Classifications

• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
• • 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
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings

Definitions

• the present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board, and more specifically, a curable resin capable of obtaining a cured product having better resolution, toughness, and heat resistance than before.
• the present invention relates to a composition, a dry film, a cured product, and a printed wiring board.
• solder resist compositions for some consumer printed wiring boards and most industrial printed wiring boards are imaged by developing after irradiation with ultraviolet rays from the viewpoint of high accuracy and high density.
• a liquid development type solder resist composition that is finish-cured (mainly cured) by at least one of irradiation is used.
• alkali development type photo solder resist compositions using an aqueous alkali solution as a developing solution have become mainstream, and are used in large quantities in the production of actual printed wiring boards.
• Patent Document 1 proposes a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound. Has been.
• phenol novolac type (cresol novolac type) epoxy acrylate resin and acrylic copolymer type resin are widely used in the alkali-soluble type.
• phenol novolac epoxy acrylate resins are not necessarily excellent in toughness, and acrylic copolymer resins are inferior in heat resistance.
• semiconductor package components are mounted on a printed wiring board, the number of connected IOs and the size of the components are simultaneously reduced, and the wiring density is rapidly increased. In order to enable high-density wiring, a curable resin composition having high resolution is required.
• an object of the present invention is to provide a curable resin composition, a dry film, a cured product, and a printed wiring board that can obtain a cured product that is superior in resolution, toughness, and heat resistance than before. There is.
• the present inventors have made the resin used in the curable resin composition a resin having a specific structure, and set the particle size of the inorganic particles as the filler to a predetermined value. By making it below the value, it was found that the above problems could be solved, and the present invention was completed.
• the curable resin composition of the present invention comprises (A) the following formulas (1), (2), An amide-imide resin having at least one structure represented by: and an alkali-soluble functional group; (B) inorganic particles having an average particle size of 200 nm or less; (C) a photopolymerization initiator; and (D) an unsaturated double bond. And a compound having the following.
• the curable resin composition of the present invention may contain a resin having a structure different from that of the (A) amidoimide resin and having an alkali-soluble functional group.
• the inorganic particles (B) having an average particle diameter of 200 nm or less are preferably silica.
• (E) thermosetting resin is included.
• the (E) thermosetting resin is preferably an epoxy resin having an alicyclic skeleton.
• the dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition of the present invention on a film.
• the cured product of the present invention is characterized in that the curable resin composition of the present invention is cured, or the resin layer of the dry film of the present invention is cured.
• the printed wiring board of the present invention is characterized by comprising the cured product of the present invention.
• a curable resin composition a dry film, a cured product, and a printed wiring board capable of obtaining a cured product having excellent resolution, toughness, and heat resistance.
• the curable resin composition of the present invention (hereinafter also referred to as “resin composition”) is (A) the following formulas (1), (2), An amide-imide resin (hereinafter also referred to as “component (A)”) having at least one structure and an alkali-soluble functional group represented by: (B) inorganic particles having an average particle size of 200 nm or less (hereinafter referred to as “(B)”) (Also referred to as “component”), (C) a photopolymerization initiator (hereinafter also referred to as “(C) component”), (D) a compound having an unsaturated double bond (hereinafter referred to as “component (D)”) Included).
• component (A) An amide-imide resin having at least one structure and an alkali-soluble functional group represented by: (B) inorganic particles having an average particle size of 200 nm or less (hereinafter referred to as “(B)”) (Also referred to as “com
• the resin composition of the present invention can be developed with a weak alkaline aqueous solution such as a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, or an ammonia aqueous solution, and it is not necessary to use a strong alkaline developer during development. Further, since development is possible with a weak alkaline aqueous solution, the environmental load is small.
• the resin composition of the present invention has a solubility in an aqueous sodium carbonate solution (30 ° C., 1 mass%) of 0.05 g / L or more per minute.
