WO2012029481A1 - Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern casting method, and print substrate - Google Patents

Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern casting method, and print substrate Download PDF

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Publication number
WO2012029481A1
WO2012029481A1 PCT/JP2011/067498 JP2011067498W WO2012029481A1 WO 2012029481 A1 WO2012029481 A1 WO 2012029481A1 JP 2011067498 W JP2011067498 W JP 2011067498W WO 2012029481 A1 WO2012029481 A1 WO 2012029481A1
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Prior art keywords
group
photosensitive
nitrogen atom
general formula
resin
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PCT/JP2011/067498
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French (fr)
Japanese (ja)
Inventor
有岡　大輔
冨澤　秀樹
南　一守
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富士フイルム株式会社
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Publication of WO2012029481A1 publication Critical patent/WO2012029481A1/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
    • G03F7/027—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
    • 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
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a photosensitive composition, a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board.
  • a photosensitive film in which a photosensitive layer is formed by applying and drying a photosensitive composition on a support has been used.
  • a laminate is formed by laminating the photosensitive film on a substrate such as a copper-clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed on the photosensitive layer. Examples include a method of forming the permanent pattern by performing exposure on the surface, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like.
  • the permanent pattern formed from the photosensitive composition functions as a protective film for preventing solder from adhering to an unnecessary part of soldering in a soldering process such as IR reflow, Sex is required.
  • insulation is required in order to function as an insulating film for maintaining electrical insulation between the electrical wirings on the substrate.
  • toughness is required to be applicable to printed circuit boards used in various environments. As a general means for improving insulation, toughness and heat resistance, it is known that it is effective to add a filler to the photosensitive composition.
  • the required level of insulation has increased due to the miniaturization of wiring patterns.
  • the use of lead-free solder due to environmental considerations has increased the solder temperature in the soldering process, and the required level of heat resistance has also increased.
  • the blending amount of the filler is increased to improve insulation, toughness, and heat resistance, there is a problem that the photosensitive composition becomes highly viscous.
  • Patent Document 1 a technique using a basic polymer dispersant has been proposed in order to prevent the viscosity from increasing due to an increase in the amount of filler added.
  • a basic polymer dispersant called Solsperse 24000 manufactured by Avicia Chemical Co., Ltd.
  • the proposed technique can prevent the increase in viscosity, there are problems in that when this technique is applied to a photosensitive composition, the resolution is lowered and development residues are generated.
  • Patent Document 2 a technique of using a resin having a specific functional group and a specific side chain for dispersing a colored pigment has been proposed.
  • Patent Document 2 shows that the resin is effective for improving dispersibility and storage stability when a fine pigment having an average particle size of 0.005 ⁇ m to 0.1 ⁇ m is used.
  • this proposal the case where a filler having an average particle size larger than 0.1 ⁇ m is used or the dispersibility in the case where the amount of the filler is large is not examined, and it is applied to the photosensitive composition. No consideration has been given to heat resistance, toughness, and insulation.
  • the photosensitive composition is excellent in heat resistance, toughness, and insulation, and the photosensitivity.
  • provision of a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed board using the composition is required.
  • the present invention is a photosensitive composition that does not have high viscosity even when the filler content is high, has high resolution, no development residue, and is excellent in heat resistance, toughness, and insulation, It is another object of the present invention to provide a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board using the photosensitive composition.
  • Means for solving the problems are as follows. That is, ⁇ 1> containing a nitrogen atom-containing resin, a resin other than the nitrogen atom-containing resin, a thermal crosslinking agent, and a filler,
  • the nitrogen atom-containing resin is bonded to the main chain having a nitrogen atom, a group having a functional group having a pKa of 14 or less, bonded to the main chain having a nitrogen atom, and the main chain.
  • ⁇ 3> The photosensitive composition according to any one of ⁇ 1> to ⁇ 2>, wherein the filler content is 10 parts by mass to 97 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. It is. ⁇ 4> The photosensitive composition according to any one of ⁇ 1> to ⁇ 3>, wherein the main chain having a nitrogen atom is a main chain composed of a polymer having an amino group. ⁇ 5> The main chain composed of a polymer having an amino group is composed of one or more selected from poly (alkyleneimine), polyallylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, and polyvinylamine.
  • Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
  • Z is a polymer residue having at least a polyester chain as a partial structure, and from a polyester having a free carboxylic acid represented by the following general formula (IV) to a carboxyl It represents a polymer residue excluding a group.
  • Z is the same as Z in the general formula (III-1).
  • a resin having a nitrogen atom-containing resin having at least one of a primary amino group and a secondary amino group, a precursor of a group partially having a functional group having a pKa of 14 or less, and a number average molecular weight of 500 The photosensitive composition according to any one of ⁇ 1> to ⁇ 9>, wherein the photosensitive composition is a resin obtained by reacting with a precursor of ⁇ 1,000,000 graft chain.
  • ⁇ 12> A photosensitive film having a photosensitive layer made of the photosensitive composition according to any one of ⁇ 1> to ⁇ 11> on a support.
  • ⁇ 13> A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of ⁇ 1> to ⁇ 11> on a substrate.
  • ⁇ 14> A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 15> A printed circuit board comprising a permanent pattern formed by the method for forming a permanent pattern according to ⁇ 14>.
  • the conventional problems can be solved, and even when the filler content is high, the viscosity is not high, the resolution is high, there is no development residue, and the heat resistance, toughness is further improved.
  • a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed circuit board using the photosensitive composition can be provided.
  • the photosensitive composition of the present invention contains at least a nitrogen atom-containing resin, a resin other than the nitrogen atom-containing resin, a thermal crosslinking agent, and a filler, a polymerizable compound, a photopolymerization initiator, and further if necessary. And other ingredients.
  • the nitrogen atom-containing resin has at least a main chain having a nitrogen atom, a group partially having a functional group having a pKa of 14 or less, and a graft chain having a number average molecular weight of 500 to 1,000,000. Furthermore, it has other configurations as required.
  • the nitrogen atom-containing resin has a main chain having the nitrogen atom.
  • the adsorptivity of the nitrogen atom-containing resin to the filler is improved, and the interaction between the fillers in the photosensitive composition can be reduced. Thereby, even when there is much content of a filler in the said photosensitive composition, it can suppress that a viscosity becomes high.
  • the main chain having a nitrogen atom is not particularly limited as long as it has a nitrogen atom, and can be appropriately selected according to the purpose, but is a main chain composed of a polymer having an amino group. It is preferable.
  • the main chain composed of the polymer having an amino group is composed of at least one selected from poly (alkyleneimine), polyallylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, and polyvinylamine.
  • the main chain is preferably a main chain composed of poly (alkyleneimine) and a main chain composed of polyallylamine.
  • the more preferable embodiment is advantageous in that the dispersibility of the filler is improved and the viscosity of the photosensitive composition can be suppressed from increasing.
  • the alkylene of the poly (alkyleneimine) include alkylene having 1 to 5 carbon atoms. Allyl of the polyallylamine may have a substituent. Examples of the substituent include a halogen atom and an alkyl group.
  • the poly (alkyleneimine) may be a chain or a network. A network shape is preferable in terms of dispersion stability and material supply.
  • the nitrogen atom-containing resin in the case where the main chain having a nitrogen atom is a main chain composed of poly (alkyleneimine) includes a repeating unit represented by the following general formula (I-1), and the following general formula A structure having a repeating unit represented by (I-2) is preferred.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group.
  • a represents each independently an integer of 1 to 5.
  • “*” Represents a connecting portion between repeating units.
  • X represents a group partially having a functional group having a pKa of 14 or less.
  • Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
  • a portion excluding X from the general formula (I-1) corresponds to the main chain having the nitrogen atom.
  • the portion excluding Y from the general formula (I-2) corresponds to the main chain having a nitrogen atom.
  • Examples of the alkyl group of R 1 and R 2 in the general formulas (I-1) and (I-2) include an alkyl group having 1 to 5 carbon atoms which may have a substituent. Examples of the substituent include a halogen atom.
  • X in the general formulas (I-1) and (I-2) is not particularly limited as long as it is a group partially having a functional group having a pKa of 14 or less, and is appropriately selected depending on the purpose. Examples thereof include a group partially having a functional group having a pKa of 14 or less, which will be described later.
  • Y in the general formulas (I-1) and (I-2) is not particularly limited as long as it is a graft chain having a number average molecular weight of 500 to 1,000,000, and is appropriately selected according to the purpose. Examples thereof include a graft chain having a number average molecular weight of 500 to 1,000,000, which will be described later.
  • the nitrogen atom-containing resin includes a repeating unit represented by the following general formula (I-3) in addition to the repeating unit represented by the general formula (I-1) and the general formula (I-2). You may have as a copolymerization component. By using such a repeating unit in combination, the dispersion performance of the filler can be improved, and the viscosity of the photosensitive composition can be suppressed from increasing.
  • R 1, R 2 and a are respectively the same as R 1, R 2 and a in the general formula (I-1).
  • “*” Represents a connecting portion between repeating units.
  • Y ′ represents a graft chain having an anionic group and a number average molecular weight of 500 to 1,000,000.
  • the portion excluding Y ⁇ from the general formula (I-3) corresponds to the main chain having the nitrogen atom.
  • the repeating unit represented by the general formula (I-3) is obtained by adding a polymer having a group that reacts with an amine to form a salt to a resin having at least one of a primary amino group and a secondary amino group. It can be formed by reacting.
  • a polymer having a group that reacts with an amine to form a salt to a resin having at least one of a primary amino group and a secondary amino group. It can be formed by reacting.
  • the anionic group CO 2 - and SO 3 - are preferable, and CO 2 - is more preferable.
  • the anionic group is preferably at the terminal position of the graft chain having a number average molecular weight of 500 to 1,000,000.
  • R 1 and R 2 are preferably hydrogen atoms.
  • a is preferably 2 in view of easy availability of raw materials.
  • the nitrogen atom-containing resin contains a primary or tertiary amino group in addition to the repeating units represented by the general formula (I-1), general formula (I-2) and general formula (I-3).
  • An alkyleneimine may be contained as a repeating unit.
  • the group shown by said X, Y, or Y ' may couple
  • Resins containing both a repeating unit in which the group represented by X and a repeating unit to which Y are bonded to an alkyleneimine repeating structure are also included in the nitrogen atom-containing resin.
  • the repeating unit represented by the general formula (I-1) is a repeating unit having a group X partially having a functional group having a pKa of 14 or less.
  • Such a repeating unit includes a residue during development, From the viewpoint of resolution, it is preferably contained in an amount of 1 mol% to 80 mol%, more preferably 3% to 50 mol% in all repeating units of the nitrogen atom-containing resin.
  • the repeating unit represented by the general formula (I-2) is a repeating unit having a graft chain Y having a number average molecular weight of 500 to 1,000,000. Therefore, the content is preferably 10 mol% to 90 mol%, more preferably 30 mol% to 70 mol%, in all the repeating units of the nitrogen atom-containing resin.
  • the content ratio of the repeating unit represented by the general formula (I-1) to the repeating unit represented by the general formula (I-2) in the nitrogen atom-containing resin is a balance between dispersion stability and hydrophilicity / hydrophobicity.
  • the repeating unit (I-1) :( I-2) is preferably in the range of 10: 1 to 1: 100, more preferably in the range of 1: 1 to 1:10. preferable.
  • the repeating unit represented by the general formula (I-3) used in combination if desired, has a graft chain having a number average molecular weight of 500 to 1,000,000 as a nitrogen atom of the main chain having the nitrogen atom. In terms of the effect, it is preferably contained in an amount of 0.5 mol% to 20 mol% in all repeating units of the nitrogen atom-containing resin, and 1 mol% to 10 mol%. It is more preferable to contain.
  • the ion binding can be confirmed by infrared spectroscopy, acid value titration, base titration and the like.
