記基材は、前記第 1の態様として、該基材上に前記感光性組成物による感光層 が形成されてなる積層体、又は前記第 2の態様として、前記感光性フィルムにおける 感光層が重なるようにして積層されてなる積層体を形成して用いることができる。即ち 、前記積層体における前記感光層に対して後述する露光することにより、露光した領 域を硬化させ、後述する現像により永久パターンを形成することができる。  [0168] The substrate is a laminate in which a photosensitive layer made of the photosensitive composition is formed on the substrate as the first aspect, or the photosensitive film in the photosensitive film as the second aspect. It is possible to form and use a laminated body in which the layers are laminated so as to overlap each other. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed area can be cured, and a permanent pattern can be formed by development to be described later.
[0169] 一積層体一  [0169] One laminate
前記第 1の態様の積層体の形成方法としては、特に制限はな 目的に応じて適宜 選択することができるが、前記基材上に、前記感光性組成物を塗布及び乾燥して形 成した感光層を積層するのが好ましい。  The method for forming the laminate of the first aspect is not particularly limited and can be appropriately selected according to the purpose, but the photosensitive composition is applied and dried on the substrate. It is preferable to laminate a photosensitive layer.
前記塗布及び乾燥の方法としては、特に制限はな 目的に応じて適宜選択するこ とができ、例えば、前記感光性フィルムにおける感光層を形成する際に行われる、前 記感光性組成物溶液の塗布及び乾燥と同様な方法で行うことができ、例えば、該感 光性組成物溶液をスピンコーター、スリットスピンコーター、ロールコーター、ダイコー ター、カーテンコーターなどを用いて塗布する方法が挙げられる。  The method for coating and drying can be appropriately selected according to the purpose without any particular limitation. For example, the method for forming the photosensitive composition solution in the photosensitive film can be performed when the photosensitive layer is formed on the photosensitive film. For example, a method of applying the photosensitive composition solution by using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like can be used.
[0170] 前記第 2の態様の積層体の形成方法としては、特に制限はな 目的に応じて適宜 選択することができる力 前記基材上に前記感光性フィルムを加熱及び加圧の少な くともいずれかを行いながら積層するのが好ましい。なお、前記感光性フィルムが前 記保護フィルムを有する場合には、該保護フィルムを剥離し、前記基材に前記感光 層が重なるようにして積層するのが好ましい。 [0170] The method for forming the laminate of the second aspect is not particularly limited. The force can be appropriately selected according to the purpose. The photosensitive film is heated and pressed little on the substrate. It is preferable to stack while performing at least one of them. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.
前記加熱温度としては、特に制限はなぐ 目的に応じて適宜選択することができる 、 ί列免 ίΐ、 70〜： 130oCカ^;子ましく、 80〜： 110oCカより女子ましレヽ。 The heating temperature is not particularly limited and can be appropriately selected according to the purpose. Ί 免 免 70, 70 ~: 130 o C ^; childlike, 80 ~: 110 o C .
前記加圧の圧力としては、特に制限はな 目的に応じて適宜選択することができ る力 ί列免«'、 0. 01〜： 1. OMPaカ好ましく、 0. 05〜： 1. OMPaカより好ましレヽ。  The pressure of the pressurization is not particularly limited, and can be appropriately selected according to the purpose. 列 column-excluded, 0.01-: 1. OMPa is preferable, 0.05-: 1. OMPa More preferred.
[0171] 前記加熱及び加圧の少なくともいずれかを行う装置としては、特に制限はなぐ 目 的に応じて適宜選択することができ、例えば、ヒートプレス、ヒートロールラミネーター（ 例えば、大成ラミネータネ土製、 VP— 11)、真空ラミネーター（例えば、名機製作所製、 MVLP500)などが好適に挙げられる。  [0171] The apparatus for performing at least one of the heating and pressurization can be appropriately selected depending on the purpose, and for example, a heat press, a heat roll laminator (for example, Taisei Laminate Earthen, VP 11), a vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho) and the like are preferable.
[0172] 〔露光工程〕  [Exposure process]
前記露光工程は、前記感光層に対し、露光を行う工程である。  The exposure step is a step of exposing the photosensitive layer.
[0173] 前記露光の対象としては、感光層を有する材料である限り、特に制限はなぐ 目的 に応じて適宜選択することができるが、例えば、基材上に前記感光性組成物又は前 記感光性フィルムが形成されてなる前記積層体に対して行われることが好ましい。  [0173] The subject of the exposure is not particularly limited as long as it is a material having a photosensitive layer, and can be appropriately selected depending on the purpose. For example, the photosensitive composition or the photosensitive composition described above is formed on a substrate. It is preferable to perform with respect to the said laminated body in which a conductive film is formed.
[0174] 前記積層体への露光としては、特に制限はなぐ 目的に応じて適宜選択することが でき、例えば、前記支持体、クッション層及び PC層を介して前記感光層を露光しても よ 前記支持体を剥離した後、前記クッション層及び PC層を介して前記感光層を 露光してもよぐ前記支持体及びクッション層を剥離した後、前記 PC層を介して前記 感光層を露光してもよぐ前記支持体、クッション層及び PC層を剥離した後、前記感 光層を露光してもよい。  [0174] The exposure of the laminate is not particularly limited and may be appropriately selected depending on the purpose. For example, the photosensitive layer may be exposed through the support, the cushion layer, and the PC layer. After peeling off the support, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling off the support and cushion layer, the photosensitive layer is exposed through the PC layer. The photosensitive layer may be exposed after the support, cushion layer and PC layer are peeled off.
[0175] 前記露光としては、特に制限はなぐ 目的に応じて適宜選択することができ、デジタ ル露光、アナログ露光等が挙げられる力 これらの中でもデジタル露光が好ましい。  [0175] The exposure is not particularly limited and can be appropriately selected according to the purpose. Among these, digital exposure, analog exposure, and the like are preferred. Digital exposure is preferable among these.
[0176] 前記デジタル露光としては、特に制限はな 目的に応じて適宜選択することがで きる力 例えば、形成するパターン形成情報に基づいて制御信号を生成し、該制御 信号に応じて変調させた光を用いて行うのが好ましい。  [0176] The digital exposure is a force that can be appropriately selected according to the purpose without any particular limitation. For example, a control signal is generated based on pattern formation information to be formed, and is modulated according to the control signal. It is preferable to use light.
[0177] 前記デジタル露光の手段としては、特に制限はなぐ 目的に応じて適宜選択するこ とができ、例えば、光を照射する光照射手段、形成するパターン情報に基づいて該 光照射手段から照射される光を変調させる光変調手段などが挙げられる。 [0177] The means for digital exposure is not particularly limited, and may be appropriately selected according to the purpose. For example, a light irradiating means for irradiating light, a light modulating means for modulating light emitted from the light irradiating means based on pattern information to be formed, and the like can be mentioned.
[0178] <光変調手段 >  [0178] <Light modulation means>
前記光変調手段としては、光を変調することができる限り、特に制限はなぐ 目的に 応じて適宜選択することができる力 例えば、 n個の描素部を有するのが好ましい。 前記 n個の描素部を有する光変調手段としては、特に制限はな 目的に応じて適 宜選択することができるが、例えば、空間光変調素子が好ましい。  The light modulating means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose. For example, it preferably has n pixel portions. The light modulation means having the n picture element portions can be appropriately selected according to the purpose without any particular limitation. For example, a spatial light modulation element is preferable.
[0179] 前記空間光変調素子としては、例えば、デジタル ·マイクロミラー ·デバイス（DMD) 、 MEMS (Micro Electro Mechanical Systems)タイプの空間光変調素子（S LM ; Special Light Modulator)、電気光学効果により透過光を変調する光学素 子（PLZT素子）、液晶光シャツタ（FLC)などが挙げられ、これらの中でも DMDが好 適に挙げられる。  [0179] Examples of the spatial light modulation element include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM; Special Light Modulator), and transmission by an electro-optic effect. Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
[0180] また、前記光変調手段は、形成するパターン情報に基づいて制御信号を生成する ノ ターン信号生成手段を有するのが好ましい。この場合、前記光変調手段は、前記 ノ ターン信号生成手段が生成した制御信号に応じて光を変調させる。  [0180] Further, it is preferable that the light modulation means has a pattern signal generation means for generating a control signal based on pattern information to be formed. In this case, the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
前記制御信号としては、特に制限はなぐ 目的に応じて適宜選択することができ、 例えば、デジタル信号が好適に挙げられる。  The control signal is not particularly limited and can be appropriately selected according to the purpose. For example, a digital signal is preferable.
[0181] 以下、前記光変調手段の一例については、特開 2005— 258431号公報の明細書 の段落「0016」から「0047」に記載されている光変調手段などが挙げられる。  Hereinafter, examples of the light modulation means include the light modulation means described in paragraphs “0016” to “0047” of the specification of JP-A-2005-258431.
[0182] 一光照射手段一  [0182] One light irradiation means
前記光照射手段としては、特に制限はなぐ 目的に応じて適宜選択することができ 、例えば、（超）高圧水銀灯、キセノン灯、カーボンアーク灯、ハロゲンランプ、複写機 用などの蛍光管、 LED,半導体レーザ等の公知光源、又は 2以上の光を合成して照 射可能な手段が挙げられ、これらの中でも 2以上の光を合成して照射可能な手段が 好ましい。  The light irradiation means is not particularly limited and can be appropriately selected according to the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, photocopier fluorescent lamp, LED, A known light source such as a semiconductor laser or means capable of combining and irradiating two or more lights can be mentioned. Among these, means capable of combining and irradiating two or more lights are preferable.
前記光照射手段から照射される光としては、例えば、支持体を介して光照射を行う 場合には、該支持体を透過し、かつ用いられる光重合開始剤や増感剤を活性化す る電磁波、紫外から可視光線、電子線、 X線、レーザ光などが挙げられ、これらの中 でもレーザ光が好ましぐ 2以上の光を合成したレーザ光（以下、「合波レーザ光」と称 することがある）がより好ましい。また支持体を剥離してから光照射を行う場合でも、同 様の光を用いることができる。 The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. UV to visible light, electron beam, X-ray, laser beam, etc. However, laser light that is preferred by laser light is more preferable laser light that combines two or more lights (hereinafter sometimes referred to as “combined laser light”). In addition, similar light can be used even when light irradiation is performed after the support is peeled off.
[0183] 前記紫外から可視光線の波長としては、例えば、 300-1, 500nm力好ましく、 32 0〜800nmカより好ましく、 330〜650nmカ特に好ましレヽ。 [0183] The wavelength of the ultraviolet to visible light is, for example, preferably 300-1,500 nm, more preferably 320-800 nm, particularly preferably 330-650 nm.
前記レーザ光の波長としては、 ί列えは、、 200〜1， 500nmカ好ましく、 300〜800n mカより好ましく、 330〜500nmカ更に好ましく、 395nm〜415nmカ特に好ましレヽ  The wavelength of the laser beam is preferably 200 to 1,500 nm, more preferably 300 to 800 nm, further preferably 330 to 500 nm, and particularly preferably 395 to 415 nm.
[0184] 前記合波レーザ光を照射可能な手段としては、例えば、複数のレーザと、マルチモ ード光ファイバと、該複数のレーザ力 それぞれ照射したレーザ光を集光して前記マ ルチモード光ファイバに結合させる集合光学系とを有する手段が好ましレ、。 [0184] Examples of means capable of irradiating the combined laser light include, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces to collect the multimode optical fiber. A means having a collective optical system to be coupled to is preferable.
[0185] 以下、前記合波レーザ光を照射可能な手段（ファイバアレイ光源）については、例 えば、特開 2005— 316431号公報の明細書の段落「0130」から「0177」に記載さ れてレ、る手段などが挙げられる。 また、前記露光は、前記変調させた光を、マイクロレンズアレイを通して行うのが好 ましぐ更にアパーチャアレイ、結像光学系等などを通して行ってもよい。  [0185] Hereinafter, the means (fiber array light source) capable of irradiating the combined laser beam is described in paragraphs “0130” to “0177” of the specification of JP-A-2005-316431, for example. And means. The exposure is preferably performed through the microlens array with the modulated light, and may be performed through an aperture array, an imaging optical system, or the like.
[0187] 前記マイクロレンズアレイとしては、特に制限はなぐ 目的に応じて適宜選択するこ とができるが、例えば、前記描素部における出射面の歪みによる収差を補正可能な 非球面を有するマイクロレンズを配列したものが好適に挙げられる。  [0187] The microlens array is not particularly limited and can be appropriately selected according to the purpose. For example, the microlens array has an aspheric surface that can correct aberration due to distortion of the exit surface in the pixel portion. Preferred examples include those in which
[0188] 前記非球面としては、特に制限はなぐ 目的に応じて適宜選択することができるが、 例えば、トーリック面が好ましい。  [0188] The aspherical surface is not particularly limited and can be appropriately selected according to the purpose. For example, a toric surface is preferable.
[0189] 以下、前記マイクロレンズアレイ、前記アパーチャアレイ、及び前記結像光学系等 について図面を参照しながら説明する。  Hereinafter, the microlens array, the aperture array, the imaging optical system, and the like will be described with reference to the drawings.
[0190] 図 2 (A)は、 DMD50、 DMD50にレーザ光を照射する光照射手段 144、 DMD50 で反射されたレーザ光を拡大して結像するレンズ系（結像光学系） 454、 458、 DM D50の各描素部に対応して多数のマイクロレンズ 474が配置されたマイクロレンズァ レイ 472、マイクロレンズアレイ 472の各マイクロレンズに対応して多数のアパーチャ 4 78が設けられたアパーチャアレイ 476、アパーチャを通過したレーザ光を被露光面 5 6に結像するレンズ系（結像光学系） 480、 482で構成される露光ヘッドを表す。 ここで、図 3に、 DMD50を構成するマイクロミラー 62の反射面の平面度を測定した 結果を示す。同図においては、反射面の同じ高さ位置を等高線で結んで示してあり 、等高線のピッチは 5nmである。なお同図に示す X方向及び y方向は、マイクロミラー 62の 2つ対角線方向であり、マイクロミラー 62は y方向に延びる回転軸を中心として 前述のように回転する。また、図 4の（A)及び（B)にはそれぞれ、上記 X方向、 y方向 に沿ったマイクロミラー 62の反射面の高さ位置変位を示す。 [0190] Fig. 2 (A) shows DMD50, light irradiating means 144 for irradiating DMD50 with laser light, and a lens system (imaging optical system) 454, 458 for enlarging the laser light reflected by DMD50. A large number of apertures corresponding to each microlens of the microlens array 472 and the microlens array 472 in which a large number of microlenses 474 are arranged corresponding to each pixel portion of the DM D50 4 This represents an exposure head composed of an aperture array 476 provided with 78 and lens systems (imaging optical systems) 480 and 482 for forming an image of the laser light that has passed through the aperture on the exposed surface 56. Here, FIG. 3 shows the result of measuring the flatness of the reflection surface of the micromirror 62 constituting the DMD 50. In the figure, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. Note that the X direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction as described above. 4A and 4B show the height position displacement of the reflecting surface of the micromirror 62 along the X direction and the y direction, respectively.
[0191] 図 3及び図 4に示した通り、マイクロミラー 62の反射面には歪みが存在し、そして特 にミラー中央部に注目してみると、 1つの対角線方向（y方向）の歪みが、別の対角線 方向（X方向）の歪みよりも大きくなつている。このため、マイクロレンズアレイ 55のマイ クロレンズ 55aで集光されたレーザ光 Bの集光位置における形状が歪むという問題が 発生し得る。 [0191] As shown in FIGS. 3 and 4, there is distortion on the reflection surface of the micromirror 62, and when attention is paid particularly to the center of the mirror, there is distortion in one diagonal direction (y direction). The distortion in another diagonal direction (X direction) is getting bigger. For this reason, the problem that the shape in the condensing position of the laser beam B condensed with the micro lens 55a of the micro lens array 55 may be distorted may occur.
[0192] 本発明の永久パターン形成方法においては前記問題を防止するために、マイクロ レンズアレイ 55のマイクロレンズ 55aが、従来とは異なる特殊な形状とされている。以 下、その点について詳しく説明する。  In the permanent pattern forming method of the present invention, in order to prevent the above problem, the microlens 55a of the microlens array 55 has a special shape different from the conventional one. This point will be explained in detail below.
[0193] 図 5の（A)及び（B)はそれぞれ、マイクロレンズアレイ 55全体の正面形状及び側面 形状を詳しく示すものである。これらの図にはマイクロレンズアレイ 55の各部の寸法も 記入してあり、それらの単位は mmである。本発明の永久パターン形成方法では、図 1に示されるように、 DMD50の 1 , 024個 X 256列のマイクロミラー 62が駆動される ものであり、それに対応させてマイクロレンズアレイ 55は、横方向に 1， 024個並んだ マイクロレンズ 55aの列を縦方向に 256列並設して構成されている。なお、同図 Aで は、マイクロレンズアレイ 55の並び順を横方向については jで、縦方向については k で示している。  [0193] FIGS. 5A and 5B respectively show the front and side shapes of the entire microlens array 55 in detail. These figures also show the dimensions of each part of the microlens array 55, and their units are mm. In the permanent pattern forming method of the present invention, as shown in FIG. 1, 1,024 × 256 rows of micromirrors 62 of DMD50 are driven, and correspondingly, microlens array 55 is formed in the horizontal direction. In other words, 1,024 microlenses 55a are arranged in 256 rows in the vertical direction. In FIG. A, the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.