• the component (A) of the resin composition of the present invention has the following formula (1) or (2), It is an amide imide resin which has at least one structure represented by these, and an alkali-soluble functional group.
• the resin composition of the present invention contains a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring, a cured product having excellent toughness and heat resistance can be obtained.
• the amidoimide resin having the structure represented by (1) is excellent in light transmittance, the resolution of the resin composition can be improved.
• the component (A) preferably has transparency.
• the transmittance of light having a wavelength of 365 nm is 70% or more in the dry coating film 25 ⁇ m of the component (A). Is preferred.
• the content of the structures of the formulas (1) and (2) in the component (A) of the resin composition of the present invention is preferably 10 to 70% by mass.
• a cured product having excellent solvent solubility and excellent physical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained.
• the amount is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
• amideimide resin having the structure represented by the formula (1) in particular, the formula (3A) or (3B) (In the formulas (3A) and (3B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group.
• a resin having a structure represented by a bond, an alkylene group such as CH 2 or C (CH 3 ) 2 ) is preferable because it has excellent physical properties such as tensile strength and elongation and dimensional stability.
• a resin having 10 to 100% by mass of the structure of the formulas (3A) and (3B) can be preferably used. More preferably, it is 20 to 80% by mass.
• an amidoimide resin containing 5 to 100 mol% of the structure of the formulas (3A) and (3B) is preferably used from the viewpoint of solubility and mechanical properties. Can do.
• the amount is more preferably 5 to 98 mol%, further preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.
• amide imide resin which has a structure represented by Formula (2), especially Formula (4A) or (4B) (In the formulas (4A) and (4B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group, It is preferable that the resin having a structure represented by a bond or an alkylene group such as CH 2 or C (CH 3 ) 2 is a cured product having excellent mechanical properties such as tensile strength and elongation. To preferred.
• a resin having a structure of formulas (4A) and (4B) of 10 to 100% by mass can be preferably used. More preferably, it is 20 to 80% by mass.
• an amideimide resin containing 2 to 95 mol% of the structures of the formulas (4A) and (4B) can also be preferably used because it exhibits good mechanical properties. More preferably, it is 10 to 80 mol%.
• a component can be obtained by a well-known method.
• the amidoimide resin having the structure (1) can be obtained using, for example, a diisocyanate compound having a biphenyl skeleton and a cyclohexane polycarboxylic acid anhydride.
• diisocyanate compound having a biphenyl skeleton examples include 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl and 4,4′-diisocyanate-3,3′-diethyl-1,1′-biphenyl.
• 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1'-biphenyl, 4,4'-diisocyanate- Examples include 3,3′-ditrifluoromethyl-1,1′-biphenyl, 4,4′-diisocyanate-2,2′-ditrifluoromethyl-1,1′-biphenyl, and the like.
• aromatic polyisocyanate compounds such as diphenylmethane diisocyanate may be used.
• cyclohexane polycarboxylic acid anhydride examples include cyclohexane tricarboxylic acid anhydride and cyclohexane tetracarboxylic acid anhydride.
• the amidoimide resin having the structure (2) can be obtained by using, for example, the diisocyanate compound having the biphenyl skeleton and the polycarboxylic acid hydrate having two acid anhydride groups.
• polycarboxylic acid anhydrides having two acid anhydride groups examples include pyromellitic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl- 2,2 ′, 3,3′-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis
• the component (A) of the resin composition of the present invention has an alkali-soluble functional group in addition to the structures of the above formulas (1) and (2). By having an alkali-soluble functional group, it becomes a resin composition capable of alkali development.
• the alkali-soluble functional group contains a carboxyl group, a phenolic hydroxyl group, a sulfo group, etc., and preferably contains a carboxyl group.
• the acid value of the component (A) in the resin composition of the present invention is preferably in the range of 20 to 120 mgKOH / g, more preferably in the range of 30 to 100 mgKOH / g. By making the acid value of the component (A) within the above range, alkali development can be performed satisfactorily, and a normal cured product pattern can be formed.