  • Examples of the nitrogen atom-containing resin in the case where the main chain having a nitrogen atom is a chain part composed of polyallylamine include a repeating unit represented by the following general formula (II-1), and a general formula (II- A structure having a repeating unit represented by 2) is preferred.
  • R 3 , R 4 , R 5 and R 6 each independently represent any of a hydrogen atom, a halogen atom and an alkyl group.
  • “*” Represents a connecting portion between repeating units.
  • X represents a group partially having a functional group having a pKa of 14 or less.
  • Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
  • the portion excluding X from the general formula (II-1) corresponds to the main chain having the nitrogen atom.
  • a portion excluding Y from the general formula (II-1) corresponds to the main chain having the nitrogen atom.
  • Examples of the alkyl group of R 3 , R 4 , R 5 and R 6 in the general formulas (II-1) and (II-2) include an alkyl having 1 to 5 carbon atoms which may have a substituent. Groups. Examples of the substituent include a halogen atom.
  • X in the general formulas (II-1) and (II-2) is not particularly limited as long as it is a group partially having a functional group having a pKa of 14 or less, and is appropriately selected depending on the purpose. Examples thereof include a group partially having a functional group having a pKa of 14 or less, which will be described later.
  • Y in the general formulas (II-1) and (II-2) is not particularly limited as long as it is a graft chain having a number average molecular weight of 500 to 1,000,000, and is appropriately selected according to the purpose. Examples thereof include a graft chain having a number average molecular weight of 500 to 1,000,000, which will be described later.
  • the nitrogen atom-containing resin includes a repeating unit represented by the following general formula (II-3) in addition to the repeating unit represented by the general formula (II-1) and the general formula (II-2). It is preferable to have it as a copolymerization component. By using such a repeating unit in combination, the dispersion performance of the filler can be improved, and the viscosity of the photosensitive composition can be suppressed from increasing.
  • R 3, R 4, R 5 and R 6 are each the same as R 3, R 4, R 5 and R 6 in the general formula (II-1) is there.
  • “*” Represents a connecting portion between repeating units.
  • Y ′ represents a graft chain having an anionic group and a number average molecular weight of 500 to 1,000,000.
  • the portion excluding Y ⁇ from the general formula (II-3) corresponds to the main chain having the nitrogen atom.
  • a polymer having a group that reacts with an amine to form a salt is added to a resin having at least one of a primary amino group and a secondary amino group. It can be formed by reacting.
  • the anionic group CO 2 - and SO 3 - are preferable, and CO 2 - is more preferable.
  • the anionic group is preferably at the terminal position of the graft chain having a number average molecular weight of 500 to 1,000,000.
  • R 3 , R 4 , R 5, and R 6 are hydrogen atoms because raw materials are easily available. It is preferable.
  • the repeating unit represented by the general formula (II-1) is a repeating unit having a group X partially having a functional group having a pKa of 14 or less.
  • Such a repeating unit includes a residue during development, From the viewpoint of resolution, it is preferably contained in an amount of 1 mol% to 80 mol%, more preferably 3% to 50 mol% in all repeating units of the nitrogen atom-containing resin.
  • the repeating unit represented by the general formula (II-2) is a repeating unit having a graft chain Y having a number average molecular weight of 500 to 1,000,000. Therefore, the content is preferably 10 mol% to 90 mol%, more preferably 30 mol% to 70 mol%, in all the repeating units of the nitrogen atom-containing resin.
  • the content ratio of the repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2) in the nitrogen atom-containing resin is a balance between dispersion stability and hydrophilicity / hydrophobicity.
  • the repeating unit (II-1) :( II-2) is preferably in the range of 10: 1 to 1: 100, and more preferably in the range of 1: 1 to 1:10. preferable.
  • the repeating unit represented by the general formula (II-3) used in combination if desired, has a graft chain having a number average molecular weight of 500 to 1,000,000 as a nitrogen atom of the main chain having the nitrogen atom. In terms of the effect, it is preferably contained in an amount of 0.5 mol% to 20 mol% in all repeating units of the nitrogen atom-containing resin, and 1 mol% to 10 mol%. It is more preferable to contain.
  • the ion binding can be confirmed by infrared spectroscopy, acid value titration, base titration and the like.
  • the number average molecular weight of the main chain having a nitrogen atom is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 to 10,000, more preferably 200 to 5,000, and more preferably 500 to 1,500 is particularly preferred. When the number average molecular weight is in the particularly preferred range, it is advantageous in terms of both the viscosity and developability of the photosensitive composition.
  • the molecular weight of the main chain having a nitrogen atom can be determined from the ratio of the hydrogen atom integral value of the terminal group and the chain portion measured by nuclear magnetic resonance spectroscopy. Further, for example, when a polymer having an amino group is used as a raw material for the nitrogen atom-containing resin, it can be determined by measuring the molecular weight of the polymer having an amino group.
  • pKa has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
  • the functional group having a pKa of 14 or less is not particularly limited as long as the physical properties satisfy this condition, and can be appropriately selected according to the purpose.
  • the pKa satisfies the above range with known functional groups. Specifically, for example, carboxylic acid (about pKa 3 to 5), sulfonic acid (about pKa-3 to -2), phosphoric acid (about pKa2), —COCH 2 CO— (about pKa 8 to 10).
  • the group partially having a functional group having a pKa of 14 or less is usually bonded directly to a nitrogen atom present in the main chain having the nitrogen atom, but the main chain nitrogen atom having the nitrogen atom.
  • a group having a functional group having a pKa of 14 or less in part may be linked not only by a covalent bond but also by an ionic bond to form a salt.
  • the nitrogen atom-containing resin may have a group partially containing a functional group having two or more different pKa values of 14 or less in the molecule.
  • the molecular weight of the group partially having a functional group having a pKa of 14 or less is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 1,000, More preferably, it is 500. When the molecular weight is within this range, developability and dispersibility are improved.
  • Examples of the group partially having a functional group having a pKa of 14 or less include a group represented by the following general formula (V-1), a group represented by the following general formula (V-2), and the following general formula A group represented by (V-3) is preferred.
  • V-1 a group represented by the following general formula (V-1)
  • V-2 a group represented by the following general formula (V-2)
  • V-3 the general formula (V-3)
  • U represents either a single bond or a divalent linking group.
  • d and e each independently represents either 0 or 1;
  • W represents either an acyl group or an alkoxycarbonyl group.
  • the divalent linking group represented by U is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkylene group, an oxygen-containing alkylene group, a cycloalkylene group, an arylene group, and an alkylene group. An oxy group is mentioned. Examples of the alkylene group include, -CH 2 -, - CH 2 CH 2 -, - CH 2 CH (CH 3) -, - (CH 2) 5 -, - CH 2 CH (n-C 10 H 21) -And the like. Examples of the oxygen-containing alkylene group include —CH 2 OCH 2 —, —CH 2 CH 2 OCH 2 CH 2 —, and the like.
  • Examples of the cycloalkylene group include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.
  • Examples of the arylene group include a phenylene group, a tolylene group, a biphenylene group, a naphthylene group, a furylene group, and a pyrrolylene group.
  • Examples of the alkyleneoxy group include an ethyleneoxy group, a propyleneoxy group, and a phenyleneoxy group.
  • an alkylene group having 1 to 30 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms are preferable, an alkylene group having 1 to 20 carbon atoms, and a cyclohexane having 5 to 10 carbon atoms.
  • An alkylene group and an arylene group having 6 to 15 carbon atoms are more preferable.
  • the d is preferably 1 from the viewpoint of productivity.
  • the e is preferably 0.
  • Examples of the acyl group for W include an acyl group having 1 to 30 carbon atoms.
  • the acyl groups having 1 to 30 carbon atoms a formyl group, an acetyl group, an n-propanoyl group, and a benzoyl group are preferable, and an acetyl group is more preferable, from the viewpoint of ease of production and availability of raw materials. .
  • alkoxycarbonyl group in W examples include, for example, methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, Pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Group and the like.
  • the content of the functional group having a pKa of 14 or less in the nitrogen atom-containing resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.01 mmol to 1 g of the nitrogen atom-containing resin. 5 mmol is preferable, and 0.05 mmol to 1 mmol is more preferable. When the content is in the more preferable range, the dispersibility and dispersion stability of the filler are improved, and the developability of the uncured portion is excellent in the photosensitive composition.
  • the acid value of the nitrogen-containing resin is preferably 5 mgKOH / g to 50 mgKOH / g from the viewpoint of developability of the photosensitive composition.
  • the acid value titration can be performed by a known method, for example, using an indicator method (a method for determining a neutralization point with an indicator), a potentiometric method, or the like.
  • indicator method a method for determining a neutralization point with an indicator
  • potentiometric method or the like.
  • titrant used in acid value titration can be used a commercially available aqueous sodium hydroxide, a functional group having a relatively high pKa (e.g., -COCH 2 CO-, phenolic hydroxyl group) as this
  • a nonaqueous titrant such as a sodium methoxide-dioxane solution and measure the acid value in a nonaqueous solvent system.
  • the group having a functional group having a pKa of 14 or less in part is bonded to a nitrogen atom present in the main chain having the nitrogen atom.
  • the nitrogen atom of the main chain having the nitrogen atom exists in the structure of an amino group, an ammonium group or an amide group, and the amino group, the ammonium group or the amide group has an acidic part on the filler surface, a hydrogen bond, an ion It is considered that the filler is adsorbed by the interaction such as bonding. Furthermore, since the group having a functional group having a pKa of 14 or less in part functions as an acid group, it can interact with a basic part of the filler (such as a nitrogen atom) or a metal atom.
  • the nitrogen atom-containing resin can adsorb both the basic part and the acidic part of the filler with a nitrogen atom and a group containing a functional group having a pKa of 14 or less, the adsorption ability is increased.
  • the dispersibility and dispersion stability are dramatically improved, and as a result, it is possible to suppress an increase in viscosity even when the content of the filler in the photosensitive composition is large.
  • a group having a functional group having a pKa of 14 or less in part also includes a functional group having a pKa of 14 or less as a partial structure, and thus functions as an alkali-soluble group. Accordingly, when the nitrogen atom-containing resin is used in a photosensitive composition, energy is applied to the coating film to be partially cured, and the unexposed portion is dissolved and removed to form a pattern. It is considered that the developability of the cured region into an alkaline developer is improved.
  • the nitrogen atom-containing resin contributes to the composite dispersibility of the filler, the improvement of the dispersion stability and the improvement of the developability of the photosensitive composition, and the photosensitive composition has high resolution and no development residue. It is thought that a thing is obtained.
  • the graft chain having a number average molecular weight of 500 to 1,000,000 is not particularly limited as long as it is a chain part bonded to the main chain having a nitrogen atom and has a number average molecular weight of 500 to 100,000.
  • known polymers such as polyesters, polyamides, polyimides, poly (meth) acrylates and the like that can be connected to the main chain having a nitrogen atom of the nitrogen atom-containing resin.
  • the binding site of the graft chain having the number average molecular weight of 500 to 1,000,000 and the main chain having a nitrogen atom is the end of the graft chain having the number average molecular weight of 500 to 1,000,000.
  • the nitrogen atom-containing resin may have two or more types of graft chains having a number average molecular weight of 500 to 1,000,000 having different structures in the molecule.
  • the graft chain having a number average molecular weight of 500 to 1,000,000 is preferably bonded to the nitrogen atom of the main chain having the nitrogen atom.
  • the bonding mode of the graft chain having a number average molecular weight of 500 to 1,000,000 and the nitrogen atom of the main chain having a nitrogen atom is any one of a covalent bond, an ionic bond, and a mixture of a covalent bond and an ionic bond. is there.
  • the graft chain having a number average molecular weight of 500 to 1,000,000 is preferably an amide bond with a nitrogen atom of the main chain having the nitrogen atom or an ionic bond as a carboxylate.