[0194] また、図 6の（A)及び（B)はそれぞれ、マイクロレンズアレイ 55における 1つのマイク 口レンズ 55aの正面形状及び側面形状を示すものである。なお同図 Aには、マイクロ レンズ 55aの等高線を併せて示してある。各マイクロレンズ 55aの光出射側の端面は 、マイクロミラー 62の反射面の歪みによる収差を補正する非球面形状とされている。 より具体的には、マイクロレンズ 55aはトーリックレンズとされており、上記 X方向に光 学的に対応する方向の曲率半径 Rx= _0. 125mm,上記 y方向に対応する方向の 曲率半径 Ry= _0. 1mmである。 [0194] Also, (A) and (B) of FIG. 6 show the front shape and side shape of one microphone opening lens 55a in the microlens array 55, respectively. In FIG. A, the contour lines of the micro lens 55a are also shown. The end surface of each microlens 55a on the light emission side has an aspherical shape that corrects aberration due to distortion of the reflection surface of the micromirror 62. More specifically, the micro lens 55a is a toric lens, and has a radius of curvature Rx = _0.125 mm in the direction optically corresponding to the X direction, and a radius of curvature R y = in the direction corresponding to the y direction. _0. 1mm.
[0195] したがって、上記 X方向及び y方向に平行な断面内におけるレーザ光 Bの集光状態 は、概略、それぞれ図 7の (A)及び (B)に示す通りとなる。つまり、x方向に平行な断 面内と y方向に平行な断面内とを比較すると、後者の断面内の方がマイクロレンズ 55 aの曲率半径がより小であって、焦点距離がより短くなつている。  Therefore, the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction is roughly as shown in FIGS. 7A and 7B, respectively. That is, when comparing the cross section parallel to the x direction and the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. ing.
[0196] マイクロレンズ 55aを前記形状とした場合の、該マイクロレンズ 55aの集光位置（焦 点位置）近傍におけるビーム径を計算機によってシミュレーションした結果を図 8A〜 図 8Dに示す。また比較のために、マイクロレンズ 55aが曲率半径 Rx = Ry=—0. lm mの球面形状である場合について、同様のシミュレーションを行った結果を図 9A〜 図 9Dに示す。なお、各図における zの値は、マイクロレンズ 55aのピント方向の評価 位置を、マイクロレンズ 55aのビーム出射面からの距離で示している。  [0196] FIGS. 8A to 8D show the simulation results of the beam diameter in the vicinity of the condensing position (focus position) of the microlens 55a when the microlens 55a has the above-described shape. For comparison, FIGS. 9A to 9D show the same simulation results for the case where the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = −0.1 mm. Note that the value of z in each figure indicates the evaluation position in the focus direction of the microlens 55a by the distance from the beam exit surface of the microlens 55a.
[0197] また、前記シミュレーションに用いたマイクロレンズ 55aの面形状は、下記計算式で 計算される。  [0197] Further, the surface shape of the microlens 55a used in the simulation is calculated by the following calculation formula.
[数 1]  [Number 1]
C 2 X 2+ C 2 Y 2 C 2 X 2 + C 2 Y 2
― 1 + S Q R T ( 1 - C 2 X 2 - C 2 Y 2 ) ― 1 + SQRT (1-C 2 X 2 -C 2 Y 2 )
[0198] 但し、前記計算式において、 Cxは、 X方向の曲率（ = 1/Rx)を意味し、 Cyは、 y方 向の曲率（ = 1/Ry)を意味し、 Xは、 X方向に関するレンズ光軸 Oからの距離を意味 し、 Yは、 y方向に関するレンズ光軸 Oからの距離を意味する。 [0198] However, in the above formula, Cx means the curvature in the X direction (= 1 / Rx), Cy means the curvature in the y direction (= 1 / Ry), and X is the X direction. Means the distance from the lens optical axis O with respect to Y, and Y means the distance from the lens optical axis O with respect to the y direction.
[0199] 図 8A〜図 8Dと図 9A〜図 9Dとを比較すると明らかなように、本発明の永久パター ン形成方法ではマイクロレンズ 55aを、 y方向に平行な断面内の焦点距離が X方向に 平行な断面内の焦点距離よりも小さいトーリックレンズとしたことにより、その集光位置 近傍におけるビーム形状の歪みが抑制される。そうであれば、歪みの無い、より高精 細な画像を感光層 150に露光可能となる。また、図 8A〜図 8Dに示す本実施形態の 方が、ビーム径の小さい領域がより広レ、、すなわち焦点深度がより大であることが分 力る。 [0200] なお、マイクロミラー 62の x方向及び y方向に関する中央部の歪の大小関係力 上 記と逆になつている場合は、 X方向に平行な断面内の焦点距離が y方向に平行な断 面内の焦点距離よりも小さいトーリックレンズからマイクロレンズを構成すれば、同様 に、歪みの無い、より高精細な画像を感光層 150に露光可能となる。 8A to 8D and FIGS. 9A to 9D, as is clear from the method for forming a permanent pattern according to the present invention, the microlens 55a has a focal length in the cross section parallel to the y direction. By using a toric lens smaller than the focal length in the cross section parallel to the beam, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, the photosensitive layer 150 can be exposed to a finer image without distortion. In addition, the present embodiment shown in FIGS. 8A to 8D can be characterized in that the region where the beam diameter is small is wider, that is, the depth of focus is larger. [0200] Note that when the micro-mirror 62 is in the opposite direction to the distortion in the center in the x and y directions, the focal length in the cross section parallel to the X direction is parallel to the y direction. If the microlens is made up of a toric lens that is smaller than the focal length in the cross section, similarly, a higher-definition image without distortion can be exposed on the photosensitive layer 150.
[0201] また、マイクロレンズアレイ 55の集光位置近傍に配置されたアパーチャアレイ 59は 、その各アパーチャ 59aに、それと対応するマイクロレンズ 55aを経た光のみが入射 するように配置されたものである。すなわち、このアパーチャアレイ 59が設けられてい ることにより、各アパーチャ 59aに、それと対応しない隣接のマイクロレンズ 55aからの 光が入射することが防止され、消光比が高められる。  [0201] In addition, the aperture array 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged so that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. . That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to enhance the extinction ratio.
[0202] 本来、上記目的で設置されるアパーチャアレイ 59のアパーチャ 59aの径をある程 度小さくすれば、マイクロレンズ 55aの集光位置におけるビーム形状の歪みを抑制す る効果も得られる。し力 そのようにした場合は、アパーチャアレイ 59で遮断される光 量がより多くなり、光利用効率が低下することになる。それに対してマイクロレンズ 55a を非球面形状とする場合は、光を遮断することがないので、光利用効率も高く保たれ る。  [0202] Essentially, if the diameter of the aperture 59a of the aperture array 59 installed for the above purpose is reduced to some extent, the effect of suppressing the distortion of the beam shape at the condensing position of the microlens 55a can also be obtained. If this is done, the amount of light blocked by the aperture array 59 will increase and the light utilization efficiency will decrease. On the other hand, when the microlens 55a has an aspherical shape, the light utilization efficiency is kept high because light is not blocked.
[0203] また、本発明の永久パターン形成方法において、マイクロレンズ 55aは、 2次の非球 面形状であってもよぐより高次 (4次、 6次 · · ·）の非球面形状であってもよい。前記高 次の非球面形状を採用することにより、ビーム形状を更に高精細にすることができる。  [0203] In addition, in the permanent pattern forming method of the present invention, the microlens 55a may have a higher-order (fourth-order, sixth-order ...) aspherical shape, which may be a second-order aspherical shape. There may be. By adopting the higher order aspherical shape, the beam shape can be further refined.
[0204] また、以上説明した実施形態では、マイクロレンズ 55aの光出射側の端面が非球面  [0204] In the embodiment described above, the end surface of the microlens 55a on the light exit side is an aspherical surface.
(トーリック面）とされている力 2つの光通過端面の一方を球面とし、他方をシリンドリ カル面としたマイクロレンズからマイクロレンズアレイを構成して、上記実施形態と同 様の効果を得ることもできる。  The force that is assumed to be a (toric surface) A microlens array can be constructed from microlenses in which one of the two light-passing end surfaces is a spherical surface and the other is a cylindrical surface, and the same effect as in the above embodiment can be obtained. it can.
[0205] 更に、以上説明した実施形態においては、マイクロレンズアレイ 55のマイクロレンズ 55aが、マイクロミラー 62の反射面の歪みによる収差を補正する非球面形状とされて いる力 このような非球面形状を採用する代わりに、マイクロレンズアレイを構成する 各マイクロレンズに、マイクロミラー 62の反射面の歪みによる収差を補正する屈折率 分布を持たせても、同様の効果を得ることができる。  Furthermore, in the embodiment described above, the microlens 55a of the microlens array 55 has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. Such an aspherical shape The same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution that corrects aberration due to distortion of the reflection surface of the micromirror 62 instead of adopting the above.
[0206] そのようなマイクロレンズ 155aの一例を図 10に示す。同図の（A)及び（B)はそれ ぞれ、このマイクロレンズ 155aの正面形状及び側面形状を示すものであり、図示の 通りこのマイクロレンズ 155aの外形形状は平行平板状である。なお、同図における X 、 y方向は、既述した通りである。 An example of such a microlens 155a is shown in FIG. (A) and (B) in the figure are Each shows a front shape and a side shape of the microlens 155a. As shown, the outer shape of the microlens 155a is a parallel plate. The X and y directions in the figure are as described above.
[0207] また、図 11の（A)及び（B)は、このマイクロレンズ 155aによる上記 X方向及び y方 向に平行な断面内におけるレーザ光 Bの集光状態を概略的に示している。このマイ クロレンズ 155aは、光軸 Oから外方に向かって次第に増大する屈折率分布を有する ものであり、同図においてマイクロレンズ 155a内に示す破線は、その屈折率が光軸 〇から所定の等ピッチで変化した位置を示している。図示の通り、 X方向に平行な断 面内と y方向に平行な断面内とを比較すると、後者の断面内の方がマイクロレンズ 15 5aの屈折率変化の割合がより大であって、焦点距離がより短くなつている。このような 屈折率分布型レンズ力 構成されるマイクロレンズアレイを用いても、前記マイクロレ ンズアレイ 55を用いる場合と同様の効果を得ることが可能である。  Further, (A) and (B) of FIG. 11 schematically show the condensing state of the laser light B in the cross section parallel to the X direction and the y direction by the microlens 155a. The microlens 155a has a refractive index distribution that gradually increases outward from the optical axis O. The broken line shown in the microlens 155a in FIG. The position changed with the pitch is shown. As shown in the figure, comparing the cross section parallel to the X direction and the cross section parallel to the y direction, the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and The distance is getting shorter. Even when a microlens array having such a gradient index lens force is used, the same effect as that obtained when the microlens array 55 is used can be obtained.
[0208] なお、先に図 6及び図 7に示したマイクロレンズ 55aのように面形状を非球面とした マイクロレンズにおいて、併せて上述のような屈折率分布を与え、面形状と屈折率分 布の双方によって、マイクロミラー 62の反射面の歪みによる収差を補正するようにし てもよい。  Incidentally, in the microlens having the aspherical surface shape like the microlens 55a previously shown in FIG. 6 and FIG. 7, the refractive index distribution as described above is also given, and the surface shape and the refractive index component are given. The aberration due to the distortion of the reflection surface of the micromirror 62 may be corrected by both the cloths.
[0209] また、上記の実施形態では、 DMD50を構成するマイクロミラー 62の反射面の歪み による収差を補正しているが、 DMD以外の空間光変調素子を用いる本発明の永久 パターン形成方法においても、その空間光変調素子の描素部の面に歪みが存在す る場合は、本発明を適用してその歪みによる収差を補正し、ビーム形状に歪みが生 じることを防止可能である。  [0209] In the above embodiment, the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected. However, the permanent pattern forming method of the present invention using a spatial light modulation element other than the DMD is also used. If there is distortion on the surface of the picture element portion of the spatial light modulator, the present invention can be applied to correct the aberration caused by the distortion and prevent the beam shape from being distorted.
[0210] 次に、前記結像光学系について更に説明する。  [0210] Next, the imaging optical system will be further described.
前記露光ヘッドでは、光照射手段 144からレーザ光が照射されると、 DMD50によ りオン方向に反射される光束線の断面積力 レンズ系 454、 458により数倍 (例えば、 2倍）に拡大される。拡大されたレーザ光は、マイクロレンズアレイ 472の各マイクロレ ンズにより DMD50の各描素部に対応して集光され、アパーチャアレイ 476の対応す るアパーチャを通過する。アパーチャを通過したレーザ光は、レンズ系 480、 482に より被露光面 56上に結像される。 [0211] この結像光学系では、 DMD50により反射されたレーザ光は、拡大レンズ 454、 45 8により数倍に拡大されて被露光面 56に投影されるので、全体の画像領域が広くな る。このとき、マイクロレンズアレイ 472及びアパーチャアレイ 476が配置されていなけ れば、図 2 (B)に示すように、被露光面 56に投影される各ビームスポット BSの 1描素 サイズ (スポットサイズ）が露光エリア 468のサイズに応じて大きなものとなり、露光エリ ァ 468の鮮鋭度を表す MTF (Modulation Transfer Function)特性が低下する In the exposure head, when the laser light is irradiated from the light irradiation means 144, the cross-sectional area force of the light beam reflected in the ON direction by the DMD 50 is enlarged several times (for example, two times) by the lens systems 454 and 458. Is done. The expanded laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50, and passes through the corresponding aperture of the aperture array 476. The laser beam that has passed through the aperture is imaged on the exposed surface 56 by the lens systems 480 and 482. [0211] In this imaging optical system, the laser beam reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. . At this time, if the microlens array 472 and the aperture array 476 are not arranged, as shown in FIG. 2B, one pixel size (spot size) of each beam spot BS projected onto the exposed surface 56 Becomes larger depending on the size of the exposure area 468, and the MTF (Modulation Transfer Function) characteristic representing the sharpness of the exposure area 468 is degraded.
[0212] —方、マイクロレンズアレイ 472及びアパーチャアレイ 476を配置した場合には、 D MD50により反射されたレーザ光は、マイクロレンズアレイ 472の各マイクロレンズに より DMD50の各描素部に対応して集光される。これにより、図 2 (C)に示すように、 露光エリアが拡大された場合でも、各ビームスポット BSのスポットサイズを所望の大き さ（例えば、 10 /i m X 10 /i m)に縮小することができ、 MTF特性の低下を防止して 高精細な露光を行うことができる。なお、露光エリア 468が傾いているのは、描素間の 隙間を無くす為に DMD50を傾けて配置しているからである。 [0212] —On the other hand, when the microlens array 472 and the aperture array 476 are arranged, the laser light reflected by the DMD50 corresponds to each pixel part of the DMD50 by each microlens of the microlens array 472. And condensed. As a result, as shown in FIG. 2C, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, 10 / im × 10 / im). It is possible to perform high-definition exposure by preventing the deterioration of MTF characteristics. The exposure area 468 is tilted because the DMD 50 is tilted in order to eliminate the gap between the pixels.
[0213] また、マイクロレンズの収差によるビームの太りがあっても、アパーチャアレイによつ て被露光面 56上でのスポットサイズが一定の大きさになるようにビームを整形するこ とができると共に、各描素に対応して設けられたアパーチャアレイを通過させることに より、隣接する描素間でのクロストークを防止することができる。  [0213] Even if the beam is thick due to the aberration of the microlens, the aperture array can shape the beam so that the spot size on the exposed surface 56 is constant. At the same time, by passing through an aperture array provided corresponding to each pixel, crosstalk between adjacent pixels can be prevented.
[0214] 更に、光照射手段 144に後述する高輝度光源を使用することにより、レンズ 458か らマイクロレンズアレイ 472の各マイクロレンズに入射する光束の角度が小さくなるの で、 P 接する描素の光束の一部が入射するのを防止することができる。即ち、高消光 比を実現することができる。  [0214] Furthermore, by using a high-intensity light source, which will be described later, as the light irradiation means 144, the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. It is possible to prevent a part of the light beam from entering. That is, a high extinction ratio can be realized.
[0215] <その他の光学系 >  [0215] <Other optical systems>
本発明の永久パターン形成方法では、公知の光学系の中から適宜選択したその 他の光学系と併用してもよぐ例えば、 1対の組合せレンズからなる光量分布補正光 学系などが挙げられる。  In the permanent pattern forming method of the present invention, it may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light quantity distribution correction optical system composed of a pair of combination lenses. .