• the weight average molecular weight of the component (A) of the resin composition of the present invention varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the tack-free property of the dried coating film, the moisture resistance of the coating film after exposure, and the resolution are good. On the other hand, when the weight average molecular weight is 150,000 or less, developability and storage stability are good. More preferably, it is 5,000 to 100,000.
• component (A) examples include Unidic V-8000 series from DIC Corporation and SOXR-U from Nippon Kogyo Paper Industries.
• the resin composition of the present invention may contain a resin having a different structure from the component (A) and having an alkali-soluble functional group (hereinafter also referred to as the component (A1)).
• a resin having a different structure from the component (A) and having an alkali-soluble functional group hereinafter also referred to as the component (A1).
• the difference between the component (A) and the structure means that it does not include the structures of the formulas (1) and (2).
• the alkali-soluble functional group of the component (A1) is the same as the alkali-soluble functional group of the component (A).
• a carboxyl group-containing resin starting from an epoxy resin a carboxyl group-containing resin having a urethane skeleton (also referred to as a carboxyl group-containing urethane resin), and a carboxyl group having a copolymer structure of an unsaturated carboxylic acid -Containing resins, carboxyl group-containing resins starting from phenolic compounds, and carboxyl group-containing resins obtained by adding compounds having one epoxy group and one or more (meth) acryloyl groups in the molecule to these carboxyl group-containing resins It is preferably at least one of resins. Specific examples of the component (A1) are shown below.
• a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
• Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
• carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
• Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
• a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
• Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of (meth) acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
• one isocyanate group and one or more (meth) acryloyl groups in the molecule such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate
• a carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal and being terminally (meth) acrylated.
• (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin as described later, and the hydroxyl groups present in the side chain are added to 2 such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
• the epoxy resin is preferably solid.
• (meth) acrylic acid was reacted with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride was added to the resulting hydroxyl group.
• Carboxyl group-containing photosensitive resin is preferably solid.
• a cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is polyvalent.
• a carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.
• one epoxy group and one or more (meth) acryloyl groups are added in the molecule such as glycidyl (meth) acrylate and ⁇ -methylglycidyl (meth) acrylate.
• a carboxyl group-containing photosensitive resin obtained by adding a compound having the same.
• (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions hereinafter.
• the acid value and weight average molecular weight of the component (A1) are in the same range as the acid value and weight average molecular weight of the component (A).
• the blending amount of the component (A1) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass with respect to 100 parts by mass in total of the component (A) and the component (A1). It is as follows. By setting it as said range, the hardened
• the resin composition of the present invention includes (B) inorganic particles having an average particle size of 200 nm or less.
• the average particle diameter of the inorganic particles is preferably 150 nm or less, and more preferably 100 nm or less.
• the reason why the average particle size of the inorganic particles is 200 nm or less is as follows. That is, normally, an ultraviolet wavelength having a wavelength of 450 nm or less is used for exposure of the resin composition. In order to improve the resolution of the resin composition, it is necessary to suppress the scattering of light. However, when the inorganic particles in the resin composition are exposed to light, the light is scattered. As the particle size is smaller, the scattering is reduced.
• the resolution is greatly improved by setting the particle size of the inorganic particles to 200 nm or less, which is about half the wavelength of ultraviolet rays for exposure. It was found that it can be improved.
• the average particle diameter is a value measured by a laser diffraction method. Nikkiso Co., Ltd. (Nanotrac wave) etc. are mentioned as a measuring apparatus by a laser diffraction method.
• the surface of the cured product is first etched by plasma treatment so that the inorganic particles can be seen, and the inorganic particles are observed with a scanning electron microscope (SEM). To do. To obtain the average particle size of the inorganic particles, measure the diameter of the observed inorganic particles in the range of 1 ⁇ m 2 , perform the operation five times including other points, and calculate the average value of the inorganic particle diameters. do it.