  • the number average molecular weight of the graft chain having the number average molecular weight of 500 to 1,000,000 can be measured by polystyrene conversion value by GPC method.
  • the number average molecular weight of the graft chain is preferably 1,000 to 50,000, and more preferably 1,000 to 30,000. When the number average molecular weight is in a more preferable range, it is advantageous in terms of dispersibility of the filler, dispersion stability, and developability of the photosensitive composition.
  • the graft chain having a number average molecular weight of 500 to 1,000,000 is preferably connected to the main chain having a nitrogen atom by 2 or more, more preferably 5 or more.
  • the graft chain having a number average molecular weight of 500 to 1,000,000 is preferably a graft chain represented by the following general formula (III-1).
  • Z is a polymer residue having at least a polyester chain as a partial structure, and from a polyester having a free carboxylic acid represented by the following general formula (IV) to a carboxyl It represents a polymer residue excluding a group.
  • Z is the same as Z in the general formula (III-1).
  • Y ′ is represented by the general formula (III -2).
  • Polyester having a free carboxylic acid represented by the general formula (IV) is, for example, (IV-1) polycondensation of carboxylic acid and lactone, (IV-2) hydroxy group (IV-3) polycondensation of dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride).
  • hydroxy group-containing carboxylic acid is preferably a straight-chain hydroxy group-containing carboxylic acid having 1 to 30 carbon atoms or a branched hydroxy group-containing carboxylic acid having 1 to 30 carbon atoms, such as glycolic acid, lactic acid, or 3-hydroxypropionic acid.
  • 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, and 2,2-bis (hydroxymethyl) butyric acid are more preferable.
  • linear aliphatic carboxylic acids having 6 to 20 carbon atoms and hydroxy group-containing carboxylic acids having 1 to 20 carbon atoms are particularly preferable.
  • These carboxylic acids may be used alone or in combination of two or more.
  • the lactone used for the polycondensation of carboxylic acid and lactone is not particularly limited and may be appropriately selected depending on the intended purpose.
  • ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -hexanolactone examples include lactone, ⁇ -octanolactone, ⁇ -valerolactone, ⁇ -hexalanolactone, ⁇ -octanolactone, ⁇ -caprolactone, ⁇ -dodecanolactone, ⁇ -methyl- ⁇ -butyrolactone, and the like.
  • ⁇ -caprolactone is preferable from the viewpoint of reactivity and availability.
  • These lactones may be used alone or in combination of two or more.
  • hydroxy group-containing carboxylic acid used for the polycondensation of the hydroxy group-containing carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the hydroxy group-containing carboxylic acid in the above (IV-1) The same is true for the preferred range.
  • dihydric alcohol used for the polycondensation of the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a linear aliphatic Examples include diols and branched aliphatic diols.
  • a diol having 2 to 30 carbon atoms is preferable, and an aliphatic diol having 2 to 20 carbon atoms is more preferable.
  • Examples of the aliphatic diol having 2 to 20 carbon atoms include ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 1,8-octanediol and the like.
  • the divalent carboxylic acid used for the polycondensation of the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Valent aliphatic carboxylic acid and branched divalent aliphatic carboxylic acid As the linear divalent aliphatic carboxylic acid and the branched divalent aliphatic carboxylic acid, a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms is preferable, and a divalent aliphatic carboxylic acid having 3 to 20 carbon atoms is preferable. Aliphatic carboxylic acids are more preferred.
  • divalent carboxylic acid having 3 to 20 carbon atoms examples include succinic acid, maleic acid, adipic acid, sebacic acid, dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid and malonic acid.
  • an acid anhydride equivalent to the divalent carboxylic acid for example, succinic anhydride, glutaric anhydride, etc.
  • succinic anhydride for example, succinic anhydride, glutaric anhydride, etc.
  • the divalent carboxylic acid and the dihydric alcohol are preferably charged at a molar ratio of 1: 1. Thereby, it becomes possible to introduce the carboxylic acid into the terminal of the polyester having the free carboxylic acid represented by the general formula (IV).
  • the polycondensation in producing the polyester having the free carboxylic acid represented by the general formula (IV) is preferably performed by adding a catalyst.
  • a catalyst that functions as a Lewis acid is preferable.
  • the catalyst that functions as the Lewis acid include Ti compounds, Sn compounds, and protonic acids.
  • the Ti compound include Ti (O—C 4 H 9 ) 4 and Ti (O—C 3 H 7 ) 4 .
  • the Sn compound include tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, stannic chloride, and butyltin dioxide.
  • the protonic acid include sulfuric acid and paratoluenesulfonic acid.
  • the amount of the catalyst in the polycondensation is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 mol% to 10 mol%, preferably 0.1 % To 5 mol% is more preferable.
  • the reaction temperature in the polycondensation is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 80 ° C to 250 ° C, more preferably 100 ° C to 180 ° C.
  • the reaction time in the polycondensation is usually 1 to 24 hours, although it varies depending on the reaction conditions.
  • the number average molecular weight of the polyester having a free carboxylic acid represented by the general formula (IV) is preferably 1,000 to 1,000,000, more preferably 2,000 to 100,000, and 3,000. ⁇ 50,000 is particularly preferred. When the number average molecular weight is in the above range, it is advantageous in that both dispersibility and developability can be achieved.
  • the number average molecular weight of the polyester having a free carboxylic acid represented by the general formula (IV) can be measured as a polystyrene converted value by the GPC method.
  • polyester having a free carboxylic acid represented by the general formula (IV) examples include (IV-1) polycondensation of carboxylic acid and lactone, and (IV-2) polycondensation of hydroxy group-containing carboxylic acid.
  • a polyester obtained by any of these is preferable from the viewpoint of ease of production.
  • the nitrogen atom-containing resin [(A-1) to (A-60)] are shown below by the specific structure of the repeating unit of the resin and the combination thereof, but the nitrogen atom-containing resin is not limited to this. It is not done.
  • p and q represent the number of linked polyester chains, and each independently represents 5 to 100,000.
  • R ′ represents either a hydrogen atom or an alkoxycarbonyl group.
  • the method for producing the nitrogen atom-containing resin examples include: (1) a resin having at least one of a primary amino group and a secondary amino group, and a precursor of a group partially having a functional group having a pKa of 14 or less. And a graft chain precursor having a number average molecular weight of 500 to 1,000,000, (2) a monomer containing a nitrogen atom, and a part of the functional group having a pKa of 14 or less And a method of polymerizing a monomer containing a group having the above and a monomer containing a graft chain having a number average molecular weight of 500 to 1,000,000.
  • the method produced by (1) is preferable.
  • the production method of (1) includes (a) a resin having at least one of a primary amino group and a secondary amino group, and a precursor of a group partially having a functional group having a pKa of 14 or less, A method of simultaneously reacting a precursor of a graft chain having a number average molecular weight of 500 to 1,000,000, (b) a resin having at least one of a primary amino group and a secondary amino group, and the pKa of 14 or less A method of reacting a precursor of a group partially having a functional group with a product of the reaction and a precursor of a graft chain having a number average molecular weight of 500 to 1,000,000, (C) After reacting a resin having at least one of a primary amino group and a secondary amino group with a precursor of a graft chain having a number average molecular weight of 500 to 1,000,000, a product of the reaction And said A method of reacting a precursor of a group having a part Ka
  • Resin having at least one of primary amino group and secondary amino group include a polymer having an amino group constituting the main chain having the nitrogen atom.
  • the polymer having an amino group include poly (alkyleneimine), polyallylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, polyvinylamine, and 3-dialkylaminopropyl (meth) acrylic acid amide.
  • examples thereof include a copolymer having as a component and a copolymer having 2-dialkylaminoethyl (meth) acrylate as a copolymer component.
  • poly (alkyleneimine) and polyallylamine are preferable.
  • a precursor of a group partially having a functional group with a pKa of 14 or less reacts with a resin having at least one of the primary amino group and the secondary amino group, and the nitrogen atom in the nitrogen atom-containing resin
  • Examples of the precursor of a group partially having a functional group having a pKa of 14 or less include a cyclic carboxylic acid anhydride, a halogen atom-containing carboxylic acid, a sultone, a diketene, a cyclic sulfocarboxylic acid anhydride, —COCH 2 COCl And cyanoacetic acid chloride.
  • a cyclic carboxylic acid anhydride, sultone, and diketene are preferable from the viewpoint of productivity.
  • the cyclic carboxylic acid anhydride is preferably a cyclic carboxylic acid anhydride having 4 to 30 carbon atoms.
  • Examples of the cyclic carboxylic acid anhydride having 4 to 30 carbon atoms include succinic anhydride, glutaric anhydride, itaconic anhydride, maleic anhydride, allyl succinic anhydride, butyl succinic anhydride, and n-octyl.
  • Examples of the halogen atom-containing carboxylic acid include chloroacetic acid, bromoacetic acid, iodoacetic acid, 4-chloro-n-butyric acid, and the like.
  • Examples of the sultone include propane sultone and 1,4-butane sultone.
  • Examples of the cyclic sulfocarboxylic acid anhydride include 2-sulfobenzoic acid anhydride.
  • Examples of the compound containing —COCH 2 COCl include ethyl malonyl chloride.
  • Precursor of graft chain having a number average molecular weight of 500 to 1,000,000 reacts with a resin having at least one of the primary amino group and secondary amino group, and the nitrogen atom in the nitrogen atom-containing resin. Represents a compound capable of binding a graft chain having a number average molecular weight of 500 to 1,000,000 to the main chain having
  • the graft chain precursor having a number average molecular weight of 500 to 1,000,000 is a number having a terminal group capable of either a covalent bond or an ionic bond with the main chain having a nitrogen atom in the nitrogen atom-containing resin.
  • a polymer having an average molecular weight of 500 to 1,000,000 is preferred, and a polymer having a number average molecular weight of 500 to 1,000,000 having a free carboxyl group at one end is more preferred.
  • Examples of the precursor of the graft chain having a number average molecular weight of 500 to 1,000,000 include, for example, a polyester having a free carboxylic acid represented by the general formula (IV) (polyester having a carboxyl group at one end) And a polyamide having a free carboxylic acid at one end, and a poly (meth) acrylic acid resin having a free carboxylic acid at one end.
  • a polyester having a free carboxylic acid represented by the general formula (IV) is more preferable.
  • the graft chain precursor having a number average molecular weight of 500 to 1,000,000 can be synthesized by a known method.
  • a polyester having a free carboxylic acid represented by the general formula (IV) IV-1 polycondensation of carboxylic acid and lactone, (IV-2) polycondensation of hydroxy group-containing carboxylic acid, (IV-3) dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride) ) Polycondensation or the like.
  • the polyamide containing a free carboxylic acid at one end can be produced by self-condensation of an amino group-containing carboxylic acid (for example, glycine, alanine, ⁇ -alanine, 2-aminobutyric acid, etc.).
  • the poly (meth) acrylic acid ester having a free carboxylic acid at one end is obtained by radical polymerization of a (meth) acrylic acid monomer in the presence of a carboxyl group-containing chain transfer agent (for example, 3-mercaptopropionic acid). Can be manufactured.
  • the reaction temperature in the production of the nitrogen atom-containing resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C.
  • the reaction time in the production is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 hour to 48 hours, more preferably 1 hour to 24 hours from the viewpoint of productivity.
  • the reaction in the production may be performed in the presence of a solvent.
  • a solvent examples include water, sulfoxide compounds (for example, dimethyl sulfoxide), ketone compounds (for example, acetone, methyl ethyl ketone, cyclohexanone, etc.), ester compounds (for example, ethyl acetate, butyl acetate, ethyl propionate, propylene glycol 1-monomethyl).