前記光量分布補正光学系は、光軸に近い中心部の光束幅に対する周辺部の光束 幅の比が入射側に比べて出射側の方が小さくなるように各出射位置における光束幅 を変化させて、光照射手段からの平行光束を DMDに照射するときに、被照射面で の光量分布が略均一になるように補正する。前記光量分布補正光学系につレ、ては、 例えば、特開 2005— 258431号公報の明細書の段落「0090」から「0105」に記載 されているものなどが挙げられる。 The light quantity distribution correcting optical system is configured so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller at the exit side than at the entrance side. When the DMD is irradiated with a parallel light beam from the light irradiation means, the light quantity distribution on the irradiated surface is corrected so as to be substantially uniform. Examples of the light amount distribution correcting optical system include those described in paragraphs “0090” to “0105” of the specification of JP-A-2005-258431.
[0216] 〔現像工程〕 [Development process]
前記現像工程は、前記露光工程により前記感光層を露光し、該感光層の露光した 領域を硬化させた後、未硬化領域を除去することにより現像し、永久パターンを形成 する工程である。  The developing step is a step of exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region to form a permanent pattern.
[0217] 前記未硬化領域の除去方法としては、特に制限はなぐ 目的に応じて適宜選択す ること力 Sでき、例えば、現像液を用いて除去する方法などが挙げられる。  [0217] The method for removing the uncured region is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include a method for removing the uncured region using a developer.
[0218] 前記現像液としては、特に制限はなぐ 目的に応じて適宜選択することができる力 例えば、アルカリ金属又はアルカリ土類金属の水酸化物若しくは炭酸塩、炭酸水素 塩、アンモニア水、 4級アンモニゥム塩の水溶液等が好適に挙げられる。これらの中 でも、炭酸ナトリウム水溶液が特に好ましい。  [0218] The developer is not particularly limited and can be appropriately selected according to the purpose. For example, alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, quaternary Preferable examples include an aqueous solution of ammonium salt. Among these, an aqueous sodium carbonate solution is particularly preferable.
[0219] 前記現像液は、界面活性剤、消泡剤、有機塩基 (例えば、ペンジノレアミン、ェチレ ンジァミン、エタノールァミン、テトラメチルアンモニゥムハイドロキサイド、ジエチレント リアミン、トリエチレンペンタミン、モルホリン、トリエタノールアミン等）や、現像を促進さ せるため有機溶剤（例えば、アルコール類、ケトン類、エステル類、エーテル類、アミ ド類、ラタトン類等）などと併用してもよい。また、前記現像液は、水又はアルカリ水溶 液と有機溶剤を混合した水系現像液であってもよぐ有機溶剤単独であってもよい。  [0219] The developer includes a surfactant, an antifoaming agent, and an organic base (for example, pendinoleamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triphenyl). Ethanolamine) and organic solvents (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination to accelerate development. The developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or an organic solvent alone.
[0220] 〔硬化処理工程〕  [0220] [Curing treatment process]
本発明の永久パターン形成方法は、更に、硬化処理工程として、加熱処理を含み 、更に必要に応じて全面露光処理を含む。  The permanent pattern forming method of the present invention further includes a heat treatment as a curing treatment step, and further includes an entire surface exposure treatment as necessary.
前記硬化処理工程は、前記現像工程が行われた後、形成された永久パターンに おける感光層に対して硬化処理を行う工程である。  The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.
[0221] 一加熱処理一  [0221] One heat treatment
前記加熱処理は、前記本発明の硬化促進剤の熱架橋効果による膜硬度の充分な 向上を図るために行うものである。前記加熱処理としては、全面加熱処理であっても よいし、パターン状に加熱処理を行うものであってもよぐこの中でも、全面加熱処理 が好ましい。 The heat treatment is performed to sufficiently improve the film hardness due to the thermal crosslinking effect of the curing accelerator of the present invention. The heat treatment may be a whole surface heat treatment Of these, heat treatment in a pattern may be performed, and among these, heat treatment on the entire surface is preferable.
[0222] 前記全面加熱処理の方法としては、前記現像工程の後に、前記永久パターンが形 成された前記積層体上の全面を加熱する方法が挙げられる。該全面加熱により、前 記永久パターンの表面の膜強度が高められる。  [0222] Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
前記全面カロ熱におけるカロ熱温度としては、 120〜250°じカ 子ましく、 120〜200°C 力 り好ましい。該加熱温度が 120°C未満であると、加熱処理による膜強度の向上が 得られないことがあり、 250°Cを超えると、前記感光性組成物中の樹脂の分解が生じ 、膜質が弱く脆くなることがある。  As the caloric temperature in the whole surface caloric fever, 120 to 250 ° C., preferably 120 to 200 ° C. is preferable. When the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C, the resin in the photosensitive composition is decomposed and the film quality is weak. May become brittle.
前記全面加熱における加熱時間としては、 10〜： 120分が好ましぐ 15〜60分がよ り好ましい。  The heating time in the entire surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
前記全面加熱を行う装置としては、特に制限はなぐ公知の装置の中から、 目的に 応じて適宜選択することができ、例えば、ドライオーブン、ホットプレート、 IRヒーター などが挙げられる。  The apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
[0223] 全面露光処理 [0223] Full exposure process
前記全面露光処理の方法としては、例えば、前記現像工程の後に、前記永久パタ ーンが形成された前記積層体上の全面を露光する方法が挙げられる。該全面露光 により、前記感光層を形成する感光性組成物中の樹脂の硬化が促進され、前記永久 パターンの表面が硬化される。  Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. By this overall exposure, curing of the resin in the photosensitive composition forming the photosensitive layer is accelerated, and the surface of the permanent pattern is cured.
前記全面露光を行う装置としては、特に制限はなぐ 目的に応じて適宜選択するこ とができるが、例えば、超高圧水銀灯などの UV露光機が好適に挙げられる。  The apparatus for performing the entire surface exposure can be appropriately selected according to the purpose without any particular limitation. For example, a UV exposure machine such as an ultra-high pressure mercury lamp is preferably used.
[0224] なお、前記基材が多層配線基板などのプリント配線板である場合には、該プリント 配線板上に本発明の永久パターンを形成し、更に、以下のように半田付けを行うこと ができる。 [0224] When the base material is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention is formed on the printed wiring board, and soldering may be performed as follows. it can.
即ち、前記現像工程により、前記永久パターンである硬化層が形成され、前記プリ ント配線板の表面に金属層が露出される。該プリント配線板の表面に露出した金属 層の部位に対して金メッキを行った後、半田付けを行う。そして、半田付けを行った 部位に、半導体や部品などを実装する。このとき、前記硬化層による永久パターンが 、保護膜あるいは絶縁膜 (層間絶縁膜)としての機能を発揮し、外部からの衝撃や隣 同士の電極の導通が防止される。 That is, the hardened layer which is the permanent pattern is formed by the developing step, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, semiconductors and parts are mounted on the soldered parts. At this time, the permanent pattern by the hardened layer is It functions as a protective film or insulating film (interlayer insulating film), and prevents external shocks and conduction between adjacent electrodes.
[0225] 本発明の永久パターン形成方法においては、保護膜、層間絶縁膜、及びソルダー レジストパターンの少なくともいずれかを形成するのが好ましレ、。前記永久パターン 形成方法により形成される永久パターンが、前記保護膜又は前記層間絶縁膜である と、配線を外部からの衝撃や曲げ力 保護することができ、特に、前記層間絶縁膜で ある場合には、例えば、多層配線基板ゃビルドアップ配線基板などへの半導体部品 の高密度実装に有用である。  [0225] In the permanent pattern formation method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern. When the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, it is possible to protect the wiring from external impact and bending force, and particularly when the permanent pattern is the interlayer insulating film. Is useful for high-density mounting of semiconductor components on, for example, multilayer wiring boards and build-up wiring boards.
[0226] 本発明の永久パターン形成方法は、高速でパターン形成が可能であるため、各種 ノ ターンの形成に広く用いることができ、特に配線パターンの形成に好適に使用する こと力 Sできる。  [0226] Since the permanent pattern forming method of the present invention enables pattern formation at a high speed, it can be widely used for forming various patterns, and can be particularly suitably used for forming wiring patterns.
また、本発明の永久パターン形成方法により形成される永久パターンは、優れた表 面硬度、絶縁性、耐熱性などを有し、保護膜、層間絶縁膜、及びソルダーレジストパ ターンとして好適に使用することができる。  The permanent pattern formed by the method for forming a permanent pattern of the present invention has excellent surface hardness, insulation, heat resistance, etc., and is suitably used as a protective film, an interlayer insulating film, and a solder resist pattern. be able to.
実施例  Example
[0227] 以下、本発明の実施例について説明するが、本発明は下記実施例に何ら限定され るものではない。なお、実施例:!〜 22及び比較例:!〜 4は、感光性組成物での実施 例及び比較例であり、実施例 23〜26及び比較例 5〜6は、熱硬化性樹脂組成物で の実施例及び比較例である。  [0227] Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples. Examples:! To 22 and Comparative Examples:! To 4 are Examples and Comparative Examples of the photosensitive composition, and Examples 23 to 26 and Comparative Examples 5 to 6 are thermosetting resin compositions. These are Examples and Comparative Examples.
[0228] (実施例 1)  [Example 1]
感光性組成物の調製  Preparation of photosensitive composition
下記組成に基づいて、感光性組成物を調製した。なお、分散溶媒としてメチルェチ ルケトンを用い、固形分濃度を 55質量％として調製した。分散は、ビーズミルを用い て行い、得られた分散液は、粒ゲージにより凝集が無いことを確認した。  A photosensitive composition was prepared based on the following composition. In addition, methyl ethyl ketone was used as a dispersion solvent, and the solid content concentration was adjusted to 55% by mass. Dispersion was performed using a bead mill, and the obtained dispersion was confirmed to be free from aggregation by a particle gauge.
〔感光性組成物溶液の組成〕  [Composition of photosensitive composition solution]
•硫酸バリウム (堺化学工業社製、 B30) 33. 4質量部  • Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) 33.4 parts by mass
•下記構造式 (47)で表されるバインダー 40. 0質量部  • Binder represented by the following structural formula (47) 40.0 parts by mass
•2, 2 ビス（4ーグリシジルフヱニル）プロパン（熱架橋剤） 15. 7質量部 -ジペンタエリスリトールへキサアタリレート 16.0質量部 • 2, 2 Bis (4-glycidylphenyl) propane (thermal crosslinking agent) 15.7 parts by mass -Dipentaerythritol hexaatalylate 16.0 parts by mass
•IRGACURE819(チバ 'スペシャルティ^ ~·ケミカルズ製） 5.8質量部  • IRGACURE819 (Ciba 'Specialty ^ Chemicals) 5.8 parts by mass
•ハイドロキノンモノメチルエーテル 0.056質量部 • Hydroquinone monomethyl ether 0.056 parts by mass
•ジシアンジアミド（ァミン系熱硬化剤） 0.77質量部  • 0.77 parts by mass of dicyandiamide (amin-based thermosetting agent)
•下記構造式（1)で表される硬化促進剤 0.47質量部  • 0.47 parts by mass of curing accelerator represented by the following structural formula (1)
[化 41] [Chemical 41]
構造式 (47)Structural formula (47)
Figure imgf000088_0001
Figure imgf000088_0001
[化 42] 構造式 （ 1 ) [Chemical formula 42] Structural formula (1)
Figure imgf000088_0002
Figure imgf000088_0002
なお、前記構造式（1)で表される硬化促進剤は、次のようにして合成した。  The curing accelerator represented by the structural formula (1) was synthesized as follows.
ナスフラスコにシスー4 シクロへキセン一 1, 2—ジカルボン酸無水物 20質量部と ァセトニトリル 100質量部を入れ、シス— 4—シクロへキセン— 1, 2—ジカルボン酸無 水物が溶解した後、ジへキシルァミン 24.3質量部を加えて 2時間攪拌した。その後 、溶媒を真空留去し、シリカゲルカラムクロマトグラフィーによって、前記構造式（1)で 示される化合物 40.9質量部を得た。このときの収率は 92。/0であった。 In an eggplant flask, 20 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride and 100 parts by mass of acetonitrile are dissolved, and the cis-4-cyclohexene-1,2-dicarboxylic acid anhydride is dissolved. 24.3 parts by mass of dihexylamine was added and stirred for 2 hours. Thereafter, the solvent was removed in vacuo, and 40.9 parts by mass of the compound represented by the structural formula (1) was obtained by silica gel column chromatography. The yield at this time is 92. / 0 .
なお、前記構造式（1)で表される硬化促進剤は、 CHC1を溶媒として1 H— NMRス The curing accelerator represented by the structural formula (1) is a 1 H-NMR spectrum using CHC1 as a solvent.
3  Three
ぺクトノレ（300MHz)を測定して同定した。スペクトルの各ピークは、 5.85-5.65 ( m;2H), 3.63-3.52(m;lH), 3.44— 3.32(m;lH), 3.26— 3.10(m;2H )， 3.01-2.87(m;lH), 2.51— 2.40(m;lH), 2.72— 2. 13(m;2H), 1.6 6-1.52(m;4H), 1.36— 1.23(m;12H), 0.94— 0.88(m;6H)である。 また、前記構造式（1)で表される硬化促進剤の感光性組成物中の含有量は 0.42 質量％である。 The pectinore (300 MHz) was measured and identified. Each peak in the spectrum is 5.85-5.65 (m; 2H), 3.63-3.52 (m; lH), 3.44—3.32 (m; lH), 3.26— 3.10 (m; 2H), 3.01-2.87 (m; lH) , 2.51-2.40 (m; lH), 2.72-2.13 (m; 2H), 1.6 6-1.52 (m; 4H), 1.36-1.23 (m; 12H), 0.94-0.88 (m; 6H) . The content of the curing accelerator represented by the structural formula (1) in the photosensitive composition is 0.42% by mass.
感光性フィルムの製造  Production of photosensitive film
得られた感光性組成物を、前記支持体としての厚み 20 μ mの PET (ポリエチレンテ レフタレート）フィルム上に、塗布し、乾燥させて、膜厚 30 z mの感光層を形成した。 次いで、該感光層の上に、前記保護フィルムとして 12 z m厚のポリプロピレンフィノレ ムをラミネートで積層し、感光性フィルムを製造した。 The obtained photosensitive composition was mixed with 20 μm thick PET (polyethylene film) as the support. The film was coated on a (phthalate) film and dried to form a photosensitive layer having a thickness of 30 zm. Next, a polypropylene film having a thickness of 12 zm was laminated as a protective film on the photosensitive layer to produce a photosensitive film.
[0231] 一永久パターンの形成一 [0231] Formation of a permanent pattern
一一積層体の調製一一  Preparation of each laminate
次に、前記基材として、配線形成済みの銅張積層板 (スルーホールなし、銅厚み 1 2 x m)の表面に化学研磨処理を施して調製した。該銅張積層板上に、前記感光性 フィルムの感光層が前記銅張積層板に接するようにして前記感光性フィルムにおけ る保護フィルムを剥がしながら、真空ラミネーター（名機製作所製、 MVLP500)を用 いて積層させ、前記銅張積層板と、前記感光層と、前記ポリエチレンテレフタレートフ イルム (支持体)とがこの順に積層された積層体を調製した。  Next, as the base material, a surface of a copper-clad laminate (with no through holes and a copper thickness of 12 × m) on which wiring was formed was prepared by chemical polishing treatment. A vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd., MVLP500) is peeled off on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film is in contact with the copper clad laminate. Thus, a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order was prepared.
前記感光性フィルムにおける保護フィルムを剥がした時点では、前記感光層の表 面に強いタック性がなぐ剥離自体も容易に行うことができた。  At the time when the protective film on the photosensitive film was peeled off, the peeling itself without strong tackiness on the surface of the photosensitive layer could be easily performed.
[0232] 露光工程  [0232] Exposure process
前記調製した積層体における感光層に対し、ポリエチレンテレフタレートフィルム（ 支持体)側から、レーザ露光装置を用いて、 405nmのレーザ光を、直径の異なる穴 部が形成されるパターンが得られるように照射して露光し、前記感光層の一部の領 域を硬化させた。  Using a laser exposure device, 405 nm laser light is irradiated from the polyethylene terephthalate film (support) side so that a pattern in which holes having different diameters are formed is applied to the photosensitive layer in the prepared laminate. Then, a portion of the photosensitive layer was cured.
[0233] 一一現像工程一一  [0233] Every development process
室温にて 10分間静置した後、前記積層体からポリエチレンテレフタレートフィルム（ 支持体）を剥がし取り、銅張積層板上の感光層の全面に、アルカリ現像液として、 1質 量％炭酸ソーダ水溶液を用い、 30°Cにて 60秒間シャワー現像し、未硬化の領域を 溶解除去した。その後、水洗し、乾燥させ、永久パターンを形成した。  After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and 1% by weight aqueous sodium carbonate solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Used and shower developed for 60 seconds at 30 ° C to dissolve and remove uncured areas. Thereafter, it was washed with water and dried to form a permanent pattern.
[0234] 一一硬化処理工程一一  [0234] Every step of the curing process
前記永久パターンが形成された積層体の全面に対して、 160°Cで 60分間、加熱処 理を施し、永久パターンの表面を硬化し、膜強度を高めた。該永久パターンを目視 で観察したところ、永久パターンの表面に気泡は認められなかった。  The entire surface of the laminate on which the permanent pattern was formed was heated at 160 ° C. for 60 minutes to cure the surface of the permanent pattern and increase the film strength. When the permanent pattern was visually observed, no bubbles were observed on the surface of the permanent pattern.