• a MARCH PLASMA SYSTEM INC AP-1000 is used as an apparatus, and POWER: 500 W, Pressure: 300 Torr, Gas: Ar, and a treatment time of 10 minutes.
• the inorganic particles include known and commonly used inorganic fillers such as silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica powder, hydrotalcite, silicin, and silicocolloid. Can be used. Among these, silica having a small linear expansion coefficient can be suitably used. In addition, these inorganic particles may be used individually by 1 type, and may be used in combination of 2 or more type.
• inorganic fillers such as silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica powder, hydrotalcite, silicin, and silicocolloid. Can be used. Among these, silica having a small linear expansion coefficient can be suitably used. In addition, these inorganic particles may be used individually by 1 type, and may be used in combination of 2 or more type.
• the blending amount of the component (B) in the resin composition of the present invention is 100 parts by mass in total of the component (A) and the component (A1) (when not including the component (A1), 100 parts by mass of the component (A)).
• the amount is preferably 10 to 150 parts by mass, more preferably 30 to 120 parts by mass.
• the resin composition of this invention is made by making (B) component 150 mass parts or less. It is possible to prevent deterioration in workability during application.
• silica having a small linear expansion coefficient can be suitably used as the component (B).
• the surface of the silica is treated with a silane coupling agent.
• a silane coupling agent are preferred. This is because precipitation and aggregation can be prevented after being dispersed in the liquid, and as a result, the storage stability is excellent.
• Examples of the organic group contained in the silane coupling agent include vinyl, epoxy, styryl, methacryloxy, acryloxy, amino, ureido, chloropropyl, mercapto, polysulfide, and isocyanate groups. Can be mentioned.
• a silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
• the resin composition of the present invention contains (C) a photopolymerization initiator.
• a photopolymerization initiator an oxime ester system including a structure represented by the general formula (I), an ⁇ -aminoacetophenone system including a structure represented by the general formula (II), and a general formula (III)
• the photopolymerization initiator an oxime ester system including a structure represented by the general formula (I), an ⁇ -aminoacetophenone system including a structure represented by the general formula (II), and a general formula (III) It is preferable to contain 1 type (s) or 2 or more types selected from the group which consists of the acylphosphine oxide type
• R 1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.
• R 2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.
• the phenyl group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.
• the alkyl group represented by R 1 and R 2 is preferably an alkyl group having 1 to 20 carbon atoms and may contain one or more oxygen atoms in the alkyl chain. Further, it may be substituted with one or more hydroxyl groups.
• the cycloalkyl group represented by R 1 and R 2 is preferably a cycloalkyl group having 5 to 8 carbon atoms.
• the alkanoyl group represented by R 1 and R 2 is preferably an alkanoyl group having 2 to 20 carbon atoms.
• the benzoyl group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a phenyl group.
• R 3 and R 4 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group
• R 5 and R 6 each independently represent a hydrogen atom or a carbon number 1 to 6 alkyl groups may be represented, or two may combine to form a cyclic alkyl ether group.
• R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group.
• R 9 and R 10 each independently represent a halogen atom, an aryl group, a halogenated aryl group, or a heterocycle-containing halogenated aryl group.
• oxime ester photopolymerization initiator examples include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.
• examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, and NCI-831 manufactured by Adeka.
• a photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiator having a carbazole structure can also be suitably used.
• Specific examples include oxime ester compounds represented by the following general formula (V).
• X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, a carbon number of 1
• An anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene Thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.)
• X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that
• R 1 represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
• R 2 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
• R 3 may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a phenyl group.
• R 4 represents a benzyl group or an acyl group represented by X—C ( ⁇ O) —, wherein X is substituted with an alkyl group having 1 to 4 carbon atoms.
• Aryl group or thienyl group A morpholino group, a thiophenyl group, or a structure represented by the following formula (VII).
• ⁇ -aminoacetophenone photopolymerization initiator examples include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.), 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a commercially available compound or a solution thereof can be used.