  • Ether 2-acetate, etc. ether compounds (eg, diethyl ether, dibutyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbon compounds (eg, pentane, hexane, etc.), aromatic hydrocarbon compounds (eg, toluene, xylene, mesitylene, etc.) ), Nitrile compounds (eg, acetonitrile, propiononitrile, etc.), amide compounds (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), carboxylic acids Compounds (eg, acetic acid, propionic acid, etc.), alcohol compounds (eg, methanol, ethanol, isopropanol, n-butanol, 3-methylbutanol, 1-methoxy-2-propanol, etc.), halogenated solvents (eg, chloroform, 1,2-dichloroethan
  • the reprecipitation method is mentioned.
  • a hydrocarbon solvent such as hexane and an alcohol solvent such as methanol.
  • the nitrogen atom-containing monomer used in the production method (2) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples thereof include 2-dialkylaminoethyl (meth) acrylate, 3- Examples thereof include dialkylaminopropyl (meth) acrylamide, vinylpyridine, N-vinylimidazole and the like.
  • a monomer containing a tertiary amino group is preferable, and 2-dialkylaminoethyl (meth) acrylate and 3-dialkylaminopropyl (meth) acrylamide are more preferable.
  • the monomer containing a group partially having a functional group having a pKa of 14 or less used in the production method of (2) includes a group partially having a functional group having a pKa of 14 or less.
  • (Meth) acrylic acid amides are preferred, and amino acids containing a (meth) acryloyl group such as N- (meth) acryloylglycine and N- (meth) acryloylalanine are more preferred.
  • Examples of the monomer containing a graft chain having a number average molecular weight of 500 to 1,000,000 used in the production method of (2) include known monomers, such as poly (meth) acrylate, polystyrene or A macromonomer having a polymerizable group at one end of the polyester is preferred.
  • Examples of such a monomer include macromonomers AA-6 (polymethyl methacrylate having a methacryloyl group at the end group), AS-6 (polystyrene having a methacryloyl group at the end group), AN-6S (manufactured by Toa Gosei Co., Ltd.).
  • the polymerization in the production method (2) is preferably performed using a radical polymerization initiator in a nitrogen atmosphere.
  • a radical polymerization initiator known radical polymerization initiators can be used, but azobisisobutyronitrile and methyl 2,2′-azobisisobutyrate are preferable from the viewpoint of adjustment of molecular weight and handling.
  • the radical polymerization initiator is preferably used in an amount of 0.01 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, based on the number of moles of all monomers.
  • a chain transfer agent may be added.
  • the chain transfer agent is preferably an all compound, more preferably an alkanethiol having 5 to 20 carbon atoms, 2-mercaptoethanol, or 2-mercaptopropionic acid.
  • the chain transfer agent is preferably used in an amount of 0.01 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, based on the number of moles of all monomers.
  • the reaction temperature in the polymerization is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 100 ° C, more preferably 70 ° C to 90 ° C.
  • polymerization According to the objective, it can select suitably, For example, the solvent illustrated by the manufacturing method of said (1) is mentioned.
  • the weight average molecular weight of the nitrogen atom-containing resin thus obtained is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3,000 to 1,000,000. 5,000 to 500,000 is more preferable. When the weight average molecular weight is in the above range, it is advantageous in terms of high developability and storage stability.
  • the content of the nitrogen atom-containing resin is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.1 to 70 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Part by mass is preferable, 1.0 part by mass to 50 parts by mass is more preferable, and 2.0 part by mass to 30 parts by mass is particularly preferable.
  • the content is less than 0.1 parts by mass, the dispersibility of the filler may decrease and the viscosity may increase.
  • the content exceeds 70 parts by mass the particles are cross-linked during dispersion of the filler, and the storage stability is improved. May decrease.
  • the content is within the particularly preferable range, it is advantageous in terms of stability after dispersing the filler.
  • the presence of nitrogen atoms in the main chain having nitrogen atoms of the nitrogen atom-containing resin can be confirmed by a method such as acid titration.
  • the presence of a functional group having a pKa of 14 or less in the nitrogen atom-containing resin, and that the group having the functional group is bonded to the nitrogen atom present in the main chain having the nitrogen atom is determined by base titration, nucleus This can be confirmed by methods such as magnetic resonance spectroscopy and infrared spectroscopy. It is confirmed by a method such as nuclear magnetic resonance spectroscopy or GPC that the graft chain having the number average molecular weight of 500 to 1,000,000 of the nitrogen atom-containing resin is bonded to the main chain having the nitrogen atom. can do.
  • the resin is not particularly limited as long as it is a resin other than the nitrogen atom-containing resin and is a compound into which an acid group for imparting a photosensitive group and alkali developability is introduced, and is appropriately selected depending on the purpose.
  • a poly (meth) acrylic resin, a polyester resin, a polyurethane resin, a polyamide resin, a polyamic acid resin, a polyether resin, a polyurea resin, a polycarbonate resin and the like into which a photosensitive group and an acid group have been introduced may be mentioned. .
  • a polymer obtained by reacting an epoxy resin having two or more epoxy groups with a vinyl group-containing organic acid and further reacting with a polybasic acid anhydride, a polyurethane comprising polyisocyanate and polyisocyanate Resins are preferred.
  • the polyurethane resin has a structure derived from polyisocyanate and polyisocyanate, and as the polyurethane resin, an acid-modified vinyl group-containing polyurethane resin is used in terms of alkali developability and toughness of a cured film. Is preferred.
  • the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a polyurethane resin having an ethylenically unsaturated bond in the side chain (ii) a carboxyl group
  • a polyurethane resin obtained by reacting a containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule examples thereof include a polyurethane resin obtained by reacting a containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule.
  • polyurethane resin having an ethylenically unsaturated bond in the side chain-- is not particularly limited and may be appropriately selected depending on the purpose.
  • the side chain may be represented by the following general formulas (1) to (3). What has at least 1 among the functional groups represented is mentioned.
  • R 1 to R 3 each independently represents either a hydrogen atom or a monovalent organic group.
  • R 1 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
  • the R 2 and R 3 are not particularly limited and may be appropriately selected depending on the purpose.
  • each of R 2 and R 3 is independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group.
  • a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.
  • X represents an oxygen atom, a sulfur atom
  • -N (R 12) - represents one of the R 12 represents a hydrogen atom or a monovalent organic group.
  • R 12 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group which may have a substituent.
  • a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
  • the substituent that can be introduced is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom.
  • R 4 to R 8 each independently represents either a hydrogen atom or a monovalent organic group.
  • R 4 to R 8 are not particularly limited and may be appropriately selected depending on the intended purpose. Hydrogen atoms, halogen atoms, amino groups, dialkylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, nitro groups , A cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, substituted An alkylamino group which may have a group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like.
  • a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.
  • Y represents any of an oxygen atom, a sulfur atom, and —N (R 12 ) —.
  • R 12 has the same meaning as R 12 in the general formula (1), and preferred examples are also the same.
  • R 9 to R 11 each independently represents a hydrogen atom or a monovalent organic group.
  • R 9 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
  • the R 10 and R 11 are not particularly limited and may be appropriately selected depending on the intended purpose.
  • a good arylsulfonyl group, and the like are preferable because of high radical reactivity.
  • Z represents an oxygen atom, a sulfur atom, —N (R 13 ) —, or an optionally substituted phenylene group.
  • R ⁇ 13 > There is no restriction
  • the alkyl group etc. which may have a substituent are mentioned. Among these, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
  • the urethane resin having an ethylenically unsaturated bond in the side chain includes at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the following general formula (5):
  • X 0 and Y 0 each independently represent a divalent organic residue.
  • At least one of the diisocyanate compound represented by the general formula (4) and the diol compound represented by the general formula (5) is a group represented by the general formulas (1) to (3). If at least one of them is present, a polyurethane resin in which the groups represented by the above general formulas (1) to (3) are introduced into the side chain as a reaction product of the diisocyanate compound and the diol compound is provided. Generated. According to such a method, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain can be easily used, rather than replacing and introducing a desired side chain after the reaction of the polyurethane resin. Can be manufactured.
  • the diisocyanate compound represented by the general formula (4) is not particularly limited and can be appropriately selected depending on the purpose.
  • a triisocyanate compound and a monofunctional alcohol having an unsaturated group Or the product obtained by addition-reacting with 1 equivalent of monofunctional amine compounds is mentioned.
  • the triisocyanate compound is not particularly limited and may be appropriately selected depending on the purpose.
  • the monofunctional alcohol having an unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs of JP-A-2005-250438 And compounds described in “0037” to “0040”.
  • the method for introducing an unsaturated group into the side chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a method using a diisocyanate compound containing is preferable.
  • the diisocyanate compound that can be obtained include compounds having an unsaturated group in the side chain described in paragraphs “0042” to “0049” of JP-A-2005-250438.
  • the polyurethane resin having an ethylenically unsaturated bond in the side chain is a diisocyanate containing the unsaturated group from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability.
  • Diisocyanate compounds other than the compounds can also be copolymerized.
  • the diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose.
  • it is a diisocyanate compound represented by the following general formula (6).
  • L 1 represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L 1 may have another functional group that does not react with an isocyanate group, for example, an ester, urethane, amide, or ureido group.
  • the diisocyanate compound represented by the general formula (6) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Aromatic diisocyanate compounds such as' -diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate; isophorone diisocyanate, 4,4 -Alicyclic diisocyanate compounds such as methylenebis (cyclohexyl
  • diol compound represented by the said General formula (5) there is no restriction
  • a method for introducing an unsaturated group into the side chain of the polyurethane resin in addition to the above-described method, a method using a diol compound containing an unsaturated group in the side chain as a raw material for producing the polyurethane resin is also preferable.
  • the diol compound containing an unsaturated group in the side chain may be, for example, a commercially available product such as trimethylolpropane monoallyl ether, and a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound;
  • the compound which is easily manufactured by reaction with compounds, such as a carboxylic acid, an acid chloride, an isocyanate, alcohol, an amine, a thiol, and a halogenated alkyl compound containing an unsaturated group may be sufficient.
  • the diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose.
  • R 1 to R 3 each independently represents a hydrogen atom or a monovalent organic group
  • A represents a divalent organic residue
  • X represents an oxygen atom, a sulfur atom, or —N (R 12 ) —, wherein R 12 represents a hydrogen atom or a monovalent organic group.
  • R 1 ⁇ R 3 and X in the general formula (G) said a general formula (1) the same meaning as R 1 ⁇ R 3 and X in preferred embodiments versa.
  • the polyurethane resin having an ethylenically unsaturated bond in the side chain is unsaturated in the side chain from the viewpoint of, for example, improving compatibility with other components in the photosensitive composition and improving storage stability.
  • a diol compound other than a diol compound containing a group can be copolymerized.
  • the diol compound other than the diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the purpose.
  • the polyether diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs “0068” to “0076” of JP-A-2005-250438. It is done.
  • the polyester diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paragraphs “0077” to “0079” and paragraphs “0083” to “0085” of JP-A-2005-250438. No. 1-No. 8 and no. 13-No. 18 and the like.
  • the polycarbonate diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the paragraphs “0080” to “0081” and paragraph “0084” of JP-A-2005-250438, No. 9-No. 12 listed compounds.
  • the diol compound which has a substituent which does not react with an isocyanate group other than the diol compound mentioned above can also be used together.
  • the diol compound having a substituent that does not react with the isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0087” to “0088” of JP-A-2005-250438 And the compounds described.
  • a diol compound having a carboxyl group can be used in combination with the diol compound described above.
  • Examples of the diol compound having a carboxyl group include those represented by the following general formulas (17) to (19).
  • R 15 represents a hydrogen atom, a substituent (for example, a cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc.), —CONH 2 , —COOR 16 , —OR 16 , —NHCONHR 16 , —NHCOOR 16 , —NHCOR 16 , —OCONHR 16 (wherein R 16 is an alkyl group having 1 to 10 carbon atoms, or aralkyl having 7 to 15 carbon atoms)
  • Each group such as a group represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group, which may have a group, and is not particularly limited.