[0235] 前記製造した感光性フィルムについて、露光感度、解像度、露光速度、及び保存 安定性の評価を行い、前記形成した永久パターンについて鉛筆硬度、及び誘電特 性の評価を行った。結果を表 4に示す。 [0235] About the produced photosensitive film, exposure sensitivity, resolution, exposure speed, and storage The stability was evaluated, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. The results are shown in Table 4.
[0236] <最短現像時間の測定 > [0236] <Measurement of shortest development time>
前記製造した感光性フィルムにおいて、前記積層体からポリエチレンテレフタレート フィルム（支持体）を剥がし取り、銅張積層板上の前記感光層の全面に 30°Cの 1質量 %炭酸ナトリウム水溶液を 0. 15MPaの圧力にてスプレーし、炭酸水素ナトリウム水 溶液のスプレー開始から銅張積層板上の感光層が溶解除去されるまでに要した時 間を測定し、これを最短現像時間とした。  In the produced photosensitive film, the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is added to the entire surface of the photosensitive layer on the copper clad laminate at 0.15 MPa. Spraying was performed under pressure, and the time required from the start of spraying of the sodium hydrogen carbonate solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.
<露光感度 >  <Exposure sensitivity>
前記製造した感光性フィルムにおいて、前記ポリエチレンテレフタレートフィルム（支 持体)側から、露光装置を用いて 0. lmj/cm2から 21/2倍間隔で 100mj/cm2まで の光エネルギー量の異なる光を照射して露光し、前記感光層の一部の領域を硬化さ せた。室温にて 10分間静置した後、前記感光性フィルムからポリエチレンテレフタレ 一トフイルム（支持体）を剥がし取り、銅張り積層板上の感光層全面に、炭酸水素ナト リウム水溶液（30°C、 1質量％)を上記の方法により求めた最短時間現像時間の 2倍 の時間スプレーし、未硬化の領域を溶解除去して、残った硬化領域の厚みを測定し た。次いで、光の照射量と、硬化層の厚さとの関係をプロットして感度曲線を得た。こ うして得た感度曲線力 硬化領域の厚さが露光前と同じ厚みとなった時の光ェネル ギー量を、感光層を硬化させるために必要な光エネルギー量とした。 In the photosensitive film described above produced, from the polyethylene terephthalate film (supporting bearing member) side, different amount of light energy from 0. LMJ / cm 2 to 100 mj / cm 2 at 2 1/2 times intervals by using the exposure apparatus Exposure was performed by irradiating light, and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive film, and an aqueous sodium bicarbonate solution (30 ° C, 1 ° C) was applied to the entire photosensitive layer on the copper-clad laminate. (% By mass) was sprayed for twice the shortest development time determined by the above method, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. The sensitivity curve force obtained in this way was the amount of light energy when the thickness of the cured region was the same as that before exposure, and the amount of light energy required to cure the photosensitive layer.
その結果得られた前記感光層を硬化させるために必要な光エネルギー量について は、表 3〜表 9に示した。  The amount of light energy required to cure the resulting photosensitive layer is shown in Tables 3-9.
[0237] <解像度 > [0237] <Resolution>
得られた前記永久パターン形成済みのプリント配線基板の表面を光学顕微鏡で観 察し、硬化層パターンの穴部に残膜が無レ、、最小の穴径を測定し、これを解像度とし た。該解像度は数値が小さいほど良好である。その結果、解像度は、 70 z mであつ た。  The surface of the printed circuit board on which the permanent pattern had been formed was observed with an optical microscope, and no residual film was found in the hole portion of the cured layer pattern. The minimum hole diameter was measured, and this was taken as the resolution. The smaller the numerical value, the better the resolution. As a result, the resolution was 70 zm.
[0238] <露光速度 >  [0238] <Exposure speed>
405nmレーザ露光装置を用いて、露光光と前記感光層とを相対的に移動させる速 度を変更し、永久パターンが形成される速度を求めた。露光は、前記調製した積層 体における感光層に対して、ポリエチレンテレフタレートフィルム（支持体)側から行つ た。なお、この設定速度が速い方が効率的な永久パターン形成が可能となる。なお、 前記 405nmレーザ露光装置は、前記 DMDからなる光変調手段を有し、露光速度 は、 13mmZsecであった。 Using a 405 nm laser exposure apparatus, the relative speed of moving the exposure light and the photosensitive layer The speed at which the permanent pattern was formed was determined by changing the degree. The exposure was performed from the polyethylene terephthalate film (support) side to the photosensitive layer in the prepared laminate. It should be noted that an efficient permanent pattern can be formed at a higher setting speed. The 405 nm laser exposure apparatus had a light modulation means composed of the DMD, and the exposure speed was 13 mmZsec.
[0239] <保存安定性 > [0239] <Storage stability>
前記製造した感光性フィルムを 60°Cドライの促進条件の下、 2日間保管した。 2日 後に露光感度及び解像度を測定し、下記基準に基づいて、保存安定性の評価を行 つた。露光感度は 30mj/cm2、解像度は 70 μ mであり、保存安定性に優れることが 認められた。 The produced photosensitive film was stored for 2 days under accelerated conditions of 60 ° C drying. Two days later, exposure sensitivity and resolution were measured, and storage stability was evaluated based on the following criteria. The exposure sensitivity was 30 mj / cm 2 and the resolution was 70 μm, indicating excellent storage stability.
〔評価基準〕  〔Evaluation criteria〕
◎：露光感度及び解像度の変化がなぐ保存安定性に極めて優れる。  A: Extremely excellent storage stability without change in exposure sensitivity and resolution.
〇：露光感度及び解像度の変化がほとんどなぐ保存安定性に優れる。 ◯: Excellent storage stability with almost no change in exposure sensitivity and resolution.
△:露光感度及び解像度が低下し、現像が困難となり、保存安定性に劣る。 Δ: Exposure sensitivity and resolution decrease, development becomes difficult, and storage stability is poor.
X：露光感度及び解像度が著しく低下し、保存安定性に極めて劣る、あるいは、保 存することができない。  X: Exposure sensitivity and resolution are remarkably lowered, and storage stability is extremely inferior or cannot be stored.
[0240] <鉛筆硬度 > [0240] <Pencil hardness>
前記永久パターン形成済みのプリント配線基板に対して、常法に従レ、金メッキを行 つた後、水溶性フラックス処理を行った。次いで、 260°Cに設定された半田槽に 5秒 間にわたって、 3回浸漬し、フラックスを水洗で除去した。そして、該フラックス除去後 の永久パターンについて、 JIS K— 5400に基づいて、鉛筆硬度を測定した。  The printed wiring board on which the permanent pattern had been formed was subjected to gold plating according to a conventional method, and then subjected to a water-soluble flux treatment. Next, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the pencil hardness was measured about the permanent pattern after this flux removal based on JIS K-5400.
その結果、鉛筆硬度は 5H以上であった。また、 目視観察を行ったところ、前記永久 ノ ターンにおける硬化膜の剥がれ、ふくれ、変色は認められなかった。  As a result, the pencil hardness was 5H or higher. Further, when visually observed, no peeling, blistering, or discoloration of the cured film in the permanent pattern was observed.
[0241] <誘電特性の測定 > [0241] <Measurement of dielectric properties>
膜厚 500 a mの硬化膜の誘電特性を、アジデント'テクノロジ一社製 LCRメーターと The dielectric properties of a cured film with a thickness of 500 am are
4291A型固体電極を用いて 25°Cで測定した結果、 1GHzでの誘電率は 3. 3でありWhen measured at 25 ° C using a 4291A type solid electrode, the dielectric constant at 1 GHz is 3.3.
、誘電正接は 0. 013であった。 The dielectric loss tangent was 0.013.
[0242] (実施例 2) 下記組成に基づいて、感光性組成物を調製し、実施例 1と同様にして感光性フィル ム及び積層体を調製し、永久パターンを形成した。 [0242] (Example 2) A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性組成物及び感光性フィルムについ て、露光感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永 久パターンについて鉛筆硬度、及び誘電特性の評価を行った。結果を表 3に示す。 〔感光性組成物溶液の組成〕  Further, the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the permanent pattern thus formed was measured for pencil hardness, And dielectric properties were evaluated. The results are shown in Table 3. [Composition of photosensitive composition solution]
'硫酸バリウム 33. 4質量部  'Barium sulfate 33.4 parts by mass
•スチレン/無水マレイン酸/プチルアタリレート共重合体（モル比 40/32/28) とベンジルァミン (該共重合体の無水物基に対して 1. 0当量）との付加反応物  • Addition reaction product of styrene / maleic anhydride / butyl acrylate copolymer (molar ratio 40/32/28) and benzylamine (1.0 equivalent to the anhydride group of the copolymer)
40. 0質量部  40.0 parts by mass
•2, 2—ビス（4ーグリシジルフヱニル）プロパン（熱架橋剤） 15. 7質量部  • 2, 2-bis (4-glycidylphenyl) propane (thermal crosslinking agent) 15.7 parts by mass
.ジペンタエリスリトールへキサアタリレート 16. 0質量部 Dipentaerythritol hexaatalylate 16.0 parts by mass
•IRGACURE819 (チバ'スペシャルティ^ ~ ·ケミカルズ製） 5. 8質量部  • IRGACURE819 (Ciba's Specialty ^ Chemicals) 5. 8 parts by mass
•ノヽイドロキノンモノメチルエーテル 0. 056質量部 • Neuroquinone monomethyl ether 0.056 parts by mass
•前記構造式（1)で表される硬化促進剤 0. 47質量部  • Curing accelerator represented by the structural formula (1) 0.47 parts by mass
'ジシアンジアミド（ァミン系熱硬化剤） 0. 77質量部  'Dicyandiamide (Amin-based thermosetting agent) 0.77 parts by mass
* 1：下記構造式 (VII)で表されるユニット Α及びユニット Βを有するマレアミド酸系 共重合体である。該ユニット Aは 2種の構成単位からなり、その内の一の構成単位に おける R1はフエニルであり、他の構成単位における R1はブチルォキシカルボニル、 R 3及び R4は水素原子である。上記ユニット Bにおける R2はべンジルである。上記ュニッ ト Aにおける繰り返し単位のモル分率 Xは、前記一の構成単位については 40モル％ であり、前記他の構成単位については 28モル％であり、上記ユニット Bにおける繰り 返し単位のモル分率 yは 32モル％である。また、前記スチレン/無水マレイン酸/ブ チルアタリレート共重合体の無水物基に対する前記ベンジルァミンの反応量は 1. 0 当量である。 * 1: A maleamic acid copolymer having unit Α and unit 表 represented by the following structural formula (VII). The unit A consists of two structural units, R 1 to definitive one of the structural units of which are phenyl, R 1 in the other structural units are butyl O alkoxycarbonyl, R 3 and R 4 are a hydrogen atom is there. R 2 in unit B is benzyl. The mole fraction X of the repeating unit in Unit A is 40 mol% for the one constituent unit and 28 mol% for the other constituent unit, and the mole fraction of the repeating unit in Unit B is the same. The rate y is 32 mol%. The reaction amount of the benzylamine with respect to the anhydride group of the styrene / maleic anhydride / butyl acrylate copolymer is 1.0 equivalent.
上記ビュル単量体であるブチルアタリレートのホモポリマーのガラス転移温度（Tg) は、 _ 54°Cである。  The glass transition temperature (Tg) of the homopolymer of butyl acrylate, which is the bulle monomer, is _54 ° C.
[化 43] 構造式 (V I I ) [Chemical 43] Structural formula (VII)
Figure imgf000093_0001
実施例 2における、前記構造式（1)で表される硬化促進剤の感光性組成物中の含 有量は 0. 42質量％である。
Figure imgf000093_0001
In Example 2, the content of the curing accelerator represented by the structural formula (1) in the photosensitive composition is 0.42% by mass.
[0243] (実施例 3) [0243] (Example 3)
実施例 1において、感光性組成物中の前記熱架橋剤、 2, 2—ビス（4ーグリシジル フエニル)プロパン 15. 7質量部を、下記構造式 (X)で表される熱架橋剤 (TEPIC) 8 . 2質量部に変えたこと以外は、実施例 1と同様にして感光性組成物を調製し、実施 例 1と同様にして感光性フィルム及び積層体を調製し、永久パターンを形成した。 また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 3に示す。  In Example 1, 15.7 parts by mass of the thermal crosslinking agent, 2,2-bis (4-glycidylphenyl) propane, in the photosensitive composition was added to the thermal crosslinking agent (TEPIC) represented by the following structural formula (X). A photosensitive composition was prepared in the same manner as in Example 1 except that the amount was changed to 8.2 parts by mass. A photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern. Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 3.
[0244] [化 44] 構造式 （X )[0244] [Chemical 44] Structural formula (X)
Figure imgf000093_0002
Figure imgf000093_0002
(実施例 4)  (Example 4)
実施例 1において、感光性組成物中の前記熱架橋剤、 2， 2—ビス (4ーグリシジル フエニル）プロパンを、ェピコート YX4000 (ジャパンエポキシレジン社製、エポキシ樹 脂）に変えたこと以外は、実施例 1と同様にして感光性組成物を調製し、実施例 1と同 様にして感光性フィルム及び積層体を調製し、永久パターンを形成した。  In Example 1, except that the thermal crosslinking agent, 2,2-bis (4-glycidylphenyl) propane, in the photosensitive composition was changed to Epicoat YX4000 (Japan Epoxy Resin, Epoxy resin). A photosensitive composition was prepared in the same manner as in Example 1, and a photosensitive film and laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 3に示す。 Further, for the photosensitive film produced in the same manner as in Example 1, the exposure sensitivity, The image quality, the exposure speed, and the storage stability were evaluated, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. The results are shown in Table 3.
[0246] (実施例 5) [Example 5]
実施例 1において、感光性組成物中の前記構造式（1)で表される硬化促進剤を、 下記構造式（2)で表される硬化促進剤に変えたこと以外は、実施例 1と同様にして感 光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層体を調製し、永 久パターンを形成した。  In Example 1, except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to a curing accelerator represented by the following structural formula (2), Example 1 and A photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 4に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 4.
[0247] [化 45]
Figure imgf000094_0001
構造式 （2 ) [0247] [Chemical 45]
Figure imgf000094_0001
Structural formula ( 2)
なお、前記構造式（2)で表される硬化促進剤は、次のようにして合成した。 ナスフラスコにシス _4—シクロへキセン一 1， 2—ジカルボン酸無水物 7.7質量部 とァセトニトリル 30質量部を入れ、シス _4—シクロへキセン— 1， 2—ジカルボン酸無 水物が溶解した後、ジォクチルァミン 12.1質量部をカ卩えて 2時間攪拌した。その後、 溶媒を真空留去し、シリカゲルカラムクロマトグラフィーによって、前記構造式 (2)で 示される化合物 9.1質量部を得た。このときの収率は 46%であった。  The curing accelerator represented by the structural formula (2) was synthesized as follows. Add 7.7 parts by mass of cis_4-cyclohexene-1,2-dicarboxylic anhydride and 30 parts by mass of acetonitrile to the eggplant flask, and after the cis_4-cyclohexene-1,2-dicarboxylic acid anhydride has dissolved, Dioctylamine 12.1 parts by mass was added and stirred for 2 hours. Thereafter, the solvent was removed in vacuo, and 9.1 parts by mass of the compound represented by the structural formula (2) was obtained by silica gel column chromatography. The yield at this time was 46%.
なお、前記構造式（1)で表される硬化促進剤は、 CHC1を溶媒として1 H— NMRス The curing accelerator represented by the structural formula (1) is a 1 H-NMR spectrum using CHC1 as a solvent.
3  Three
ぺクトノレ（300MHz)を測定して同定した。スペクトルの各ピークは、 5.85-5.60 ( m;2H), 3.62-3.52(m;lH), 3.43— 3.32(m;lH), 3.26— 3.10(m;3H )， 3.05-2.87(m;2H), 2.51— 2.35(m;lH), 2.22— 2. 13(m;2H), 1.7 0-1.50(m;4H), 1.36— 1.23(m;20H), 0.94— 0.85(m;6H)である。また 、前記構造式（2)で表される硬化促進剤の感光性組成物中の含有量は 0.42質量 %である。  The pectinore (300 MHz) was measured and identified. Each peak of the spectrum is 5.85-5.60 (m; 2H), 3.62-3.52 (m; lH), 3.43—3.32 (m; lH), 3.26— 3.10 (m; 3H), 3.05-2.87 (m; 2H) , 2.51-2.35 (m; lH), 2.22-2.13 (m; 2H), 1.7 0-1.50 (m; 4H), 1.36-1.23 (m; 20H), 0.94-0.85 (m; 6H) . In addition, the content of the curing accelerator represented by the structural formula (2) in the photosensitive composition is 0.42% by mass.