• 4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.)
• acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl). ) -2,4,4-trimethyl-pentylphosphine oxide.
• examples of commercially available products include Lucilin TPO and Irgacure 819 manufactured by BASF.
• titanocene photopolymerization initiator bis ( ⁇ 5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium is used. Can be mentioned. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.
• photopolymerization initiators examples include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2 Thioxanthones such as 1,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethylketone
• one or more known photosensitizers such as tertiary amines such as triethanolamine can be used in combination.
• a 3-substituted coumarin dye, a leuco dye, or the like can be used in combination as a curing aid, if necessary.
• the blending ratio of the component (C) is 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)).
• the amount is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 15 parts by mass.
• the resin composition of the present invention contains (D) a compound having an unsaturated double bond.
• the component (D) can be photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the resin composition of the present invention in an alkaline aqueous solution.
• polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaery
• Polyacid acrylates of sidyl ether not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, And at least one of the methacrylates corresponding to the acrylate.
• an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
• a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
• a hydroxy acrylate such as pentaerythritol triacrylate
• a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
• an epoxy urethane acrylate compound obtained by reacting a half urethane compound.
• Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
• a compound having an ethylenically unsaturated group in the molecule as described above may be used alone or in combination of two or more.
• the blending ratio of the component (D) is preferably 1 to 60 parts by mass per 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)).
• the amount is more preferably 5 to 50 parts by mass, still more preferably 10 to 40 parts by mass.
• the resin composition of the present invention preferably contains (E) a thermosetting resin (hereinafter also referred to as “component (E)”).
• thermosetting resins include polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc. in one molecule such as two or more cyclic ether groups and / or cyclic thioether groups, polyisocyanate compounds, block isocyanate compounds, etc.
• thermosetting resins such as bismaleimide, oxazine, cyclocarbonate compounds and carbodiimide resins Can be mentioned.
• the epoxy resin a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used.
• the epoxy resin may be liquid or may be solid or semi-solid.
• Polyfunctional epoxy resins include: bisphenol A type epoxy resins; brominated epoxy resins; novolac type epoxy resins; bisphenol F type epoxy resins; hydrogenated bisphenol A type epoxy resins; glycidyl amine type epoxy resins; Epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; Resin; Diglycidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl meta Acrylate copolymer based epoxy resins; polybuta
• the epoxy resin is preferably a bisphenol A type or bisphenol F type novolak type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, a biphenol novolak type (biphenylaralkyl type) epoxy resin, a naphthalene type epoxy resin or a mixture thereof. .
• thermosetting resin an epoxy resin having a naphthalene skeleton is preferable as the thermosetting resin.
• naphthalene has a planar structure, can reduce the coefficient of linear expansion, and can further improve heat resistance.
• thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available epoxy resins having a naphthalene skeleton include ESN-190 and ESN-360 manufactured by Nippon Steel Chemical, EPICRON HP-4032 and EPICRON HP-4032D manufactured by DIC.
• thermosetting resin having an alicyclic skeleton is preferable, for example, a dicyclopentadiene skeleton-containing thermosetting resin is preferable, and a dicyclopentadiene skeleton-containing epoxy resin is particularly preferable. Further, a thermosetting resin having an alicyclic skeleton is preferable because an effect of improving the glass transition temperature is obtained as compared with an epoxy resin having a chain skeleton.
• the blending ratio of the component (E) is preferably 10 to 100 parts by mass per 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). More preferably, it is 10 to 80 parts by mass. (E) By making the compounding quantity of a component into the said range, the composition which has heat resistance and has both favorable developability and photoreactivity can be obtained.
• thermosetting catalyst When the resin composition of the present invention contains (E) a thermosetting resin, a thermosetting catalyst may be included.
• the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Examples include amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide, and phosphorus compounds such
• thermosetting catalysts examples include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
• the blending amount of the thermosetting catalyst is 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). On the other hand, it is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass.