  • a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable.
  • L 9 , L 10 and L 11 may be the same or different from each other, and may be a single bond, a substituent (for example, alkyl, aralkyl, aryl, alkoxy). And each group of halogeno are preferred.), As long as they represent a divalent aliphatic or aromatic hydrocarbon group which may have a substituent, and can be appropriately selected according to the purpose.
  • an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable.
  • the L 9 to L 11 may have other functional groups that do not react with isocyanate groups, such as carbonyl, ester, urethane, amide, ureido, and ether groups.
  • Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and may be appropriately selected according to the purpose.
  • An aromatic group having 6 to 15 carbon atoms is preferable.
  • the diol compound having a carboxyl group represented by the general formulas (17) to (19) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • 3,5-dihydroxybenzoic acid, 2 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4- Hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) ) -3-carboxy-propionamide and the like.
  • the polyurethane resin having an ethylenically unsaturated bond group in the side chain is a resin further having a carboxyl group in the side chain, and more specifically, the vinyl group in the side chain is 0.05 mmol.
  • the side chain preferably has a carboxyl group, and the acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and 35 mgKOH / g to 100 mgKOH / g. g is particularly preferred.
  • the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
  • the compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs “0095” to “2005” of JP-A-2005-250438 can be selected. And the compounds described in “0101”.
  • the polyurethane resin having an ethylenically unsaturated bond in the side chain is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. Is done.
  • the molar ratio (M a : M b ) of the diisocyanate and diol compound used in the synthesis is not particularly limited and can be appropriately selected according to the purpose, and is preferably 1: 1 to 1.2: 1.
  • a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.
  • the amount of introduction in the polyurethane resin having an ethylenically unsaturated bond in the side chain of the ethylenically unsaturated bond group is not particularly limited and can be appropriately selected according to the purpose. 0.05 mmol / g to 3.0 mmol / g is preferable, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable. Furthermore, in the polyurethane resin having an ethylenically unsaturated bond in the side chain, it is preferable that a carboxyl group is introduced into the side chain together with the ethylenically unsaturated bond group.
  • the acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and particularly preferably 35 mgKOH / g to 100 mgKOH / g.
  • the molecular weight of the polyurethane resin having an ethylenically unsaturated bond in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2,000 to 50,000 in terms of weight average molecular weight. 30,000 to 30,000 is more preferable.
  • the photosensitive composition when used for a photosensitive solder resist, it is excellent in crack resistance and heat resistance, and is excellent in developability of non-image areas with an alkaline developer.
  • polyurethane resin having an ethylenically unsaturated bond in the side chain those having an unsaturated group in the polymer terminal and main chain are also preferably used.
  • Polyurethane resin having an ethylenically unsaturated bond in the side chain, or between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated bond in the side chain by having an unsaturated group at the polymer terminal and main chain Crosslinking reactivity is improved, and the strength of the photocured product is increased.
  • a material having excellent toughness can be provided.
  • the unsaturated group has a carbon-carbon double bond from the viewpoint of easy occurrence of a crosslinking reaction.
  • Examples of the method for introducing an unsaturated group at the polymer terminal include the following methods. That is, in the process of synthesizing a polyurethane resin having an ethylenically unsaturated bond in the side chain described above, in the process of treating with a residual isocyanate group at the polymer terminal and an alcohol or an amine, an alcohol having an unsaturated group Alternatively, amines or the like may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
  • the unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.
  • the ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
  • the amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the vinyl group equivalent is preferably 0.05 mmol / g to 3.0 mmol / g, preferably 0.5 mmol. / G to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.
  • a method for introducing an unsaturated group into the main chain there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin.
  • the diol compound having an unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, cis-2-butene-1,4-diol, trans-2-butene-1 , 4-diol, polybutadiene diol, and the like.
  • the polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin.
  • the polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.
  • polyurethane resin having an ethylenically unsaturated bond in the side chain examples include, for example, P-1 to P— shown in paragraphs “0293” to “0310” of JP-A-2005-250438. 31 polymers, and the like. Among these, polymers of P-27 and P-28 shown in paragraphs “0308” and “0309” are preferable.
  • a polyurethane resin obtained by reacting the carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule includes a carboxyl group-containing polyurethane having a diisocyanate and a carboxylic acid group-containing diol as essential components; And a polyurethane resin obtained by reacting a compound having an epoxy group and a vinyl group.
  • a low molecular weight diol having a weight average molecular weight of 300 or less or a low molecular diol having a weight average molecular weight of 500 or more may be added as a copolymer component to the polyurethane resin.
  • the polyurethane resin includes a divalent aliphatic or aromatic hydrocarbon diisocyanate which may have a substituent, a COOH group and two OH groups via any one of a C atom and an N atom.
  • a reaction product comprising a carboxylic acid-containing diol as an essential component, which is obtained by reacting the obtained reaction product with a compound having an epoxy group and a vinyl group in the molecule via a —COO— bond It may be.
  • the polyurethane resin includes at least one selected from diisocyanates represented by the following general formula (XI) and carboxylic acid group-containing diols represented by the following general formulas (XII-1) to (XII-3): And at least one selected from polymer diols having a weight average molecular weight in the range of 800 to 3,000 represented by the following general formulas (XIII-1) to (XIII-5) according to the purpose:
  • R 1 may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Represents an aromatic or aromatic hydrocarbon. If necessary, R 1 may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.
  • a substituent for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable.
  • R 1 may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.
  • R 2 represents a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH 2 , —COOR 6 , —OR 6 , —NHCONHR 6 , —NHCOOR 6 , —NHCOR 6 , —OCONHR 6 , —CONHR 6 (wherein R 6 is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) Represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group.
  • a substituent for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH 2 , —COOR 6 , —OR 6
  • R 3 , R 4 and R 5 may be the same or different, and each may be a single bond, a substituent (for example, an alkyl group or an aralkyl group).
  • An aryl group, an alkoxy group, and a halogeno group are preferable).
  • an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable.
  • any other functional group that does not react with an isocyanate group for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. You may have. In addition, you may form a ring by 2 or 3 of said R ⁇ 2 >, R ⁇ 3 >, R ⁇ 4 > and R ⁇ 5 >.
  • Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and is preferably an aromatic group having 6 to 15 carbon atoms.
  • R 7 , R 8 , R 9 , R 10 and R 11 may be the same or different, respectively.
  • R 7 , R 9 , R 10 and R 11 are each preferably an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene or carbon having 2 to 10 carbon atoms Several to 10 arylene groups are more preferred.
  • R 8 represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms is More preferred.
  • R 7 , R 8 , R 9 , R 10 and R 11 other functional groups that do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups , An amide group, a ureido group, or a halogen atom.
  • R 12 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group, or a halogen atom.
  • a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or one carbon atom is preferable. More preferred are ⁇ 6 alkyl and aryl groups having 6 to 10 carbon atoms.
  • R 12 may have other functional groups that do not react with isocyanate groups, such as alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms.
  • R 13 represents an aryl group or a cyano group, preferably an aryl group or a cyano group having 6 to 10 carbon atoms.
  • m represents an integer of 2 to 4.
  • n 1 , n 2 , n 3 , n 4 and n 5 each represents an integer of 2 or more, and an integer of 2 to 100 is preferable.
  • n 6 represents 0 or an integer of 2 or more, preferably 0 or an integer of 2 to 100.
  • R 14 represents a hydrogen atom or a methyl group
  • R 15 represents an alkylene group having 1 to 10 carbon atoms
  • R 16 represents a carbon atom.
  • p represents 0 or an integer of 1 to 10.
  • the polyurethane resin may further be copolymerized with a low molecular weight diol containing no carboxylic acid group as a fifth component.
  • a low molecular weight diol examples include those represented by the general formulas (XIII-1) to (XIII-5).
  • the weight average molecular weight is 500 or less.
  • the low molecular weight diol containing no carboxylic acid group can be added as long as the alkali solubility is not lowered and the elastic modulus of the cured film can be kept sufficiently low.
  • a diisocyanate represented by the general formula (XI) and at least one selected from carboxylic acid group-containing diols represented by the general formulas (XII-1) to (XII-3) are essential.
  • a component depending on the purpose, at least one selected from polymer diols having a weight average molecular weight of 800 to 3,000, represented by general formulas (XIII-1) to (XIII-5),
  • a reaction product with a low molecular weight diol containing no carboxylic acid group and having a weight average molecular weight of 500 or less represented by formulas (XIII-1) to (XIII-5) is further added to formulas (XIV-1) to (XIV-16).
  • the acid value is 20 mgKOH / g to 12
  • Alkali-soluble photocrosslinking polyurethane resin is mg KOH / g are preferred.
  • These polymer compounds may be used alone or in combination of two or more.
  • the content of the acid-modified vinyl group-containing polyurethane resin is preferably 2 to 30 parts by mass and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition.
  • the content is less than 2 parts by mass, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 30 parts by mass, the developability may deteriorate and the toughness of the cured film may decrease.
  • the diisocyanate compound and the diol compound are synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating.
  • the molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. If an isocyanate group remains at the end of the polymer, the molar ratio can be reduced by treatment with alcohols or amines. It is synthesized in such a way that no isocyanate groups remain entangled.
  • diisocyanate is not particularly limited and may be appropriately selected depending on the purpose.
  • High molecular weight diol The high molecular weight diol compound represented by the general formulas (XIII-1) to (XIII-5) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as disclosed in JP-A-2007-2030 And compounds described in paragraphs “0022” to “0046”.
  • diol compound having a carboxyl group represented by the general formulas (XII-1) to (XII-3) is not particularly limited and may be appropriately selected depending on the intended purpose. And the compounds described in paragraph “0047” of the publication No. 2030.
  • the carboxylic acid group-free low molecular weight diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0048” of JP-A-2007-2030. Can be mentioned.
  • the copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80% or less, and particularly preferably 50% or less in the low molecular weight diol. When the copolymerization amount exceeds 95 mol%, a urethane resin having good developability may not be obtained.
  • polyurethane resin obtained by reacting the above (ii) carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule include, for example, paragraphs “0314” to JP-A-2007-2030.
  • Glycidyl acrylate as an epoxy group and vinyl group-containing compound in the polymers U1 to U4 and U6 to U11 shown in “0315” is converted to glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400 (Daicel). Chemical)), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400 (manufactured by Daicel Chemical)), and the like.
  • the content of the acid-modified vinyl group-containing polyurethane resin in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% by mass to 80% by mass, and preferably 20% by mass. Is more preferably from 75 to 75% by weight, particularly preferably from 30 to 70% by weight. If the content is less than 5% by mass, good crack resistance may not be maintained, and if it exceeds 80% by mass, the heat resistance may fail. On the other hand, when the content is within the particularly preferable range, it is advantageous in terms of both good crack resistance and heat resistance.
  • the weight average molecular weight of the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2,000 to 60,000, and preferably 5,000 to 50,000. More preferred is 3,000 to 30,000. When the weight average molecular weight is less than 2,000, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 60,000, coating suitability and developability may be deteriorated. .
  • the weight average molecular weight is determined using, for example, a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.), a 0.5 mass% THF solution as a sample solution, and a column using one TSKgel HZM-M. Then, 200 ⁇ L of sample is injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or a UV detector (detection wavelength 254 nm). Next, the weight average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
  • the acid value of the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. 35 mg KOH / g to 100 mg KOH / g is particularly preferable. If the acid value is less than 20 mgKOH / g, the developability may be insufficient, and if it exceeds 120 mgKOH / g, the development rate may be too high, and development control may be difficult. In addition, the said acid value can be measured based on JISK0070, for example. However, if the sample does not dissolve, dioxane or tetrahydrofuran is used as the solvent.