[0248] (実施例 6) [Example 6]
実施例 1において、感光性組成物中の感光性組成物中の前記構造式（ 1 )で表され る硬化促進剤をを、下記構造式（3)で表される硬化促進剤に変えたこと以外は、実 施例 1と同様にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム及 び積層体を調製し、永久パターンを形成した。 In Example 1, it is represented by the structural formula (1) in the photosensitive composition in the photosensitive composition. A photosensitive composition was prepared in the same manner as in Example 1 except that the curing accelerator was changed to a curing accelerator represented by the following structural formula (3). A photosensitive film and a laminate were prepared to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 4に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 4.
[0249] [化 46]
Figure imgf000095_0001
[0249] [Chem 46]
Figure imgf000095_0001
なお、前記構造式（3)で表される硬化促進剤は、次のようにして合成した。 ナスフラスコにシス _4—シクロへキセン一 1， 2—ジカルボン酸無水物 2.92質量 部とクロ口ホルム 30質量部を入れ、シス _4—シクロへキセン一 1， 2—ジカルボン酸 無水物が溶解した後、 4 ベンジルピペリジン 3.37質量部をカ卩えて 2時間攪拌した 。その後、溶媒を真空留去し、酢酸ェチルで再結晶化することによって、前記構造式 (3)で示される化合物 4.5質量部を得た。このときの収率は 72%であった。  The curing accelerator represented by the structural formula (3) was synthesized as follows. Place 2.92 parts by mass of cis_4-cyclohexene-1,2-dicarboxylic acid anhydride and 30 parts by mass of cycloform in an eggplant flask and dissolve the cis_4-cyclohexene-1,2-dicarboxylic acid anhydride. 4) 3.37 parts by mass of benzylpiperidine was added and stirred for 2 hours. Thereafter, the solvent was distilled off in vacuo, and recrystallization was performed with ethyl acetate to obtain 4.5 parts by mass of the compound represented by the structural formula (3). The yield at this time was 72%.
なお、前記構造式（3)で表される硬化促進剤は、 CHC1を溶媒として1 H— NMRス The curing accelerator represented by the structural formula (3) is a 1 H-NMR spectrum using CHC1 as a solvent.
3  Three
ぺクトノレ（300MHz)を測定して同定した。スペクトルの各ピークは、 7.32-7.19( m;4H), 7.14(d;lH), 5.84— 5.77(m;lH), 5.72— 5.62(m;lH), 4.71 -4.62(m;lH), 3.87(d;lH), 3.23— 3.03(m;3H), 2.85(d;lH), 2.69 —2.50(m;lH), 2.46— 2.28(m;lH), 1.86— 1.76(m;3H), 1.26— 1.1 6(m;2H)である。また、前記構造式（3)で表される硬化促進剤の感光性組成物中 の含有量は 0.42質量％である。  The pectinore (300 MHz) was measured and identified. Each peak in the spectrum is 7.32-7.19 (m; 4H), 7.14 (d; lH), 5.84-5.77 (m; lH), 5.72-5.62 (m; lH), 4.71 -4.62 (m; lH), 3.87 (d; lH), 3.23-3.03 (m; 3H), 2.85 (d; lH), 2.69 -2.50 (m; lH), 2.46-2.28 (m; lH), 1.86-1.76 (m; 3H), 1.26 — 1.1 6 (m; 2H). The content of the curing accelerator represented by the structural formula (3) in the photosensitive composition is 0.42% by mass.
[0250] (実施例 7) [0250] (Example 7)
実施例 1において、感光性組成物中の感光性組成物中の前記構造式（ 1 )で表され る硬化促進剤を、下記構造式 (4)で表される硬化促進剤に変えたこと以外は、実施 例 1と同様にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び 積層体を調製し、永久パターンを形成した。  In Example 1, except that the curing accelerator represented by the structural formula (1) in the photosensitive composition in the photosensitive composition was changed to a curing accelerator represented by the following structural formula (4). Prepared a photosensitive composition in the same manner as in Example 1, prepared a photosensitive film and laminate in the same manner as in Example 1, and formed a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 4に示す。 Further, for the photosensitive film produced in the same manner as in Example 1, the exposure sensitivity, The image quality, the exposure speed, and the storage stability were evaluated, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. The results are shown in Table 4.
[0251] [化 47]
Figure imgf000096_0001
[0251] [Chemical 47]
Figure imgf000096_0001
なお、前記構造式 (4)で表される硬化促進剤は、次のようにして合成した。 ナスフラスコにシス一 4一シクロへキセン一 1， 2 _ジカルボン酸無水物 5質量部とァ セトニトリル 40質量部を入れ、シス _4—シクロへキセン— 1， 2—ジカルボン酸無水 物が溶解した後、 N—メチル一ペンジノレアミン 3. 97質量部をカ卩えて 2時間攪拌した その後、溶媒を真空留去し、
Figure imgf000096_0002
て 、刖目 ΰ構造 式 (4)で示される化合物 4. 5質量部を得た。このときの収率は 76%であった。 The curing accelerator represented by the structural formula (4) was synthesized as follows. Place 5 parts by mass of cis-1,4-cyclohexene-1,2-dicarboxylic acid anhydride and 40 parts by mass of acetonitrile in the eggplant flask and dissolve the cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. , N-methyl monopendinoleamine 3. 97 parts by weight was added and stirred for 2 hours.
Figure imgf000096_0002
As a result, 4.5 parts by mass of the compound represented by the structural formula (4) was obtained. The yield at this time was 76%.
なお、前記構造式 (4)で表される硬化促進剤は、 CHC1を溶媒として1 H— NMRス The curing accelerator represented by the structural formula (4) is a 1 H-NMR spectrum using CHC1 as a solvent.
3  Three
ぺクトノレ（300MHz)を測定して同定した。スペクトルの各ピークは、 7.44-7. 15 ( m;5H), 5.86-5. 67(m;2H), 4. 75—4. 51(m;2H), 3. 31— 3. 24(m;lH ), 3. 13-3.00(m;4H), 2. 92— 2. 81(m;lH), 2. 51— 2. 37(m;lH), 2. 3 1-2. 18(m;lH), 2. 10-2. 04(m;lH)である。また、前記構造式（4)で表され る硬化促進剤の感光性組成物中の含有量は 0.42質量％である。  The pectinore (300 MHz) was measured and identified. Each peak in the spectrum is 7.44-7.15 (m; 5H), 5.86-5.67 (m; 2H), 4.75—4.51 (m; 2H), 3.31—3.24 (m ; lH), 3.13-3.00 (m; 4H), 2.92— 2.81 (m; lH), 2.51— 2.37 (m; lH), 2.3 3 1-2.18 ( m; lH), 2. 10-2.04 (m; lH). The content of the curing accelerator represented by the structural formula (4) in the photosensitive composition is 0.42% by mass.
[0252] (実施例 8) [0252] (Example 8)
実施例 1において、感光性組成物中の前記構造式（1)で表される硬化促進剤を、 下記構造式 (5)で表される硬化促進剤に変えたこと以外は、実施例 1と同様にして感 光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層体を調製し、永 久パターンを形成した。  In Example 1, except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to a curing accelerator represented by the following structural formula (5), Example 1 and A photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 4に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 4.
[0253] [化 48] なお、前記構造式（5)で表される硬化促進剤は、次のようにして合成した。 [0253] [Chemical 48] The curing accelerator represented by the structural formula (5) was synthesized as follows.
ナスフラスコにシス一 4一シクロへキセン一 1， 2 _ジカルボン酸無水物 30質量部と ァセトニトリノレ 100質量部を入れ、シス _4—シクロへキセン— 1 , 2—ジカルボン酸無 水物が溶解した後、ピぺラジン 8. 49質量部を加えて 2時間攪拌した。その後、懸濁 液をろ過することによって、前記構造式（5)で表れされる示される化合物 35. 9質量 部を得た。このときの収率は 93%であった。  Place 30 parts by weight of cis-4-cyclohexene-1,2-dicarboxylic anhydride and 100 parts by weight of acetonitrinol in the eggplant flask, and then dissolve the cis_4-cyclohexene-1,2-dicarboxylic acid anhydride. Piperazine 8.49 parts by mass was added and stirred for 2 hours. Thereafter, the suspension was filtered to obtain 35.9 parts by mass of the compound represented by the structural formula (5). The yield at this time was 93%.
なお、前記構造式（5)で表される硬化促進剤は、 DMSOを溶媒として1 H— NMR スぺクトノレ（300MHz)を測定して同定した。スペクトルの各ピークは、 5. 69 - 5. 55 (m ; 4H) , 3. 57 - 3. 22 (m ; 14H) , 2. 72— 2. 40 (m ; 8H) , 2. 40— 2. 15 (m ; 6 H)である。前記構造式（5)で表される硬化促進剤の感光性組成物中の含有量は 0. 42質量％である。 The curing accelerator represented by the structural formula (5) was identified by measuring 1 H-NMR spectrum (300 MHz) using DMSO as a solvent. Each peak in the spectrum is 5.69-5.55 (m; 4H), 3.57-3.22 (m; 14H), 2.72—2.40 (m; 8H), 2.40—2 15 (m; 6 H). The content of the curing accelerator represented by the structural formula (5) in the photosensitive composition is 0.42% by mass.
[0254] (実施例 9〜： 12) [Examples 9 to 12]
実施例 1、 2、 5及び 6において、露光装置を下記に説明するパターン形成装置に 代えた以外は、実施例 2と同様にして前記製造した感光性組成物及び感光性フィル ムについて、露光感度、解像度、露光速度の評価を行い、前記形成した永久パター ンについて鉛筆硬度、及び誘電特性の評価を行った。結果を表 5に示す。  In Examples 1, 2, 5 and 6, the exposure sensitivity of the photosensitive composition and the photosensitive film produced in the same manner as in Example 2 except that the exposure apparatus was replaced with the pattern forming apparatus described below. Then, resolution and exposure speed were evaluated, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. The results are shown in Table 5.
[0255] < <パターン形成装置 > > [0255] <<Pattern forming device>>
前記光照射手段として図 12〜： 17に示す合波レーザ光源と、前記光変調手段とし て図 1に示す主走查方向にマイクロミラーが 1， 024個配列されたマイクロミラー列が 、副走查方向に 768組配列された内、 1， 024個 X 256列のみを駆動するように制御 した DMD50と、図 2に示した一方の面がトーリック面であるマイクロレンズ 474をァレ 記感光層に結像する光学系 480、 482とを有するパターン形成装置を用いた。  As the light irradiating means, a combined laser light source shown in FIGS. 12 to 17 and a micromirror array in which 1,024 micromirrors are arranged in the main running direction shown in FIG. Among the 768 pairs arranged in the vertical direction, DMD50 controlled to drive only 1,024 x 256 rows, and microlens 474 whose one side is toric as shown in FIG. A pattern forming apparatus having optical systems 480 and 482 for forming an image is used.
[0256] また、前記マイクロレンズにおけるトーリック面は以下に説明するものを用いた。 [0256] The toric surface of the microlens described below was used.
まず、 DMD50の前記描素部としてのマイクロレンズ 474の出射面における歪みを 補正するため、該出射面の歪みを測定した。結果を図 3に示した。図 3においては、 反射面の同じ高さ位置を等高線で結んで示してあり、等高線のピッチは 5nmである。 なお、同図に示す X方向及び y方向は、マイクロミラー 62の 2つ対角線方向であり、マ イク口ミラー 62は y方向に延びる回転軸を中心として回転する。また、図 4A及び図 4 Bにはそれぞれ、上記 X方向、 y方向に沿ったマイクロミラー 62の反射面の高さ位置 変位を示した。 First, in order to correct the distortion on the exit surface of the microlens 474 serving as the pixel portion of the DMD 50, the strain on the exit surface was measured. The results are shown in FIG. In FIG. 3, the same height position of the reflecting surface is shown connected by contour lines, and the pitch of the contour lines is 5 nm. The X direction and the y direction shown in the figure are the two diagonal directions of the micromirror 62, and The mouth mirror 62 rotates about a rotation axis extending in the y direction. 4A and 4B show the height position displacement of the reflection surface of the micromirror 62 along the X direction and the y direction, respectively.
図 3及び図 4に示した通り、マイクロミラー 62の反射面には歪みが存在し、そして特 にミラー中央部に注目してみると、 1つの対角線方向（y方向）の歪み力 別の対角線 方向（X方向）の歪みよりも大きくなつていることが判る。このため、このままではマイク 口レンズアレイ 55のマイクロレンズ 55aで集光されたレーザ光 Bの集光位置における 形状が歪んでしまうことが判る。  As shown in FIGS. 3 and 4, there is distortion on the reflecting surface of the micromirror 62, and when looking at the center of the mirror in particular, the distortion force in one diagonal direction (y direction) is another diagonal line. It can be seen that the distortion is larger than the distortion in the direction (X direction). For this reason, it can be seen that the shape of the laser beam B collected by the microlens 55a of the microphone port lens array 55 is distorted in this state.
[0257] 図 5A及び図 5Bには、マイクロレンズアレイ 55全体の正面形状及び側面形状をそ れぞれ詳しく示した。これらの図には、マイクロレンズアレイ 55の各部の寸法も記入し てあり、それらの単位は mmである。先に図 1を参照して説明したように DMD50の 1 , 024個 X 256列のマイクロミラー 62が駆動されるものであり、それに対応させてマイク 口レンズアレイ 55は、横方向に 1, 024個並んだマイクロレンズ 55aの列を縦方向に 2 56列並設して構成されている。なお、同図 Aでは、マイクロレンズアレイ 55の並び順 を横方向については jで、縦方向については kで示している。  [0257] FIGS. 5A and 5B show the front and side shapes of the entire microlens array 55 in detail. In these drawings, the dimensions of each part of the microlens array 55 are also entered, and their unit is mm. As described above with reference to FIG. 1, 1,024 × 256 rows of micromirrors 62 of DMD50 are driven. Correspondingly, microphone mouth lens array 55 has 1,024 in the horizontal direction. The microlenses 55a are arranged in a row with 256 rows arranged in the vertical direction. In FIG. A, the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.
[0258] また、図 6A及び図 6Bには、マイクロレンズアレイ 55における 1つのマイクロレンズ 5 5aの正面形状及び側面形状をそれぞれ示した。なお、同図 Aには、マイクロレンズ 5 5aの等高線を併せて示してある。各マイクロレンズ 55aの光出射側の端面は、マイク 口ミラー 62の反射面の歪みによる収差を補正する非球面形状とされている。より具体 的には、マイクロレンズ 55aはトーリックレンズとされており、前記 X方向に光学的に対 応する方向の曲率半径 Rx=— 0. 125mm,前記 y方向に対応する方向の曲率半径 Ry= -0. 1mmである。  [0258] FIGS. 6A and 6B show a front shape and a side shape of one microlens 55a in the microlens array 55, respectively. In FIG. A, the contour lines of the microlens 55a are also shown. The end surface on the light exit side of each microlens 55a has an aspherical shape that corrects aberration due to distortion of the reflection surface of the microphone mirror 62. More specifically, the micro lens 55a is a toric lens, and has a radius of curvature Rx = −0.125 mm in the direction optically corresponding to the X direction, and a radius of curvature Ry = in the direction corresponding to the y direction. -0. 1mm.
[0259] したがって、前記 X方向及び y方向に平行な断面内におけるレーザ光 Bの集光状態 は、概略、それぞれ図 7A及び図 7Bに示す通りとなる。つまり、 X方向に平行な断面 内と y方向に平行な断面内とを比較すると、後者の断面内の方がマイクロレンズ 55a の曲率半径がより小であって、焦点距離がより短くなつていることが判る。  Therefore, the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction is roughly as shown in FIGS. 7A and 7B, respectively. In other words, comparing the cross section parallel to the X direction and the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. I understand that.
[0260] なお、マイクロレンズ 55aを前記形状とした場合の、該マイクロレンズ 55aの集光位 置 (焦点位置)近傍におけるビーム径を計算機によってシミュレーションした結果を図 8A、図 8B、図 8C、及び図 8Dに示す。また比較のために、マイクロレンズ 55aが曲率 半径 Rx = Ry= _0. 1mmの球面形状である場合について、同様のシミュレーション を行った結果を図 9A、図 9B、図 9C、及び図 9Dに示す。なお、各図における zの値 は、マイクロレンズ 55aのピント方向の評価位置を、マイクロレンズ 55aのビーム出射 面からの距離で示してレ、る。 [0260] When the microlens 55a is shaped as described above, the result of simulating the beam diameter near the condensing position (focal position) of the microlens 55a by a computer is shown in FIG. It is shown in FIG. 8A, FIG. 8B, FIG. 8C and FIG. 8D. For comparison, FIG. 9A, FIG. 9B, FIG. 9C, and FIG. 9D show the results of similar simulations when the microlens 55a has a spherical shape with a curvature radius of Rx = Ry = _0.1 mm. Note that the value of z in each figure indicates the evaluation position in the focus direction of the microlens 55a by the distance from the beam exit surface of the microlens 55a.
[0261] また、前記シミュレーションに用いたマイクロレンズ 55aの面形状は、下記計算式で 計算される。 [0261] The surface shape of the microlens 55a used in the simulation is calculated by the following equation.