• the resin composition of the present invention can use an organic solvent for the preparation of the composition or for adjusting the viscosity for application to a substrate or a carrier film.
• organic solvent examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.
• ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, Esters such as propylene glycol butyl ether acetate; ethanol, propanol Ethylene glycol, or propylene glycol; octane, alipha
• the resin composition of the present invention comprises (A) an amide-imide resin having at least one structure represented by the above formula (1) or (2) and an alkali-soluble functional group, and (B) an inorganic having an average particle size of 200 nm or less. It is characterized by containing particles, (C) a photoinitiator, and (D) a compound having an unsaturated double bond, and there is no particular limitation for the rest.
• a known and commonly used colorant for example, a white colorant such as titanium oxide, a black colorant such as carbon black or titanium black, phthalocyanine blue, phthalocyanine green, or disazo yellow is used as necessary. Etc.), thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents and the like can be added.
• the resin composition of the present invention is suitable for forming an insulating cured film on a printed wiring board, more preferably for forming an insulating permanent film, and for forming a coverlay, solder resist, and interlayer insulating material. Is optimal.
• the resin composition of this invention can also be used for formation of a solder dam etc.
• the resin composition of the present invention may be a liquid type or a dry film type obtained by drying a liquid type resin composition.
• the liquid resin composition may be a two-component type from the viewpoint of storage stability, but may be a one-component type.
• the dry film of the present invention has a resin layer obtained by applying the resin composition of the present invention on a film (hereinafter also referred to as “carrier film”) and then drying it.
• the dry film of the present invention is prepared by diluting the resin composition of the present invention with an organic solvent so as to have an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure It can be obtained by applying a uniform thickness on a carrier film with a coater, spray coater or the like, and usually drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes.
• the coating film thickness is not particularly limited, but in general, the film thickness after drying may be appropriately set in the range of 5 to 150 ⁇ m, preferably 10 to 60 ⁇ m.
• the film is not limited to a carrier film but may be a cover film.
• a plastic film can be suitably used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used.
• the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
• a peelable cover film may be laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the coating film.
• a peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.
• Volatile drying performed after the resin composition of the present invention is applied on a carrier film is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with an air heating heat source using steam). And a method of spraying the hot air against the support from a nozzle).
• the cured product of the present invention is a product obtained by curing the resin composition of the present invention and a product obtained by curing the resin layer of the dry film of the present invention.
• the cured product of the present invention is obtained by applying an active energy ray to the coating film obtained after applying the resin composition of the present invention and evaporating and drying the solvent, or by irradiating the active film with an active energy ray. It can be obtained by curing an exposed portion which is a portion irradiated with active energy rays.
• the printed wiring board of the present invention comprises the cured product of the present invention.
• the printed wiring board of this invention can be obtained by the method of apply
• the resin composition of the present invention is directly coated on the printed wiring board on which a circuit is formed, and after forming a coating film of the resin composition, laser light, etc. Directly irradiate the active energy rays according to the pattern or selectively irradiate the active energy rays through the photomask on which the pattern is formed, and develop the unexposed area with a dilute alkaline aqueous solution to form a resist pattern. To do.
• the printed wiring board having the cured product pattern is manufactured by irradiating the resist pattern with active energy rays at, for example, 500 to 2000 mJ / cm 2 and curing it by heating to a temperature of about 140 to 180 ° C., for example. Irradiation of the active energy ray to the resist pattern is performed in order to almost completely cure the component (D) that did not react by exposure when forming an image of the resist pattern.
• the carrier film is peeled off and developed in the same manner as described above. Thereafter, the resin layer is irradiated with active energy rays and heated to a temperature of about 140 to 180 ° C. for curing to produce a printed wiring board having a cured product pattern.
• the cured film pattern may be formed by a photolithography method or a screen printing method.