  • the vinyl group equivalent of the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 mmol / g to 3.0 mmol / g, preferably 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.
  • the vinyl group equivalent can be determined, for example, by measuring the bromine number. The bromine number can be measured according to, for example, JIS K2605.
  • the photosensitive composition of the present invention it is preferable to add another resin to the photosensitive composition of the present invention in an amount of 50% by mass or less based on the polyurethane resin as necessary.
  • the other resin include polyamide resin, epoxy resin, polyacetal resin, acrylic resin, methacrylic resin, polystyrene resin, and novolac type phenol resin.
  • the content of the resin is preferably 5 to 80 parts by mass, and more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition.
  • the content is 5 parts by mass or more, developability and exposure sensitivity are good, and when the content is 80 parts by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.
  • the thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose.
  • an epoxy compound for example, at least two oxirane groups in one molecule
  • An oxetane compound having at least two oxetanyl groups in one molecule, an epoxy compound having an oxirane group as described in JP-A-2007-47729, and a ⁇ -position Examples include an epoxy compound having an alkyl group, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a compound obtained by reacting an isocyanate group of a polyisocyanate and a derivative thereof with a blocking agent, and a melamine derivative.
  • Examples of the epoxy compound include an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound having at least two epoxy groups having an alkyl group at the ⁇ -position in one molecule.
  • Examples of the epoxy compound having at least two oxirane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc.
  • Cyclic epoxy resin (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, water Bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin) , Brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP- 7200, HP-7200H; manufactured by Dainippon Ink and Chemicals, Inc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline
  • an epoxy compound containing at least two epoxy groups having an alkyl group at the ⁇ -position can be used, and the ⁇ -position is an alkyl group.
  • Particularly preferred are compounds containing an epoxy group substituted with a (specifically, a ⁇ -alkyl-substituted glycidyl group or the like).
  • all of two or more epoxy groups contained in one molecule may be a ⁇ -alkyl-substituted glycidyl group, and at least one epoxy group May be a ⁇ -alkyl-substituted glycidyl group.
  • oxetane compound examples include oxetane compounds having at least two oxetanyl groups in one molecule. Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or cop
  • polyisocyanate compound a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is an aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene).
  • bifunctional isocyanate for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene.
  • Diisocyanate bis (4-isocyanate-phenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.
  • the bifunctional isocyanate trimethylolpropane, pentalithol tol
  • Polyfunctional alcohols such as glycerin and the like
  • hexamethylene diisocyanate hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.
  • an isocyanate group blocking agent in a compound obtained by reacting a blocking agent with the polyisocyanate compound that is, a compound obtained by reacting a blocking agent with an isocyanate group of polyisocyanate and derivatives thereof, alcohols (for example, isopropanol, tert-butanol, etc.), lactams (eg, ⁇ -caprolactam, etc.), phenols (eg, phenol, cresol, p-tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol, p -Nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, methyl ethyl ketoxy) Arm, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclo
  • Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.
  • the content of the thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is 1 to 50 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Preferably, 3 parts by mass to 30 parts by mass is more preferable. If the said content is 1 mass part or more, the film
  • filler examples include inorganic fillers and organic fillers.
  • the inorganic filler is not particularly limited and may be appropriately selected from known ones.
  • kaolin barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, water
  • examples thereof include aluminum oxide and mica.
  • silica is preferable from the viewpoint of heat resistance, toughness, insulation, and dielectric constant.
  • silica examples include silicon oxide powder, finely divided silicon oxide, gas phase method silica, amorphous silica, crystalline silica, fused silica, and spherical silica.
  • a commercial item can be used as said silica, for example, the silica marketed from Admatex, Tatsumori, etc. is mentioned.
  • the organic filler is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine resin, benzoguanamine resin, and cross-linked polystyrene resin.
  • the average particle size of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 ⁇ m to 20 ⁇ m, more preferably 0.02 ⁇ m to 10 ⁇ m, and particularly preferably 0.05 ⁇ m to 5 ⁇ m. preferable.
  • the average particle diameter is less than 0.01 ⁇ m, sufficient heat resistance may not be obtained, and when it exceeds 20 ⁇ m, resolution may be deteriorated.
  • the average particle diameter is in the particularly preferred range, it is advantageous in that both resolution and heat resistance can be achieved.
  • the average particle diameter of the filler can be measured by a laser diffraction / scattering method.
  • the content of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 parts by mass to 97 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition, 15 parts by mass to 95 parts by mass is more preferable, and 25 parts by mass to 95 parts by mass is particularly preferable.
  • the content is less than 10 parts by mass, sufficient heat resistance may not be obtained, and when it exceeds 97 parts by mass, resolution may be deteriorated.
  • the content is within the particularly preferable range, it is advantageous in that both resolution and heat resistance can be achieved.
  • Examples of the ethylenically unsaturated bond include (meth) acryloyl group, (meth) acrylamide group, vinylphenyl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester, and the like. .
  • the compound having one or more ethylenically unsaturated bonds is not particularly limited and may be appropriately selected depending on the intended purpose.
  • at least one selected from monomers having a (meth) acryl group is Preferably mentioned.
  • polyethyleneglycol mono (meth) acrylate polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth)
  • Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) acrylate, dipentaerythritol penta (meth)
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.
  • the content of the polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. It is 5 to 50 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Preferably, 10 parts by weight to 40 parts by weight is more preferable. When the content is 5 parts by mass or more, developability and exposure sensitivity are good, and when the content is 50 parts by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.
  • the photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone
  • Acetophenone compounds such as N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthra Anthraquinone compounds such as N, N-
  • the content of the photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Mass parts are preferred, and 2 to 15 parts by mass are more preferred. If the content is 0.5 parts by mass or more, the exposed part can be prevented from eluting during development, and if it is 20 parts by mass or less, the heat resistance can be prevented from decreasing. .
  • the other components include solvents, sensitizers, adhesion promoters, thermal polymerization inhibitors, colorants, other additives, and other auxiliary agents (for example, conductive particles, erasing agents, etc.). You may use together a foaming agent, a flame retardant, a leveling agent, a peeling accelerator, antioxidant, a fragrance
  • the solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate
  • Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chlor
  • 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 generating radicals, acids, etc. It is possible to generate a useful group of The sensitizer is not particularly limited and may be appropriately selected from known sensitizers.
  • polynuclear aromatics for example, pyrene, perylene, triphenylene
  • xanthenes for example, Fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • cyanines eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine
  • merocyanines eg, merocyanine, carbomerocyanine
  • thiazines eg, thionine, methylene blue
  • Toluidine blue acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrid) N-methylacridone, N-butylacridone, N-butyl-
  • Examples of the combination 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) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.
  • the content of the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.05 to 30 parts by mass with respect to 100 parts by mass of the solid content in the photosensitive composition. Part by mass is preferable, 0.1 to 20 parts by mass is more preferable, and 0.2 to 10 parts by mass is particularly preferable. When the content is less than 0.05 parts by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease. When the photosensitive composition is a photosensitive film, the sensitizer may be precipitated from the photosensitive layer in the photosensitive film during storage.
  • the adhesion promoter has a function of improving adhesion between layers, adhesion between the photosensitive layer and the substrate, and electrolytic corrosion.
  • the adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine, acetoguanamine, benzoguatemine, melamine-phenol formalin resin, ethyldiamino-S-triazine, 2,4-diamino. And triazine compounds such as -S-triazine and 2,4-diamino-6-xylyl-S-triazine.
  • triazine compounds include the following structural formulas (B) to (D) manufactured by Shikoku Chemical Industries; 2MZ-AZINE (structural formula (B)), 2E4MZ-AZINE (structural formula (C)), CllZ -AZINE (structural formula (D)) and the like. These compounds increase the adhesion to the copper circuit, improve the PCT resistance, and have an effect on electrolytic corrosion. These can be used alone or in combination of two or more.
  • the content of the adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.1 to 40 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Part is preferable, and 0.1 to 20 parts by mass is more preferable.
  • the thermal polymerization inhibitor is preferably added to prevent thermal polymerization or temporal polymerization of the polymerizable compound and improve storage stability.
  • the thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples thereof include 4-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, ⁇ -naphthol, 2,6-di-t-butyl-4-cresol, 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, phenothiazine, nitroso compound, nitroso compound Such as chelates with Al and the like.
  • the content of the thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound. 0.005 to 2 parts by mass is more preferable, and 0.01 to 1 part by mass is particularly preferable. When the content is less than 0.001 part by mass, stability during storage may be reduced, and when it exceeds 5 parts by mass, sensitivity to active energy rays may be reduced.
  • coloring agent there is no restriction
  • coloring pigment there is no restriction
  • Pigment Black 1 carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more.
  • the content of the color pigment can be determined in consideration of the exposure sensitivity and resolution of the photosensitive layer at the time of forming a permanent pattern, and varies depending on the type of the color pigment. 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the solid content of the composition.
  • the other additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thixotropic agents such as benton, montmorillonite, aerosol, amide wax, silicone-based, fluorine-based, and polymer-based. Additives such as antifoaming agents and leveling agents can be used.
  • the photosensitive film of the present invention has at least a support and a photosensitive layer comprising the photosensitive composition of the present invention on the support, and further has other layers as necessary.
  • the support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.
  • the support is preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro
  • plastic films such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
  • the thickness of the support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 2 ⁇ m to 150 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m, and particularly preferably 8 ⁇ m to 50 ⁇ m.
  • the shape of the support is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably long.
  • the length of the long support is not particularly limited, and examples thereof include those having a length of 10 m to 20,000 m.
  • the said photosensitive layer is a layer which consists of the said photosensitive composition, there will be no restriction
  • the number of laminated photosensitive layers is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be one layer or two or more layers.
  • Examples of the method for forming the photosensitive layer include a method in which the photosensitive composition of the present invention is directly applied on the support and laminated by drying.
  • the application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc.
  • coating is mentioned.
  • the drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually 60 ° C. to 110 ° C. for about 30 seconds to 15 minutes.
  • the thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 1 ⁇ m to 100 ⁇ m, more preferably 2 ⁇ m to 50 ⁇ m, and particularly preferably 4 ⁇ m to 30 ⁇ m.
  • the other layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a protective film a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorption layer, a surface protective layer, etc.
  • the said photosensitive film may have these layers individually by 1 type, and may have 2 or more types.
  • the photosensitive film may have a protective film on the photosensitive layer.
  • the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
  • the thickness of the protective film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 ⁇ m to 100 ⁇ m, more preferably 8 ⁇ m to 50 ⁇ m, and particularly preferably 10 ⁇ m to 30 ⁇ m.
  • Examples of the combination of the support and the protective film include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. It is done.
  • interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer.
  • coating of a primer layer corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment
  • examples thereof include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.
  • the photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape.
  • the length of the long photosensitive film is not particularly limited, and can be appropriately selected from a range of, for example, 10 m to 20,000 m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form.
  • a separator especially moisture-proof and desiccant-containing
  • a separator especially moisture-proof and desiccant-containing
  • the protective film may be surface-treated 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 polyvinyl alcohol is formed on the surface of the protective film.
  • the undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 ° C. to 150 ° C. for 1 to 30 minutes.
  • the drying temperature is particularly preferably 50 ° C to 120 ° C.
  • the photosensitive laminate has at least a substrate and a photosensitive layer provided on the substrate, and is formed by laminating other layers appropriately selected according to the purpose.
  • the photosensitive layer is transferred from the photosensitive film produced by the manufacturing method described above, and has the same configuration as described above.
  • the substrate is a substrate to be processed on which a photosensitive layer is formed, or a member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited and is appropriately selected depending on the purpose. For example, it can be arbitrarily selected from those having a high surface smoothness to those having a rough surface.
  • a plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.