[数 3]  [Equation 3]
_ C X 2 X 2+ C y 2 Y 2 _ CX 2 X 2 + C y 2 Y 2
― 1 + S Q R T { 1 - C χ 2 X 2 - C y 2 Y 2 ) ― 1 + SQRT (1-C χ 2 X 2 -C y 2 Y 2 )
[0262] ただし、前記計算式において、 Cxは、 X方向の曲率（ = lZRx)を意味し、 Cyは、 y 方向の曲率（ = 1/Ry)を意味し、 Xは、 X方向に関するレンズ光軸 Oからの距離を意 味し、 Yは、 y方向に関するレンズ光軸 Oからの距離を意味する。 [0262] However, in the above formula, Cx means the curvature in the X direction (= lZRx), Cy means the curvature in the y direction (= 1 / Ry), and X is the lens light in the X direction. This means the distance from the axis O, and Y means the distance from the lens optical axis O in the y direction.
[0263] 図 8A〜Dと図 9A〜Dとを比較すると明らかなように、マイクロレンズ 55aを、 y方向 に平行な断面内の焦点距離力 方向に平行な断面内の焦点距離よりも小さいトーリツ クレンズとしたことにより、その集光位置近傍におけるビーム形状の歪みが抑制される 。この結果、歪みの無い、より高精細なパターンを感光層 150に露光可能となる。ま た、図 8A〜Dに示す本実施形態の方が、ビーム径の小さい領域がより広レ、、すなわ ち焦点深度がより大であることが判る。  [0263] As can be seen by comparing Figs. 8A to 9D and Figs. 9A to 9D, the microlens 55a has a focal length force in the cross section parallel to the y direction, and is smaller than the focal length in the cross section parallel to the direction. By using the cleanse, distortion of the beam shape in the vicinity of the condensing position is suppressed. As a result, a higher-definition pattern without distortion can be exposed on the photosensitive layer 150. In addition, it can be seen that in the present embodiment shown in FIGS. 8A to 8D, the region where the beam diameter is small is wider, that is, the focal depth is larger.
[0264] また、マイクロレンズアレイ 55の集光位置近傍に配置されたアパーチャアレイ 59は 、その各アパーチャ 59aに、それと対応するマイクロレンズ 55aを経た光のみが入射 するように配置されたものである。すなわち、このアパーチャアレイ 59が設けられてい ることにより、各アパーチャ 59aに、それと対応しない隣接のマイクロレンズ 55aからの 光が入射することが防止され、消光比が高められる。  [0264] The aperture array 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged so that only light that has passed through the corresponding microlens 55a is incident on each aperture 59a. . That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to enhance the extinction ratio.
[0265] (実施例 13)  [Example 13]
実施例 1において、感光性組成物中の構造式（1)で表される硬化促進剤の添加量 を 21. 3質量部に変えたこと以外は、実施例 1と同様にして感光性組成物を調製し、 実施例 1と同様にして感光性フィルム及び積層体を調製し、永久パターンを形成した 。なお、実施例 13における、前記構造式（1)で表される硬化促進剤の感光性組成物 中の含有量は 16. 0質量％である。 In Example 1, the photosensitive composition was the same as Example 1 except that the addition amount of the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to 21.3 parts by mass. A photosensitive film and a laminate were prepared in the same manner as in Example 1, and a permanent pattern was formed. . In Example 13, the content of the curing accelerator represented by the structural formula (1) in the photosensitive composition was 16.0% by mass.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 6に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 6.
[0266] (実施例 14)  [Example 14]
実施例 1において、感光性組成物中の構造式（1)で表される硬化促進剤の添加量 を 0. 005質量部に変えたこと以外は、実施例 1と同様にして感光性組成物を調製し 、実施例 1と同様にして感光性フィルム及び積層体を調製し、永久パターンを形成し た。なお、実施例 14における、前記構造式（1)で表される硬化促進剤の感光性組成 物中の含有量は 0. 0048質量％である。  The photosensitive composition was the same as in Example 1, except that the addition amount of the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to 0.005 parts by mass in Example 1. A photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern. In Example 14, the content of the curing accelerator represented by the structural formula (1) in the photosensitive composition is 0.000048% by mass.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 6に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 6.
[0267] (実施例 15)  [Example 15]
下記組成に基づいて、感光性組成物を調製し、実施例 1と同様にして感光性フィル ム及び積層体を調製し、永久パターンを形成した。  A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性組成物及び感光性フィルムについ て、露光感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永 久パターンについて鉛筆硬度、及び誘電特性の評価を行った。結果を表 6に示す。 また、前記構造式（1)で表される硬化促進剤の感光性組成物中の含有量は 0. 42 質量％である。  Further, the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the permanent pattern thus formed was measured for pencil hardness, And dielectric properties were evaluated. The results are shown in Table 6. The content of the curing accelerator represented by the structural formula (1) in the photosensitive composition is 0.42% by mass.
〔感光性組成物溶液の組成〕  [Composition of photosensitive composition solution]
•硫酸バリウム (堺化学工業社製、 B30) 33. 4質量部  • Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) 33.4 parts by mass
•下記構造式 (V)で表されるバインダー 40. 0質量部 • Binder 40.0 parts by mass represented by the following structural formula (V)
•下記構造式 (VIII)で表される熱架橋剤（エポキシ当量： 214gZeq.、粘度： 62, 0• Thermal crosslinking agent represented by the following structural formula (VIII) (epoxy equivalent: 214 gZeq., Viscosity: 62, 0
00mPa- s) 15. 7質量部 00mPa- s) 15.7 parts by mass
.ジペンタエリスリトールへキサアタリレート 16. 0質量部 • IRGACURE819 (チバ'スペシャルティ、 'ケミカルズ製） 5. 8質量部 Dipentaerythritol hexaatalylate 16.0 parts by mass • IRGACURE819 (Ciba 'Specialty,'Chemicals') 5. 8 parts by mass
'ノヽイドロキノンモノメチルエーテル 0. 056質量部  'Noduloquinone monomethyl ether 0.056 parts by mass
'ジシアンジアミド（ァミン系熱硬化剤） 0. 77質量部  'Dicyandiamide (Amin-based thermosetting agent) 0.77 parts by mass
'前記構造式（1)で表される硬化促進剤 0. 47質量部  'A curing accelerator represented by the structural formula (1) 0.47 parts by mass
[化 49]  [Chemical 49]
Figure imgf000101_0001
構造式 （V )
Figure imgf000101_0001
Structural formula (V)
[0269] [化 50] 構造式 (V I I I ) [0269] [Chemical formula 50] Structural formula (V I I I)
Figure imgf000101_0002
Figure imgf000101_0002
[0270] (実施例 16)  [0270] (Example 16)
実施例 15において、感光性組成物中の前記構造式（1)で表される硬化促進剤を、 前記構造式（2)で表される硬化促進剤に変えたこと以外は、実施例 15と同様にして 感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層体を調製し、 永久パターンを形成した。  In Example 15, Example 15 was changed except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to the curing accelerator represented by the structural formula (2). A photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 6に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 6.
[0271] (実施例 17) [Example 17]
実施例 15において、感光性組成物中の前記構造式（1)で表される硬化促進剤を、 前記構造式 (3)で表される硬化促進剤に変えたこと以外は、実施例 15と同様にして 感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層体を調製し、 永久パターンを形成した。  In Example 15, Example 15 except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was changed to the curing accelerator represented by the structural formula (3). A photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 7に示す。 Further, for the photosensitive film produced in the same manner as in Example 1, the exposure sensitivity, The image quality, the exposure speed, and the storage stability were evaluated, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. The results are shown in Table 7.
[0272] (実施例 18)  [0272] (Example 18)
実施例 15において、感光性組成物中の前記構造式 (V)で表されるバインダーを、 スチレン Z無水マレイン酸 Zブチルアタリレート共重合体（モノレ比 40Z32Z28)とべ ンジルァミン (該共重合体の無水物基に対して 1. 0当量）との付加反応物に変えたこ と以外は、実施例 15と同様にして感光性組成物を調製し、実施例 1と同様にして感 光性フィルム及び積層体を調製し、永久パターンを形成した。  In Example 15, the binder represented by the structural formula (V) in the photosensitive composition was changed to styrene Z maleic anhydride Z butyl acrylate copolymer (mono ratio 40Z32Z28) and benzylamine (anhydrous copolymer). A photosensitive composition was prepared in the same manner as in Example 15 except that it was changed to an addition reaction product of 1.0 equivalent to the physical group). A body was prepared to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 7に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 7.
[0273] (実施例 19)  [0273] (Example 19)
実施例 1において、感光性組成物中の前記構造式 (47)で表されるバインダー 40 質量部を 20質量部に変え、以下に示す合成例 1で得られた不飽和基を有するアタリ ル樹脂（B1)を 20質量部添加したこと以外は、実施例 1と同様にして感光性組成物 を調製し、実施例 1と同様にして感光性フィルム及び積層体を調製し、永久パターン を形成した。  In Example 1, 40 parts by mass of the binder represented by the structural formula (47) in the photosensitive composition is changed to 20 parts by mass, and the allyl resin having an unsaturated group obtained in Synthesis Example 1 shown below. A photosensitive composition was prepared in the same manner as in Example 1 except that 20 parts by mass of (B1) was added, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern. .
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 7に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 7.
[0274] 一合成例 1 (アクリル樹脂 (B1)の合成）一 [0274] Synthesis Example 1 (Synthesis of acrylic resin (B1))
メチルメタタリレート 45. 1質量部、メタクリノレ酸 47. 3質量部、ァゾイソバレロ二トリノレ 1質量部、プロピレングリコールモノメチルエーテル 215質量部力もなる混合溶液を 窒素ガス雰囲気下、 90°Cの反応容器中に 3時間かけて滴下した。滴下後 4時間反応 し、アクリル樹脂 (A1)を得た。  Methyl metatalylate 45.1 parts by weight, methacrynoreic acid 47.3 parts by weight, azoisovalero nitrinole 1 part by weight, propylene glycol monomethyl ether 215 parts by weight In a nitrogen gas atmosphere in a 90 ° C reaction vessel It was dripped over 3 hours. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin (A1).
次に、得られたアクリル樹脂 (A1)溶液にサイクロマー A200 (ダイセルィ匕学工業（ 株）製） 54. 7質量部及びハイドロキノンモノメチルエーテル 0. 2質量部、トリフエニル フォスフィン 1質量部をカ卩えて、空気を吹き込みながら 80°Cで 8時間反応させて、不 飽和基を有するアクリル樹脂（Bl)溶液（固形分酸価； 111、 Mw; 18, 000、二重結 合当量 2. 3mmolZg、プロピレングリコールモノメチルエーテル 41質量0 /0溶液）を得 た。 Next, the obtained acrylic resin (A1) solution was charged with 54.7 parts by mass of cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd.), 0.2 part by mass of hydroquinone monomethyl ether, and 1 part by mass of triphenylphosphine. , React for 8 hours at 80 ° C while blowing air. Acrylic resin having an unsaturated group (Bl) to obtain a solution of (acid value of solid content;; 111, Mw 18, 000 , double bonds eq 2. 3mmolZg, propylene glycol monomethyl ether 41 mass 0/0 solution).
[0275] (実施例 20)  [0275] (Example 20)
実施例 1において、感光性組成物中の前記構造式 (47)で表されるバインダー 40 質量部を 20質量部に変え、以下に示す合成例 2で得られた不飽和基を有するアタリ ル樹脂（B2)を 20質量部添加したこと以外は、実施例 1と同様にして感光性組成物 を調製し、実施例 1と同様にして感光性フィルム及び積層体を調製し、永久パターン を形成した。  In Example 1, 40 parts by mass of the binder represented by the structural formula (47) in the photosensitive composition was changed to 20 parts by mass, and the allyl resin having an unsaturated group obtained in Synthesis Example 2 shown below. A photosensitive composition was prepared in the same manner as in Example 1 except that 20 parts by mass of (B2) was added, and a photosensitive film and laminate were prepared in the same manner as in Example 1 to form a permanent pattern. .
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 7に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 7.
[0276] 合成例 2 (アクリル樹脂 (B2)の合成） [0276] Synthesis Example 2 (Synthesis of acrylic resin (B2))
メチルメタタリレート 45. 1質量部、メタクリル酸 47. 3質量部、ァゾイソバレロ二トリル 1質量部、プロピレングリコールモノメチルエーテル 215質量部からなる混合溶液を 窒素ガス雰囲気下、 90°Cの反応容器中に 3時間かけて滴下した。滴下後 4時間反応 し、アクリル樹脂 (A2)を得た。  A mixed solution consisting of 45.1 parts by weight of methyl metatalylate, 47.3 parts by weight of methacrylic acid, 1 part by weight of azoisovaleronitryl, and 215 parts by weight of propylene glycol monomethyl ether was placed in a 90 ° C reaction vessel under a nitrogen gas atmosphere It was dripped over 3 hours. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin (A2).
次に、得られたアクリル樹脂 (A2)溶液にグリシジルメタタリレート 35. 9質量部及び ハイドロキノンモノメチルエーテル 0. 2質量部、トリフエニルフォスフィン 1質量部を加 えて、空気を吹き込みながら 80°Cで 8時間反応させて、不飽和基を有するアクリル樹 脂（B2)溶液（固形分酸価； 104、 Mw; 20, 000、二重結合当量 2. 0  Next, 35.9 parts by mass of glycidyl methacrylate and 0.2 part by mass of hydroquinone monomethyl ether and 1 part by mass of triphenylphosphine were added to the resulting acrylic resin (A2) solution, and 80 ° C while blowing air. For 8 hours, and an acrylic resin (B2) solution having an unsaturated group (solid content acid value; 104, Mw; 20,000, double bond equivalent 2.0)
mmol/g、プロピレングリコールモノメチルエーテル 37質量0 /0溶液）を得た。 mmol / g, to obtain a propylene glycol monomethyl ether 37 mass 0/0 solution).
[0277] (実施例 21) [0277] (Example 21)
実施例 1において、感光性組成物中の前記構造式（1)で表される硬化促進剤 0. 4 7質量部を 1. 24質量部とし、ジシアンジアミドを添カ卩しなかったこと以外は、実施例 1 と同様にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層 体を調製し、永久パターンを形成した。  In Example 1, except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was 0.47 parts by mass, 1.24 parts by mass, and dicyandiamide was not added. A photosensitive composition was prepared in the same manner as in Example 1, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 8に示す。 Further, for the photosensitive film produced in the same manner as in Example 1, the exposure sensitivity, The image quality, the exposure speed, and the storage stability were evaluated, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. The results are shown in Table 8.
[0278] (実施例 22)  [Example 22]
実施例 2において、感光性組成物中の前記構造式（1)で表される硬化促進剤 0. 4 7質量部を 1. 24質量部とし、ジシアンジアミドを添カ卩しなかったこと以外は、実施例 1 と同様にして感光性組成物を調製し、実施例 1と同様にして感光性フィルム及び積層 体を調製し、永久パターンを形成した。  In Example 2, except that the curing accelerator represented by the structural formula (1) in the photosensitive composition was 0.47 parts by mass, 1.24 parts by mass, and dicyandiamide was not added. A photosensitive composition was prepared in the same manner as in Example 1, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 8に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 8.
[0279] (比較例 1)  [0279] (Comparative Example 1)
下記組成に基づいて、感光性組成物を調製し、実施例 1と同様にして感光性フィル ム及び積層体を調製し、永久パターンを形成した。  A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性組成物及び感光性フィルムについ て、露光感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永 久パターンについて鉛筆硬度、及び誘電特性の評価を行った。結果を表 9に示す。 〔感光性組成物溶液の組成〕  Further, the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the permanent pattern thus formed was measured for pencil hardness, And dielectric properties were evaluated. The results are shown in Table 9. [Composition of photosensitive composition solution]
•硫酸バリウム (堺化学工業社製、 B30) 31. 6質量部  • Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) 31. 6 parts by mass
•前記構造式 (47)で表されるバインダー 40. 0質量部  • 40.0 parts by mass of the binder represented by the structural formula (47)
•2, 2_ビス（4—グリシジルフヱニル）プロパン（熱架橋剤） 10. 8質量部 •下記構造式 (XI)で表されるモノマー 16. 0質量部  • 2, 2_bis (4-glycidylphenyl) propane (thermal crosslinking agent) 10.8 parts by mass • Monomer represented by the following structural formula (XI) 16.0 parts by mass
•IRGACURE819 (チバ 'スペシャルティ^ ~ ·ケミカルズ製） 6. 0質量部  • IRGACURE819 (Ciba 'Specialty ^ Chemicals) 6.0 parts by mass
•ジシアンジアミド（ァミン系熱硬化剤） 0. 60質量部  • Dicyandiamide (Amin-based thermosetting agent) 0.60 parts by mass
• 2Ε4ΜΖ (熱硬化促進剤） *2 0. 48質量部 • 2Ε4ΜΖ (thermosetting accelerator) * 2 0.48 parts by mass
* 2：下記構造式 (48 )で表される 2 _ェチル _ 4 _メチルイミダゾール（四国化成 (株 )製）  * 2: 2_Ethyl_4_Methylimidazole (Shikoku Kasei Co., Ltd.) represented by the following structural formula (48)
[0280] [化 51] 構造式 (X I )
Figure imgf000105_0001
[0280] [Chemical 51] Structural formula (XI)
Figure imgf000105_0001
[化 52]  [Chemical 52]
2 E4MZ  2 E4MZ
E t 構造式 (48) E t Structural formula (48)
Μ θ  Μ θ
[0281] (比較例 2)  [0281] (Comparative Example 2)
比較例 1において、感光性組成物中の前記熱硬化促進剤、 2Ε4ΜΖを、下記構造 式（49)で表される 2ΜΑΟΚ (2, 4—ジァミノ _6 _〔2'—メチルイミダゾリル一（1 ' )〕 —ェチル _s_トリァジンのイソシァヌル酸付加物、四国化成工業 (株)製）に変えたこ と以外は、実施例 1と同様にして感光性組成物を調製し、実施例 1と同様にして感光 性フィルム及び積層体を調製し、永久パターンを形成した。 In Comparative Example 1, the thermosetting accelerator in the photosensitive composition, 2 感光 4 、, is represented by 2ΜΑΟΚ (2,4-diamino_6_ [2'-methylimidazolyl mono (1 ')) represented by the following structural formula (49). ] A photosensitive composition was prepared in the same manner as in Example 1 except that it was changed to an isocyanuric acid adduct of ethyl _ s _triazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.). A photosensitive film and a laminate were prepared and a permanent pattern was formed.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 8に示す。  Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 8.