• a direct drawing apparatus such as a direct imaging apparatus that directly draws an image with active energy rays by CAD data from a computer can be used.
• a light source for the direct drawing apparatus either a mercury short arc lamp, an LED, or a laser beam having a maximum wavelength in the range of 350 to 410 nm may be used.
• the exposure amount for forming the image of the resist pattern varies depending on the film thickness and the like, but can be generally in the range of 20 to 1500 mJ / cm 2 , preferably 20 to 1200 mJ / cm 2 .
• a developing method As a developing method, a dipping method, a shower method, a spray method, a brush method, etc. can be adopted, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate An aqueous alkali solution such as ammonia or amines can be used.
• Examples 1 to 25 and Comparative Examples 1 to 3 Resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Tables 1 to 4 below.
• the obtained resin composition was applied on the entire surface of a patterned copper foil substrate for evaluation by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thereafter, the obtained evaluation substrate is exposed to a resist pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Developed for seconds. After forming the resist pattern of the cured product, it was cured by UV irradiation at 180 ° C.
• the amide imide resin (A-1), other resins (A1-1), and (A1-2) were synthesized according to the following synthesis method.
• the obtained evaluation substrate was evaluated for resolution, tensile strength, elongation, linear expansion coefficient, and glass transition point.
• the average particle size of the inorganic particles in Tables 1 to 4 is a value measured by a laser diffraction method.
• the optimal exposure amount was calculated
• Resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Tables 1 to 4 below. Next, the copper-clad laminated substrate was polished with buffalo, washed with water and dried, and the obtained resin composition was applied by a screen printing method and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, exposure was performed using a high-pressure mercury lamp exposure apparatus through a photomask (manufactured by Eastman Kodak Company, Step Tablet No. 2).
• the irradiated piece was used as a test piece, and after developing for 60 seconds with a developer having a spray pressure of 2 kg / cm 2 (1 mass% sodium carbonate aqueous solution at 30 ° C.), the number of steps of the remaining coating film was visually determined. The exposure amount at which the number of steps of the remaining coating film was 10 was determined as the appropriate exposure amount.
• polyamideimide resin (A1) having a resin solid content of 17% with a viscosity of 7 Pa ⁇ s at 25 ° C. and a solution acid value of 5.3 (KOHmg / g) (resin composition in which the resin is dissolved in ⁇ -butyrolactone) Got.
• the solid content acid value of the resin was 31.2 (KOH mg / g).
• the polyamideimide resin (A-1) is a resin having a structure of the above formulas (1) and (2) and a carboxyl group.
• reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
• the nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq.
• a novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
• A Stress at break 80 N / mm 2 or more / elongation 3% or more
• B Stress at break 50 N / mm 2 or more, less than 80 N / mm 2 / elongation 2% or more and less than 3%
• C Stress at break 50 less than N / mm 2 / elongation Less than 2%
• Tg 180 ° C. or more / CTE less than 40 ppm
• B Tg 150 ° C. or more, less than 180 ° C./CTE less than 50 ppm, 40 ppm or more
• C Tg less than 150 ° C./CTE 50 ppm or more
• developability that is, (change in weight of substrate: g) / (volume of developer: L) was calculated and evaluated. It can be seen that the higher the developability value, the faster the development speed.
• a composition containing a general polyimide resin (TECHMIGHT E2020, manufactured by Air Water Co., Ltd.)
• the developability is 0.01 g / L or less, which is almost insoluble.
• Amidoimide resin (A-2): SOXR-U (resin solid content 20%) (manufactured by Nippon Kogyo Paper Industries Co., Ltd.), corresponding to other carboxyl group-containing amidoimide resins having the structure of the above formula (2) (A1 -1): carboxyl group-containing resin synthesized in Synthesis Example 2 (solid content 65%)
• the resin composition of the present invention can obtain a cured product having excellent resolution, heat resistance, and toughness. Moreover, it turns out that the dry film obtained from the resin composition of this invention is excellent in workability

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