  • Examples of the method for producing the photosensitive laminate include a method in which at least the photosensitive layer in the photosensitive film of the present invention is transferred and laminated while performing at least one of heating and pressurization.
  • the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing.
  • the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate
  • the heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 15 to 180 ° C. is preferable, and 60 to 140 ° C. is more preferable.
  • the pressurizing pressure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the pressure is preferably 0.1 MPa to 1.0 MPa, more preferably 0.2 MPa to 0.8 MPa.
  • An apparatus for performing at least one of the heating is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a laminator for example, VP-II manufactured by Taisei Laminator Co., Ltd., VP130 manufactured by Nichigo Morton Co., Ltd.
  • Etc. are preferable.
  • the photosensitive film of the present invention and the photosensitive laminate can suppress the unnecessary film from remaining on the substrate after development, a high-definition permanent pattern (protective film, interlayer insulating film, and solder resist) Pattern etc.) can be formed efficiently. Therefore, it can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be suitably used particularly for forming a permanent pattern on a printed circuit board.
  • the permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps such as a development step appropriately selected as necessary.
  • the said exposure process is a process of exposing with respect to the photosensitive layer formed with the photosensitive composition of this invention.
  • the photosensitive composition of the present invention is as described above.
  • the object of exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose.
  • the photosensitive film of the present invention is heated on a substrate and heated. It is preferably performed on a laminate formed by laminating while performing at least one of pressurization.
  • the exposure is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include digital exposure and analog exposure. Of these, digital exposure is preferable.
  • the developer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • alkaline aqueous solutions examples thereof include alkaline aqueous solutions, aqueous developers and organic solvents, and among these, weakly alkaline aqueous solutions are preferred.
  • the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus
  • Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.
  • the pH of the weak alkaline aqueous solution is preferably about 8 to 12, for example, and more preferably about 9 to 11.
  • Examples of the weak alkaline aqueous solution include a 0.1% by mass to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
  • the temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.
  • the developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.).
  • the developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.
  • the curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
  • limiting in particular as said hardening process Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.
  • 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 development.
  • the entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
  • 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 development.
  • the entire surface heating increases the film strength of the surface of the permanent pattern.
  • the heating temperature in the entire surface heating is preferably 120 ° C. to 250 ° C., more preferably 120 ° C. to 200 ° C. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the resin in the photosensitive composition is decomposed to prevent the film quality from being weak and brittle.
  • the heating time in the entire surface heating is preferably 10 minutes to 120 minutes, more preferably 15 minutes to 60 minutes.
  • an apparatus which performs the said whole surface heating According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.
  • the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern
  • the permanent pattern is formed on the printed wiring board by the permanent pattern forming method.
  • soldering can be performed as follows. That is, by the development, a hardened layer that is the permanent pattern is formed, 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, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.
  • the printed circuit board of the present invention has at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further has other configurations appropriately selected as necessary.
  • Table 1 shows the weight average molecular weight, number average molecular weight, and number of lactone repeating units of the obtained polyester (i-1) measured by GPC method. The reaction scheme is shown below.
  • polyester (i-2) was obtained in the same manner as in Synthesis Example 1, except that the type and amount of carboxylic acid in Example 1 were changed to the type and amount of carboxylic acid shown in Table 1.
  • Table 1 shows the weight average molecular weight, number average molecular weight, and number of lactone repeating units of the obtained polyester (i-2) measured by GPC method.
  • 3.8 g propylene glycol 1-monomethyl ether 2-acetate
  • succinic anhydride corresponding to a precursor of a group partially having a functional group having a pKa of 14 or less
  • PGMEA propylene glycol 1-monomethyl ether 2-acetate
  • the nitrogen atom-containing resin (J-1) comprises a main chain having a nitrogen atom derived from polyethyleneimine, a graft chain having a number average molecular weight of 500 to 1,000,000 derived from polyester (i-1), an anhydrous succinate It has a group having a functional group (carboxy group) whose pKa derived from an acid is 14 or less.
  • a synthesis scheme is shown below.
  • the obtained nitrogen atom-containing resin contains 10 mol% of repeating units in which X is —COCH 2 CH 2 CO 2 H in the repeating unit represented by the general formula (I-1). It can be seen that the repeating unit represented by I-2) is a nitrogen atom-containing resin containing 50 mol% of Y being poly ( ⁇ -caprolactone). Moreover, the weight average molecular weight by GPC method was 24,000. Table 2 shows the acid value of the intermediate, the amine value, and the acid value, amine value, and weight average molecular weight of the nitrogen atom-containing resin.
  • SP-006 is a polyethyleneimine (number average molecular weight 600) manufactured by Nippon Shokubai Co., Ltd.
  • PAA-01A is a polyallylamine (number average molecular weight 800) dehydrated product manufactured by Nippon Shokubai Co., Ltd.
  • the acid-modified vinyl group-containing polyurethane resin U1 obtained above has a solid content acid value of 70 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) is 8,000.
  • the vinyl group equivalent was 1.5 mmol / g.
  • the acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
  • the weight average molecular weight was measured using a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.).
  • a 0.5 mass% THF solution was used as a sample solution, 62 columns of TSKgelGMH were used, 200 ⁇ L of a sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C.
  • the weight average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
  • the said vinyl group equivalent was calculated
  • reaction solution was cooled to 60 ° C., charged with 13.8 parts by mass of triphenylphosphine, heated to 100 ° C., reacted for about 32 hours, and reacted with an acid value of 0.5 mg KOH / g (hydroxyl group, 12 Equivalent).
  • 364.7 parts by mass (2.4 mol) of tetrahydrophthalic anhydride, 137.5 parts by mass of carbitol acetate, and 58.8 parts by mass of solvent naphtha were added to this and heated to 95 ° C. for about 6 hours.
  • the reaction and cooling were performed to obtain a carboxyl group-containing photosensitive polyurethane resin U2 having a solid content concentration of 40% by mass.
  • the obtained carboxyl group-containing photosensitive polyurethane resin U1 had an acid value of 70 mgKOH / g, a weight average molecular weight of 12,000, and a vinyl group equivalent of 1.5 mmol / g.
  • Example 1 Provide of photosensitive laminate> -Preparation of photosensitive composition- A photosensitive composition having the following composition was prepared. In addition, content of the filler in the obtained photosensitive composition was 30 mass parts with respect to 100 mass parts of solid content of the photosensitive composition.
  • composition of photosensitive composition 32.3 parts by mass (solid content: 45% by mass) of the acid-modified vinyl group-containing polyurethane resin U1 solution obtained in Synthesis Example 6
  • the pigment dispersion is prepared as follows. That is, the following components were mixed in advance, and then dispersed with a motor mill M-250 (manufactured by Eiger) using zirconia beads having a diameter of 1.0 mm at a peripheral speed of 9 m / s for 3 hours.
  • the photosensitive composition was applied onto a polyethylene terephthalate film having a thickness of 16 ⁇ m as a support (manufactured by Toray Industries, Inc., 16FB50) and dried to form a photosensitive layer having a thickness of 30 ⁇ m on the support.
  • a 20 ⁇ m-thick polypropylene film manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200
  • a protective layer was laminated to produce a photosensitive film.
  • a substrate was prepared by subjecting the surface of a copper-clad laminate (no through holes, copper thickness 12 ⁇ m) to chemical polishing treatment.
  • a vacuum laminator manufactured by Nichigo Morton Co., Ltd., VP130
  • a photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
  • the pressure bonding conditions were such that the vacuuming time was 40 seconds, the pressure bonding temperature was 70 ° C., the pressure bonding pressure was 0.2 MPa, and the pressure application time was 10 seconds.
  • the photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.).
  • a round hole pattern is exposed on the polyethylene terephthalate film (support) of the resulting photosensitive laminate so that a round hole with a diameter of 50 ⁇ m to 200 ⁇ m can be formed. Went.
  • the exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the photosensitive film in the sensitivity evaluation.
  • the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
  • the entire surface of the photosensitive layer on the copper clad laminate was sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as a developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve and remove uncured areas. .
  • the surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, there is no residue at the bottom of the round hole of the pattern, there are no abnormalities such as blistering / peeling of the pattern, and space
  • the minimum round hole pattern width that can be formed was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution. The results are shown in Table 3 below.
  • a round hole having a diameter of 90 ⁇ m or less can be resolved, and the resolution is excellent.
  • ⁇ A round hole having a diameter exceeding 120 ⁇ m and not more than 200 ⁇ m can be resolved, and the resolution is slightly inferior.
  • X A round hole cannot be resolved and the resolution is inferior.
  • ⁇ Development residue >> The development residue was evaluated by the state of the residue of the 300 ⁇ m round hole pattern in the resolution evaluation. The results are shown in Table 3 below.
  • X Residues are observed in the round hole pattern, and the development residue removability is poor.
  • a solder resist layer is formed on a printed circuit board obtained by laminating a copper foil having a thickness of 12 ⁇ m on a glass epoxy base material on the photosensitive laminate, and a HMW-201GX type exposure made by Oak Seisakusho through a 2 mm square photomask. The exposure was performed with an optimum exposure dose (300 mJ / cm 2 to 1 J / cm 2 ) that can form a 2 mm square pattern. Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes.
  • the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm 2 using an ultraviolet irradiation device manufactured by Oak Seisakusho. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist having a 2 mm square opening was formed. The obtained substrate was exposed to an atmosphere of ⁇ 65 ° C. for 15 minutes, then exposed to an atmosphere of 150 ° C. for 15 minutes, and then exposed to the air of ⁇ 65 ° C. again for 1,000 times. The crack and peeling degree on the solder resist of the evaluation substrate through the thermal cycle were observed with an optical microscope. The results are shown in Table 3 below.
  • the copper foil of the printed circuit board obtained by laminating a copper foil having a thickness of 12 ⁇ m on a glass epoxy substrate is etched, the line width / space width is 50 ⁇ m / 50 ⁇ m, the lines are not in contact with each other, and the same facing each other
  • a comb electrode on the surface was obtained.
  • the photosensitive laminate was formed on the comb-shaped electrode of this substrate, a solder resist layer was formed by a conventional method, and exposure was performed with an optimum exposure amount (300 mJ / cm 2 to 1 J / cm 2 ).
  • Example 2 In Example 1, the photosensitive laminate was prepared in the same manner as in Example 1 except that the amount of silica was changed from 30 parts by mass to 40 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Prepared and evaluated. The results are shown in Table 3.
  • Example 3 the photosensitive laminate was prepared in the same manner as in Example 1 except that the amount of silica was changed from 30 parts by mass to 15 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Prepared and evaluated. The results are shown in Table 3.
  • Example 4 A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that the nitrogen atom-containing resin (J-1) was replaced with the nitrogen atom-containing resin (J-2) in Example 1. The results are shown in Table 3.
  • Example 5 A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that the nitrogen atom-containing resin (J-1) was replaced with the nitrogen atom-containing resin (J-3) in Example 1. The results are shown in Table 3.
  • Example 6 A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that the acid-modified vinyl group-containing polyurethane resin U1 was replaced with the carboxyl group-containing photosensitive polyurethane resin U2 in Example 1. The results are shown in Table 3.
  • Example 7 A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that silica was replaced with silica (manufactured by Admatech, SO-C3, average particle size: 0.9 ⁇ m) in Example 1. The results are shown in Table 3.
  • Example 8 A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that silica was changed to silica (manufactured by Admatech, SO-C1, average particle diameter of 0.25 ⁇ m) in Example 1. The results are shown in Table 3.
  • Example 9 A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that silica was replaced with alumina (manufactured by Shin-Etsu Quartz, AO-802, average particle size 0.7 ⁇ m) in Example 1. The results are shown in Table 3.
  • Example 1 A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that the nitrogen atom-containing resin (J-1) was replaced with the acid-modified vinyl group-containing polyurethane resin U1 in Example 1. The results are shown in Table 3.