[0282] [化 53] [0282] [Chemical 53]
2MAOK  2MAOK
N H 2 O NH 2 O
N =< 义  N = <义
N 構造式 (49)  N Structural formula (49)
ΝΎ Ν Η 2 Ο Ν Ο Ν Ύ Ν Η 2 Ο Ν Ο
M e ' Η  M e 'Η
[0283] (比較例 3)  [0283] (Comparative Example 3)
下記組成に基づいて、感光性組成物を調製し、実施例 1と同様にして感光性フィル ム及び積層体を調製し、永久パターンを形成した。  A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性フィルムについて、露光感度、解 像度、露光速度、及び保存安定性の評価を行い、前記形成した永久パターンについ て鉛筆硬度、及び誘電特性の評価を行った。結果を表 9に示す。 〔感光性組成物溶液の組成〕 Further, the photosensitive film produced in the same manner as in Example 1 was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was measured for pencil hardness and dielectric properties. Evaluation was performed. The results are shown in Table 9. [Composition of photosensitive composition solution]
•前記構造式 (47)で表されるバインダー 40. 0質量部  • 40.0 parts by mass of the binder represented by the structural formula (47)
'ェピコート YX4000 (ジャパンエポキシレジン社製、エポキシ樹脂）  'Epicoat YX4000 (made by Japan Epoxy Resin, epoxy resin)
10. 8質量部  10.8 parts by mass
•前記構造式 (XI)で表されるモノマー 16. 0質量部  • Monomer represented by the structural formula (XI) 16.0 parts by mass
•IRGACURE819 (チバ 'スペシャルティ^ ~ ·ケミカルズ製） 6. 0質量部  • IRGACURE819 (Ciba 'Specialty ^ Chemicals) 6.0 parts by mass
•ジシアンジアミド（ァミン系熱硬化剤） 0. 60質量部  • Dicyandiamide (Amin-based thermosetting agent) 0.60 parts by mass
•前記構造式 (48)で表される 2Ε4ΜΖ (熱硬化促進剤） 0. 16質量部  • 2Ε4ΜΖ (thermosetting accelerator) represented by the structural formula (48) 0.16 parts by mass
[0284] (比較例 4) [0284] (Comparative Example 4)
下記組成に基づいて、感光性組成物を調製し、実施例 1と同様にして感光性フィル ム及び積層体を調製し、永久パターンを形成した。  A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
また、実施例 1と同様にして前記製造した感光性組成物及び感光性フィルムについ て、露光感度、解像度、露光速度、及び保存安定性の評価を行い、前記形成した永 久パターンについて鉛筆硬度、及び誘電特性の評価を行った。結果を表 9に示す。 〔感光性組成物溶液の組成〕  Further, the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the permanent pattern thus formed was measured for pencil hardness, And dielectric properties were evaluated. The results are shown in Table 9. [Composition of photosensitive composition solution]
'硫酸バリウム (堺化学工業社製、 Β30) 29. 2質量部  'Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., Β30) 29.2 parts by mass
前記構造式 (47)で表されるバインダー 40. 0質量部 前記構造式 (X)で表される熱架橋剤 (TEPIC) 5. 6質量咅 前記構造式 (XI)で表されるモノマー 16. 0質量部 Binder represented by the structural formula (47) 40.0 parts by mass Thermal crosslinking agent (TEPIC) represented by the structural formula (X) 5.6 parts by mass Monomer represented by the structural formula (XI) 16. 0 parts by mass
'IRGACURE819 (チバ 'スペシャルティ^ ~ ·ケミカルズ製） 6. 0質量部 'IRGACURE819 (Ciba' Specialty ^ · Made by Chemicals) 6.0 parts by mass
'ミン系熱硬化剤） 0. 60質量部  'Min-based thermosetting agent) 0.60 parts by mass
前記構造式 (49)で表される 2ΜΑΟΚ (熱硬化促進剤） 0. 40質量部  2ΜΑΟΚ (thermosetting accelerator) represented by the structural formula (49) 0.40 parts by mass
[0285] [表 3]
Figure imgf000107_0001
[0285] [Table 3]
Figure imgf000107_0001
[0286] [表 4]
Figure imgf000107_0002
[0286] [Table 4]
Figure imgf000107_0002
[0287] [表 5]
Figure imgf000108_0001
[0287] [Table 5]
Figure imgf000108_0001
[0288] [表 6]
Figure imgf000108_0002
[0288] [Table 6]
Figure imgf000108_0002
[0289] [表 7]
Figure imgf000109_0001
[0289] [Table 7]
Figure imgf000109_0001
[0290] [表 8] 実施例 21 実施例 22 [0290] [Table 8] Example 21 Example 22
I*'キシァクリレ-ト 無水マレイン酸 ノインダ一 I * 'xyacrylate maleic anhydride noindaichi
感 構造式（47) 共重合体 光 2,2-ビス 2,2—ビス 性 熱架橋剤 (4-ゲリシシ 'ルフ 1 レ） (4-ゲリシシ'ルフ Iニル） 組 フ'口 Λ'ン ロ Λ'ン 成  Sensitivity Structural formula (47) Copolymer Light 2,2-bis 2,2-bis property Thermal cross-linking agent (4-Gelicy's Ruf 1 Le) (4-Gelicy's Ruf I Nyl) Λ '
エホ'キシ潜在 I*'キシ潜在 物 硬化促進剤 硬化促進剤 硬化促進剤 構造式（1) 構造式（1) 露光感度  Eho'Xi latent I * 'Xi latent product Curing accelerator Curing accelerator Curing accelerator Structural formula (1) Structural formula (1) Exposure sensitivity
25 25 25 25
(mJノ cm2) (mJ cm 2 )
解像度（/ m) 70 70 Resolution (/ m) 70 70
Λ光 l£度 (mm/ s) 10 10 評 鉛筆硬度 5Η 5Η 価 Λ light l £ degree (mm / s) 10 10 Rating Pencil hardness 5Η 5Η
誘電率 3.7 3.4 誘電正接 0.014 0.015 保存安定性 © ©  Dielectric constant 3.7 3.4 Dissipation factor 0.014 0.015 Storage stability © ©
[0291] [表 9]
Figure imgf000110_0001
[0291] [Table 9]
Figure imgf000110_0001
[0292] (実施例 23)  [0292] (Example 23)
一熱硬化性樹脂組成物の調製一  Preparation of one thermosetting resin composition
下記組成に基づレ、て、熱硬化性組成物を調製した。  A thermosetting composition was prepared based on the following composition.
〔熱硬化性樹脂組成物の組成〕  [Composition of thermosetting resin composition]
'ェピコート 828 (油化シェル社製、エポキシ樹脂） 100質量部  'Epicoat 828 (Epoxy Shell, epoxy resin) 100 parts by mass
-メチルテトラヒドロ無水フタル酸（日本ゼオン社製、 QH— 200、硬化剤）  -Methyltetrahydrophthalic anhydride (Nippon Zeon, QH-200, curing agent)
95質量部  95 parts by mass
•前記構造式（1)で表される硬化促進剤 4. 5質量部 上記組成でエポキシ樹脂、硬化剤及び硬化促進剤を混合し、ミキサー（7， OOOrp m、 1分間）で撹拌することにより、実施例 23の熱硬化性樹脂を調製した。  • Curing accelerator represented by the structural formula (1) 4.5 parts by mass By mixing the epoxy resin, curing agent and curing accelerator with the above composition, and stirring with a mixer (7, OOOrpm, 1 minute) A thermosetting resin of Example 23 was prepared.
[0293] 前記製造した熱硬化性樹脂組成物について、ゲル化時間、耐熱性及び貯蔵安定 性の評価を行った。結果を表 10に示す。 [0293] The thermosetting resin composition produced was evaluated for gelation time, heat resistance and storage stability. The results are shown in Table 10.
<ゲル化時間 >  <Gelification time>
得られた熱硬化性樹脂組成物について、 JIS K5059 (1997)に準じ、 150°Cで熱 板法によりゲルィ匕時間を測定した。  The gelling time of the obtained thermosetting resin composition was measured by a hot plate method at 150 ° C. according to JIS K5059 (1997).
<耐熱性 >  <Heat resistance>
得られた熱硬化性樹脂組成物について、硬化樹脂の耐熱性の指標である熱変形 温度を測定した。該熱変形温度は、 JIS K7207 (1997)に準じ、 HDTテスター S-3 M (東洋精機）を用いて測定した。樹脂の硬化条件は 150°C、 2時間で行った。 <貯蔵安定性 > About the obtained thermosetting resin composition, the heat deformation temperature which is an index of the heat resistance of the cured resin was measured. The heat distortion temperature is in accordance with JIS K7207 (1997), HDT tester S-3 Measurement was performed using M (Toyo Seiki). The resin was cured at 150 ° C for 2 hours. <Storage stability>
40°Cで貯蔵した熱硬化性樹脂組成物について、 B型粘度計を用いて樹脂組成物 の粘度を測定し、樹脂粘度が初期粘度の 2倍になった時間を評価時間とした。この 評価時間をもとに、下記評価基準により、貯蔵安定性を評価した。  For the thermosetting resin composition stored at 40 ° C, the viscosity of the resin composition was measured using a B-type viscometer, and the time when the resin viscosity was twice the initial viscosity was taken as the evaluation time. Based on this evaluation time, storage stability was evaluated according to the following evaluation criteria.
◎ : 48時間超  ◎: Over 48 hours
〇： 24時間超 48時間以内  ○: Over 24 hours within 48 hours
△ : 10時間超 24時間以内  △: Over 10 hours within 24 hours
X : 10時間以内  X: Within 10 hours
[0294] (実施例 24〜26) [0294] (Examples 24 to 26)
実施例 23において、前記構造式（1)で示される硬化促進剤を、表 9に示す硬化促 進剤に代えたこと以外は、実施例 23と同様にして、実施例 24〜26の熱硬化性樹脂 組成物を調製した。なお、実施例 26では、硬化剤を添加せず、硬化促進剤の添カロ 量を 20質量部とした。  In Example 23, the heat curing of Examples 24-26 was performed in the same manner as in Example 23 except that the curing accelerator represented by the structural formula (1) was replaced with the curing accelerator shown in Table 9. Resin composition was prepared. In Example 26, the curing agent was not added, and the addition amount of the curing accelerator was 20 parts by mass.
得られた各熱硬化性樹脂組成物について、実施例 23と同様に、ゲル化時間、耐熱 性及び貯蔵安定性の評価を行った。結果を表 10に示す。  Each thermosetting resin composition obtained was evaluated in the same manner as in Example 23 for gelation time, heat resistance, and storage stability. The results are shown in Table 10.
[0295] (比較例 5〜6) [0295] (Comparative Examples 5 to 6)
実施例 23において、構造式（1)で示される硬化促進剤を、表 10に示す従来の硬 化促進剤に代え、外部刺激によりアミンを生成し、分子内にカルボキシル基とアミド基 とを 1対 1の比で有する構造である化合物からなる硬化促進剤を使用しなかったこと 以外は、実施例 23と同様にして、比較例 5〜6の熱硬化性樹脂組成物を調製した。 得られた各熱硬化性樹脂組成物について、実施例 23と同様に、ゲル化時間、耐熱 性及び貯蔵安定性の評価を行った。結果を表 11に示す。  In Example 23, the curing accelerator represented by the structural formula (1) was replaced with the conventional curing accelerator shown in Table 10, and an amine was generated by external stimulation, and a carboxyl group and an amide group were formed in the molecule. Thermosetting resin compositions of Comparative Examples 5 to 6 were prepared in the same manner as in Example 23 except that a curing accelerator composed of a compound having a structure having a ratio of 1 to 1 was not used. Each thermosetting resin composition obtained was evaluated in the same manner as in Example 23 for gelation time, heat resistance, and storage stability. The results are shown in Table 11.
[0296] [表 10] 実施例 23 実施例 24 実施例 25 実施例 26 熱 [0296] [Table 10] Example 23 Example 24 Example 25 Example 26 Heat
硬 エポキシ樹脂 ェビコ一卜 828 ェビコ一卜 828 工ビコ一卜 828 工ビコ一卜 828 化  Hard Epoxy Resin Ebico 1 828 Ebico 1 828 Industrial Bico 1 828 Industrial Bico 1 828
性 メチル亍トラヒト'口 メチル亍トラヒト'口 メチル亍トラヒト'口  Sex Methyl Trachit 'Mouth Methyl Trachit' Mouth Methyl Trachit 'Mouth
樹 硬化剤 - 無水フタル酸 無水フタル酸 無水フタル酸  Tree Hardener-Phthalic anhydride Phthalic anhydride Phthalic anhydride
脂  Fat
組 エホ'キシ潜在 エホ 'キシ潜在 L卞'キシ潜在 I木'キシ潜在 成 硬化促進剤 硬化促進剤 硬化促進剤 硬化促進剤 硬化促進剤 物 構造式（1 ) 構造式（2) 構造式（5) 構造式（5) ゲル化時間 (分） 7.2 8.9 6.4 1 5.5 評 熱変形温度 C) 1 26 1 23 1 28 1 20 価  Pair Eho 'Xi latent Eho' Xi latent L 卞 'Xi latent I Tree' Xi latent Lamination curing accelerator Curing accelerator Curing accelerator Curing accelerator Curing accelerator Material Structural formula (1) Structural formula (2) Structural formula (5 ) Structural formula (5) Gelation time (min) 7.2 8.9 6.4 1 5.5 Rating Thermal deformation temperature C) 1 26 1 23 1 28 1 20
貯蔵安定性 © © © ◎  Storage stability © © © ◎
[表 11] [Table 11]
Figure imgf000112_0001
Figure imgf000112_0001
表 3〜表 9の結果より、外部刺激によりアミンを生成し、分子内にカルボキシノレ基と アミド基とを 1対 1の比で有する構造の化合物からなる本発明の硬化促進剤を使用し た実施例 1〜22の感光性組成物及びこの感光性組成物を用いて製造した感光性フ イルムにおける感光層は、保存安定性、露光感度及び解像度に優れ、前記感光性フ イルムを用いて形成した永久パターンにおける硬化層の表面硬度も誘電特性も良好 であることが確認された。特に、前記硬化促進剤の感光性組成物中での含有量が 0 . 01〜： 15質量％である実施例 1〜： 12の感光性フィルムは、保存安定性及び誘電特 性の双方が極めて優れていることが判った。また、本発明の硬化促進剤のみを用い 、アミン系熱硬化剤であるジシアンジアミドを使用しなかった実施例 21及び 22では、 解像度、鉛筆硬度、誘電特性などを殆ど低下させることなぐ特に高感度な感光性フ イルムが得られることが判った。  From the results in Tables 3 to 9, the curing accelerator of the present invention comprising an amine generated by an external stimulus and composed of a compound having a structure having a carboxynole group and an amide group in a 1: 1 ratio in the molecule was used. The photosensitive composition of Examples 1 to 22 and the photosensitive layer in the photosensitive film produced using this photosensitive composition are excellent in storage stability, exposure sensitivity and resolution, and are formed using the photosensitive film. It was confirmed that the surface hardness and dielectric properties of the cured layer in the permanent pattern were good. In particular, the photosensitive film of Examples 1 to 12 in which the content of the curing accelerator in the photosensitive composition is 0.01 to 15% by mass is extremely excellent in both storage stability and dielectric properties. It turned out to be excellent. In Examples 21 and 22 in which only the curing accelerator of the present invention was used and dicyandiamide, which is an amine-based thermosetting agent, was not used, the sensitivity, pencil hardness, dielectric properties, etc. were hardly lowered and the sensitivity was particularly high. It was found that a photosensitive film was obtained.
また、実施例 1、 2、 5及び 6と同様の感光性フィルムを用いた実施例 9〜： 12では、 高輝度光源と高速変調可能であり、かつトーリックレンズによる光学系歪み補正が可 能なパターン形成装置を用いたため、解像度及び露光速度が優れることが認められ 、高精細な永久パターンが形成されることが確認された。 Moreover, in Examples 9 to 12 using the same photosensitive film as Examples 1, 2, 5 and 6, A high-intensity light source and high-speed modulation is possible, and a pattern forming device that can correct optical distortion with a toric lens is used. Was confirmed.
これに対して、本発明の硬化促進剤を使用しなかった比較例 1〜4の感光性フィル ムは、保存安定性に劣っていた。  On the other hand, the photosensitive films of Comparative Examples 1 to 4 which did not use the curing accelerator of the present invention were inferior in storage stability.
また、表 9〜表 10の結果より、前記本発明の硬化促進剤を使用した実施例 23〜26 の熱硬化性樹脂組成物は、本発明の硬化促進剤を使用しなかった比較例 5〜6に 比べ、貯蔵安定性に優れてレ、ることが半つた。  Moreover, from the results of Table 9 to Table 10, the thermosetting resin compositions of Examples 23 to 26 using the curing accelerator of the present invention were comparative examples 5 to 5 in which the curing accelerator of the present invention was not used. Compared to 6, it has half the storage stability.
産業上の利用可能性 Industrial applicability
本発明の硬化促進剤は、保存時の常温下では反応を生じず、保存安定性に優れ 、加熱により、加熱により硬化促進効果及び熱架橋効果を発現し、エポキシ樹脂化 合物などの樹脂との反応を開始して、硬化膜の良好な膜硬度が得られるため、プリン ト配線板（多層配線基板、ビルドアップ配線基板等）の保護膜、層間絶縁膜、及びソ ノレダーレジストパターン、並びに、カラーフィルタや柱材、リブ材、スぺーサ一、隔壁 などのディスプレイ用部材、ホログラム、マイクロマシン、プルーフ、接着剤、熱硬化性 組成物、永久パターン形成用の感光性組成物などに好適に用いることができる。 また、本発明の硬化促進剤を使用した本発明の熱硬化性樹脂組成物は、熱によつ て硬化可能で保存安定性に優れ、硬化後は優れた耐薬品性、硬度、耐熱性、誘電 特性、電気絶縁性などを発現できるため、接着剤などに好適に用いることができる。 また、本発明の硬化促進剤を使用した本発明の感光性組成物及び該感光性組成 物を用いた感光性フィルムは、 UV露光により画像形成可能で、表面のタック性が小 さぐラミネート性及び取扱い性が良好で、保存安定性に優れ、高感度で現像性にも 優れ、現像後に優れた耐薬品性、表面硬度、耐熱性、誘電特性などを発現するため 、プリント配線板（多層配線基板、ビルドアップ配線基板等）の保護膜、層間絶縁膜、 及びソルダーレジストパターン、並びに、カラーフィルタや柱材、リブ材、スぺーサ一、 隔壁などのディスプレイ用部材、ホログラム、マイクロマシン、プルーフなどの永久パ ターン形成用として広く用いることができる。  The curing accelerator of the present invention does not react at room temperature during storage, is excellent in storage stability, exhibits a curing acceleration effect and a thermal cross-linking effect by heating, and is effective with a resin such as an epoxy resin compound. In order to obtain a good hardness of the cured film, the protective film of the printed wiring board (multilayer wiring board, build-up wiring board, etc.), interlayer insulating film, sono-redder resist pattern, and Suitable for display members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, adhesives, thermosetting compositions, photosensitive compositions for permanent pattern formation, etc. Can be used. In addition, the thermosetting resin composition of the present invention using the curing accelerator of the present invention is curable by heat and has excellent storage stability. After curing, it has excellent chemical resistance, hardness, heat resistance, Since it can exhibit dielectric properties, electrical insulation, etc., it can be suitably used for adhesives. In addition, the photosensitive composition of the present invention using the curing accelerator of the present invention and the photosensitive film using the photosensitive composition are capable of forming an image by UV exposure and have a laminating property and a small surface tackiness. Printed wiring board (multi-layer wiring board) because it has good handling properties, excellent storage stability, high sensitivity, excellent developability, and excellent chemical resistance, surface hardness, heat resistance, dielectric properties, etc. after development. , Build-up wiring boards, etc.), protective films, interlayer insulation films, solder resist patterns, color filters, pillar materials, rib materials, spacers, partition members, display materials, holograms, micromachines, proofs, etc. It can be widely used for forming a permanent pattern.
また、本発明の永久パターンは耐薬品性、表面硬度、耐熱性、誘電特性、電気絶 縁性に優れる。このため、プリント配線板（多層配線基板、ビルドアップ配線基板等） の保護膜、層間絶縁膜、ソルダーレジストパターン、並びに、カラーフィルタや柱材、 リブ材、スぺーサ一、隔壁などのディスプレイ用部材、ホログラム、マイクロマシン、プ ルーフなどの永久パターン形成用として広く用いることができるとして好適に使用す ること力 Sできる。 Further, the permanent pattern of the present invention has chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation. Excellent edge. For this reason, it is used for protective films on printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, and displays such as color filters, pillar materials, rib materials, spacers, and partition walls. It can be used suitably as it can be widely used for forming permanent patterns such as members, holograms, micromachines, and proofs.

Claims

請求の範囲 [1] 外部刺激によりアミンを生成し、分子内にカルボキシノレ基とアミド基とを 1対 1の比で 有する構造であることを特徴とする硬化促進剤。 [2] 外部刺激が、 80°C以上の加熱である請求の範囲第 1項に記載の硬化促進剤。 [3] 下記一般式（1)、（2)、（3)、（4)、（5)及び（6)のいずれかで表される請求の範囲 第 1項から第 2項のいずれかに記載の硬化促進剤。 Claims [1] A curing accelerator characterized by having a structure in which an amine is generated by an external stimulus and a carboxynole group and an amide group are in a ratio of 1: 1 in the molecule. [2] The curing accelerator according to claim 1, wherein the external stimulus is heating at 80 ° C. or higher. [3] Claims represented by any one of the following general formulas (1), (2), (3), (4), (5) and (6) The curing accelerator as described.
[化 1]  [Chemical 1]
—般式 （ 1 )—General formula (1)
Figure imgf000115_0001
Figure imgf000115_0001
[化 2]  [Chemical 2]
—般式 （2 )—General formula (2)
Figure imgf000115_0002
Figure imgf000115_0002
[化 3]  [Chemical 3]
—般式 （3 )
Figure imgf000115_0003
—General formula (3)
Figure imgf000115_0003
[化 4]  [Chemical 4]
—般式 （4 )
Figure imgf000115_0004
—General formula (4)
Figure imgf000115_0004
[化 5]  [Chemical 5]
—般式 ( 5 )
Figure imgf000115_0005
[化 6] —General formula (5)
Figure imgf000115_0005
[Chemical 6]
—般式 （6)—General formula (6)
Figure imgf000116_0001
Figure imgf000116_0001
ただし、前記一般式（1)、（2)、 （3)、（4)、（5)及び (6)中、 R^R18は、水素原子、 及び置換基のいずれかを表し、 Ai A6は、 2価の置換基を表し、 〜!^11は、単結合However, in said general formula (1), (2), (3), (4), (5) and (6), R ^ R 18 represents either a hydrogen atom or a substituent, and Ai A 6 represents a divalent substituent, and ~! ^ 11 is a single bond
、二重結合、及び 2価の置換基のいずれかを表す。 Represents a double bond or a divalent substituent.
[4] エポキシ樹脂化合物と、請求の範囲第 1項から第 3項のいずれかに記載の硬化促 進剤と、を少なくとも含むことを特徴とする熱硬化性樹脂組成物。 [4] A thermosetting resin composition comprising at least an epoxy resin compound and the curing accelerator according to any one of claims 1 to 3.
[5] 硬化促進剤の含有量が、 0. 01 50質量％である請求の範囲第 4項に記載の熱 硬化性樹脂組成物。 [5] The thermosetting resin composition according to claim 4, wherein the content of the curing accelerator is 0.01 to 50% by mass.
[6] (A) 1分子中に 1個以上のカルボキシノレ基及びエステル基のいずれかを有する重 合体と、（B)重合性化合物と、 （C)光重合開始剤と、（D)請求の範囲第 1項から第 3 項のいずれかに記載の硬化促進剤と、を少なくとも含むことを特徴とする感光性組成 物。  [6] (A) a polymer having one or more carboxynole groups and ester groups in one molecule, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) claim A curing composition comprising at least the curing accelerator according to any one of items 1 to 3 of the above range.
[7] (E)熱架橋剤を更に含む請求の範囲第 6項に記載の感光性組成物。  [7] The photosensitive composition according to claim 6, further comprising (E) a thermal crosslinking agent.
[8] (D)硬化促進剤の含有量が、 0. 01 40質量％である請求の範囲第 6項に記載の 感光性組成物。  [8] The photosensitive composition according to claim 6, wherein the content of (D) the curing accelerator is 0.01 to 40% by mass.
[9] (E)熱架橋剤力 分子内に 2つ以上のォキシラン基を有するエポキシ化合物である 請求の範囲第 7項から第 8項のいずれかに記載の感光性組成物。  [9] The photosensitive composition according to any one of [7] to [8], which is an epoxy compound having two or more oxosilane groups in the molecule.
[10] (E)熱架橋剤が、下記一般式（7) （9)のレ、ずれかで表される化合物である請求 の範囲第 7項から第 9項のいずれかに記載の感光性組成物。  [10] The photosensitivity according to any one of claims 7 to 9, wherein (E) the thermal crosslinking agent is a compound represented by the following general formula (7) (9): Composition.
[化 7] 一般式（7) [Chemical 7] General formula (7)
Figure imgf000116_0002
一般式 (8)
Figure imgf000116_0002
General formula (8)
Figure imgf000117_0001
Figure imgf000117_0001
ただし、前記一般式（7)、（8)、及び（9)中、 Pは、酸素原子、カルボニル基、アミド 基、ウレタン基、アルキレン基、及びァリーレン基のいずれかを表し、 Qは、ホウ素原 子、窒素原子、アルキレン基、及びァリーレン基のいずれかを表し、 Wは、 2つの X26 と結合を有するナフタレンを表し、 A21 A25は、単結合、アルキレン基、及びァリーレ ン基のいずれかを表し、 X21 X26は、 OCONH― NHCOO NHCO— 、及び CONH のいずれかを表す。 R21 R26は、水素原子、ハロゲン原子、アル キル基、及びァリール基のいずれかを表す。 However, in the general formulas (7), (8), and (9), P represents an oxygen atom, a carbonyl group, an amide group, a urethane group, an alkylene group, or an arylene group, and Q represents boron. Represents an atom, a nitrogen atom, an alkylene group, or an arylene group, W represents naphthalene having a bond with two X 26 s , A 21 A 25 represents a single bond, an alkylene group, or an arylene group. X 21 X 26 represents any one of OCONH—NHCOO NHCO— and CONH. R 21 R 26 represents any one of a hydrogen atom, a halogen atom, an alkyl group, and an aryl group.
[11] (E)熱架橋剤力 分子内に 2つ以上のォキセタニル基を有するォキセタン化合物で ある請求の範囲第 7項から第 10項のいずれかに記載の感光性組成物。  [11] (E) Thermal crosslinking agent power The photosensitive composition according to any one of claims 7 to 10, which is an oxetane compound having two or more oxetanyl groups in the molecule.
[12] (A)重合体が、エポキシアタリレートイ匕合物である請求の範囲第 6項から第 11項の レ、ずれかに記載の感光性組成物。  [12] The photosensitive composition according to any one of claims 6 to 11, wherein (A) the polymer is an epoxy atalyte toy compound.
[13] (A)重合体が、側鎖に (メタ）アタリロイル基、及び酸性基を有するビニル共重合体 の少なくとも 1種を含む請求の範囲第 6項から第 11項のいずれかに記載の感光性組 成物。  [13] (A) The polymer according to any one of claims 6 to 11, wherein the polymer (A) contains at least one kind of vinyl copolymer having a (meth) atallyloyl group and an acidic group in a side chain. Photosensitive composition.
[14] (A)重合体が、エポキシアタリレートイ匕合物と、側鎖に (メタ）アタリロイル基、及び酸 性基を有するビニル共重合体の少なくとも 1種を含む請求の範囲第 6項から第 11項 のいずれかに記載の感光性組成物。  [14] The claim (A), wherein the polymer (A) comprises at least one of an epoxy atalytoy compound, a vinyl copolymer having a (meth) attalyloyl group and an acid group in the side chain. To 11. The photosensitive composition according to any one of items 11 to 11.
[15] (A)重合体が、下記構造式 (III)で表される請求の範囲第 12項に記載の感光性組 成物。 [15] The photosensitive composition according to item 12, wherein the polymer (A) is represented by the following structural formula (III).
[化 8]
Figure imgf000118_0001
構造式 （I I I ) [Chemical 8]
Figure imgf000118_0001
Structural formula (III)
ただし、前記構造式 (III)中、 Xは水素原子、及び少なくとも酸性基を含む置換基の いずれかを表し、 Yはメチレン基、イソプロピリデン基、及びスルホニル基のいずれか を表し、 nは、 1〜20の整数を表す。  However, in the structural formula (III), X represents any one of a hydrogen atom and a substituent containing at least an acidic group, Y represents any one of a methylene group, an isopropylidene group, and a sulfonyl group, and n represents Represents an integer of 1-20.
[16] (A)重合体が、無水マレイン酸共重合体の無水物基に対して 0. 1〜： 1. 2当量の 1 級アミンィヒ合物を反応させて得られる共重合体である請求の範囲第 6項から第 8項の レ、ずれかに記載の感光性組成物。  [16] (A) The polymer is a copolymer obtained by reacting 0.1 to: 1.2 equivalents of a primary amine-rich compound with respect to the anhydride group of the maleic anhydride copolymer. The photosensitive composition according to any one of items 6 to 8 in the above range.
[17] 支持体と、該支持体上に、請求の範囲第 6項から第 16項のいずれかに記載の感光 性組成物が積層されてなる感光層とを有することを特徴とする感光性フィルム。  [17] A photosensitive material comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to any one of claims 6 to 16 on the support. the film.
[18] 感光層が、光照射手段からの光を受光し出射する描素部を n個有する光変調手段 により、前記光照射手段からの光を変調させた後、前記描素部における出射面の歪 みによる収差を補正可能な非球面を有するマイクロレンズを配列したマイクロレンズ アレイを通した光で、露光される請求の範囲第 17項に記載の感光性フィルム。 [18] After the photosensitive layer modulates the light from the light irradiating means by the light modulating means having n picture elements for receiving and emitting the light from the light irradiating means, the emission surface of the picture element portion 18. The photosensitive film according to claim 17, wherein the photosensitive film is exposed with light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting an aberration due to distortion of the lens are arranged.
[19] 請求の範囲第 6項から第 16項のいずれかに記載の感光性組成物を、基材の表面 に塗布し、乾燥して感光層を形成した後、露光し、現像し、加熱することを特徴とする 永久パターン形成方法。  [19] The photosensitive composition according to any one of claims 6 to 16 is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated. A method for forming a permanent pattern.
[20] 請求の範囲第 17項から第 18項のいずれかに記載の感光性フィルムを、加熱及び 加圧の少なくともいずれかの下において基材の表面に積層した後、露光し、現像し、 加熱することを特徴とする永久パターン形成方法。  [20] The photosensitive film according to any one of claims 17 to 18 is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed. A method for forming a permanent pattern, comprising heating.
[21] 基材が、配線形成済みのプリント配線基板である請求の範囲第 19項から第 20項の レ、ずれかに記載の永久パターン形成方法。  [21] The permanent pattern forming method according to any one of [19] to [20], wherein the base material is a printed wiring board on which wiring has been formed.
[22] 露光が、光変調手段により光を変調させた後、前記光変調手段における描素部の 出射面の歪みによる収差を補正可能な非球面を有するマイクロレンズを配列したマイ クロレンズアレイを通して行われる請求の範囲第 19項から第 21項のいずれかに記載 の永久パターン形成方法。 [22] After exposure, the light is modulated by the light modulation means, and then passes through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means are arranged. The permanent pattern forming method according to any one of claims 19 to 21, which is performed.
[23] 加熱が、 120〜250°Cで行われる全面加熱処理である請求の範囲第 19項から第 2 2項のいずれかに記載の永久パターン形成方法。 [23] The claims 19 to 2, wherein the heating is a whole surface heat treatment performed at 120 to 250 ° C. 3. The permanent pattern forming method according to any one of items 2.
[24] 現像が行われた後、感光層に対して全面露光処理を行う請求の範囲第 19項から 第 23項のいずれかに記載の永久パターン形成方法。 [24] The permanent pattern forming method according to any one of [19] to [23], wherein after the development, the entire surface exposure process is performed on the photosensitive layer.
[25] 請求の範囲第 19項から第 24項のいずれかに記載の永久パターン形成方法により 形成されることを特徴とする永久パターン。 [25] A permanent pattern formed by the method for forming a permanent pattern according to any one of items 19 to 24.
PCT/JP2006/311654 2005-06-14 2006-06-09 Curing accelerator, thermosetting resin composition, photosensitive composition, photosensitive film, permanent pattern and method for forming same WO2006134846A1 (en)

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