  • Example 2 In Example 1, the nitrogen atom-containing resin (J-1) was replaced with Solsperse 24000 (manufactured by Lubrizol, a basic dispersant (different from the nitrogen atom-containing resin in the photosensitive composition of the present invention)). Except for the above, a photosensitive laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 3 a photosensitive laminate was prepared in the same manner as in Example 1 except that the nitrogen atom-containing resin (J-1) was replaced with Solsperse 26000 (Lubrisol, acid group-containing resin). evaluated. The results are shown in Table 3. Solsperse 26000 is different from the nitrogen atom-containing resin in the photosensitive composition of the present invention, and is widely used as a dispersant for the photosensitive composition for color filters.
  • the photosensitive composition of the present invention has high viscosity even when the filler content is high, has high resolution, no development residue, and is excellent in heat resistance, toughness, and insulation. It can be suitably used as a solder resist.

Abstract

A photosensitive composition comprises a nitrogen atom-containing resin, a resin other than the nitrogen atom-containing resin, a thermal crosslinking agent, and filler. The nitrogen atom-containing resin has a principal chain containing a nitrogen atom, a group including as one part a functional group bonded to the nitrogen atom present in the principal chain and having a pKa of 14 or less, and a graft chain bonded to the nitrogen atom-containing principal chain and having a number average molecular weight of 500-1,000,000.

Description

感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board
　本発明は、感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板に関する。 The present invention relates to a photosensitive composition, a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board.
　従来より、ソルダーレジストなどの永久パターンを形成する際には、支持体上に感光性組成物を塗布、乾燥することにより感光層を形成させた感光性フィルムが用いられている。前記永久パターンの製造方法としては、例えば、前記永久パターンが形成される銅張積層板等の基体上に、前記感光性フィルムを積層させて積層体を形成し、該積層体における前記感光層に対して露光を行い、該露光後、前記感光層を現像してパターンを形成させ、その後硬化処理等を行うことにより前記永久パターンを形成する方法が挙げられる。 Conventionally, when a permanent pattern such as a solder resist is formed, a photosensitive film in which a photosensitive layer is formed by applying and drying a photosensitive composition on a support has been used. As the method for producing the permanent pattern, for example, a laminate is formed by laminating the photosensitive film on a substrate such as a copper-clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed on the photosensitive layer. Examples include a method of forming the permanent pattern by performing exposure on the surface, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like.
　前記感光性組成物から形成される前記永久パターンは、ＩＲリフローなど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の保護膜として機能するために、耐熱性が要求されている。また、基体上の電気配線同士の電気的絶縁を保つための絶縁膜として機能するために、絶縁性が要求されている。また、様々な環境において使用されるプリント基板に適用できるよう強靭性が要求されている。
　絶縁性、強靭性及び耐熱性の向上の一般的な手段としては、感光性組成物にフィラーを配合させることが有効であることが知られている。 Since the permanent pattern formed from the photosensitive composition functions as a protective film for preventing solder from adhering to an unnecessary part of soldering in a soldering process such as IR reflow, Sex is required. Moreover, in order to function as an insulating film for maintaining electrical insulation between the electrical wirings on the substrate, insulation is required. Further, toughness is required to be applicable to printed circuit boards used in various environments.
As a general means for improving insulation, toughness and heat resistance, it is known that it is effective to add a filler to the photosensitive composition.
　近年、プリント基板においては、高密度化、小型化、軽量化などの高機能化に伴い、配線パターンの微細化が要求されている。
　そこで、前記感光性組成物に対しては、前記感光性組成物により形成される永久パターンの微細化、すなわち高解像性及び低現像残渣が求められている。また、微細な配線パターンへの追随性が必要であるために、低粘度化が要求されている。 In recent years, printed circuit boards have been required to have finer wiring patterns with higher functions such as higher density, smaller size, and lighter weight.
Therefore, miniaturization of the permanent pattern formed by the photosensitive composition, that is, high resolution and low development residue is required for the photosensitive composition. Further, since it is necessary to follow a fine wiring pattern, a reduction in viscosity is required.
　また、配線パターンの微細化により絶縁性の要求レベルも高くなっている。くわえて、環境への配慮による鉛フリー半田の使用により、ソルダリング工程における半田温度が上昇しており、耐熱性の要求レベルも高くなっている。
　しかし、フィラーの配合量の増加させて絶縁性、強靭性及び耐熱性を向上させようとすると、感光性組成物が高粘度化するという問題がある。 In addition, the required level of insulation has increased due to the miniaturization of wiring patterns. In addition, the use of lead-free solder due to environmental considerations has increased the solder temperature in the soldering process, and the required level of heat resistance has also increased.
However, if the blending amount of the filler is increased to improve insulation, toughness, and heat resistance, there is a problem that the photosensitive composition becomes highly viscous.
　そこで、絶縁性樹脂組成物において、フィラーの配合量を多くすることによる高粘度化を防ぐために、塩基性の高分子分散剤を用いる技術が提案されている（特許文献１）。この提案の技術においては、具体的には、ソルスパース２４０００（アビシア化学社製）という塩基性の高分子分散剤が用いられている。
　しかし、この提案の技術においては、高粘度化を防ぐことはできるものの、感光性組成物にこの技術を適用した場合、解像性の低下、現像残渣の発生が生じるという問題がある。 Therefore, in the insulating resin composition, a technique using a basic polymer dispersant has been proposed in order to prevent the viscosity from increasing due to an increase in the amount of filler added (Patent Document 1). In the proposed technique, specifically, a basic polymer dispersant called Solsperse 24000 (manufactured by Avicia Chemical Co., Ltd.) is used.
However, although the proposed technique can prevent the increase in viscosity, there are problems in that when this technique is applied to a photosensitive composition, the resolution is lowered and development residues are generated.
　カラーフィルタに用いる着色硬化性組成物において、着色顔料の分散に特定の官能基及び特定の側鎖を有する樹脂を用いる技術が提案されている（特許文献２）。この提案の技術では、平均粒子径が０．００５μｍ～０．１μｍという微細な顔料を用いた際の分散性、保存安定性を改良するために前記樹脂が有効であることが示されている。
　しかし、この提案において、平均粒子径が０．１μｍよりも大きなフィラーを用いた場合や、フィラーの配合量が多い場合の分散性については検討されておらず、また、感光性組成物に適用した場合の耐熱性、強靭性、絶縁性についても何ら検討されていない。 In a colored curable composition used for a color filter, a technique of using a resin having a specific functional group and a specific side chain for dispersing a colored pigment has been proposed (Patent Document 2). This proposed technique shows that the resin is effective for improving dispersibility and storage stability when a fine pigment having an average particle size of 0.005 μm to 0.1 μm is used.
However, in this proposal, the case where a filler having an average particle size larger than 0.1 μm is used or the dispersibility in the case where the amount of the filler is large is not examined, and it is applied to the photosensitive composition. No consideration has been given to heat resistance, toughness, and insulation.
　したがって、フィラーの含有量が多い場合においても粘度が高くならず、かつ解像性が高く、現像残渣がなく、さらに、耐熱性、強靭性、絶縁性に優れる感光性組成物、並びに該感光性組成物を用いた感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板の提供が求められているのが現状である。 Therefore, even when the filler content is large, the viscosity is not high, the resolution is high, there is no development residue, and the photosensitive composition is excellent in heat resistance, toughness, and insulation, and the photosensitivity. At present, provision of a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed board using the composition is required.
特開２００１－９６６８８号公報JP 2001-96688 A 特開２００１－１６０３１８号公報JP 2001-160318 A
　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、フィラーの含有量が多い場合においても粘度が高くならず、かつ解像性が高く、現像残渣がなく、さらに、耐熱性、強靭性、絶縁性に優れる感光性組成物、並びに該感光性組成物を用いた感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板を提供することを目的とする。 This invention makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention is a photosensitive composition that does not have high viscosity even when the filler content is high, has high resolution, no development residue, and is excellent in heat resistance, toughness, and insulation, It is another object of the present invention to provide a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board using the photosensitive composition.
　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、
　＜１＞　窒素原子含有樹脂、該窒素原子含有樹脂以外の樹脂、熱架橋剤、及びフィラーを含有し、
　前記窒素原子含有樹脂が、窒素原子を有する主鎖と、前記主鎖に存在する窒素原子と結合し、かつｐＫａが１４以下である官能基を一部に有する基と、前記主鎖と結合し、かつ数平均分子量が５００～１，０００，０００のグラフト鎖とを有することを特徴とする感光性組成物である。
　＜２＞　フィラーが、シリカである前記＜１＞に記載の感光性組成物である。
　＜３＞　フィラーの含有量が、感光性組成物の固形分１００質量部に対して、１０質量部～９７質量部である前記＜１＞から＜２＞のいずれかに記載の感光性組成物である。
　＜４＞　窒素原子を有する主鎖が、アミノ基を有する重合体から構成される主鎖である前記＜１＞から＜３＞のいずれかに記載の感光性組成物である。
　＜５＞　アミノ基を有する重合体から構成される主鎖が、ポリ（アルキレンイミン）、ポリアリルアミン、ポリジアリルアミン、メタキシレンジアミン－エピクロルヒドリン重縮合物、及びポリビニルアミンから選択される１種以上で構成される主鎖である前記＜４＞に記載の感光性組成物である。
　＜６＞　ｐＫａが１４以下である官能基を一部に有する基が、下記一般式（Ｖ－１）から（Ｖ－３）で表される基のいずれかである前記＜１＞から＜５＞のいずれかに記載の感光性組成物である。
Figure JPOXMLDOC01-appb-C000006
 　ただし、前記一般式（Ｖ－１）、及び前記一般式（Ｖ－２）中、Ｕは単結合及び二価の連結基のいずれかを表す。ｄ及びｅは、それぞれ独立に、０及び１のいずれかを表す。
　前記一般式（Ｖ－３）中、Ｗは、アシル基及びアルコキシカルボニル基のいずれかを表す。
　＜７＞　窒素原子含有樹脂が、下記一般式（Ｉ－１）で表される繰返し単位、及び下記一般式（Ｉ－２）で表される繰返し単位を有する前記＜１＞から＜６＞のいずれかに記載の感光性組成物である。
Figure JPOXMLDOC01-appb-C000007
 　ただし、前記一般式（Ｉ－１）及び（Ｉ－２）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子、ハロゲン原子、及びアルキル基のいずれかを表す。ａは、それぞれ独立に、１～５の整数のいずれかを表す。「＊」は、繰返し単位間の連結部を表す。Ｘは、ｐＫａが１４以下である官能基を一部に有する基を表す。Ｙは、数平均分子量が５００～１，０００，０００のグラフト鎖を表す。
　＜８＞　窒素原子含有樹脂が、下記一般式（ＩＩ－１）で表される繰返し単位、及び下記一般式（ＩＩ－２）で表される繰返し単位を有する前記＜１＞から＜６＞のいずれかに記載の感光性組成物である。
Figure JPOXMLDOC01-appb-C000008
 　ただし、前記一般式（ＩＩ－１）及び（ＩＩ－２）中、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子、及びアルキル基のいずれかを表す。「＊」は、繰返し単位間の連結部を表す。Ｘは、ｐＫａが１４以下である官能基を一部に有する基を表す。Ｙは、数平均分子量が５００～１，０００，０００のグラフト鎖を表す。
　＜９＞　数平均分子量が５００～１，０００，０００のグラフト鎖が、下記一般式（ＩＩＩ－１）で表されるグラフト鎖である前記＜１＞から＜８＞のいずれかに記載の感光性組成物である。
Figure JPOXMLDOC01-appb-C000009
 　ただし、前記一般式（ＩＩＩ－１）中、Ｚは、ポリエステル鎖を部分構造として少なくとも有する重合体残基であって、下記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルからカルボキシル基を除いた重合体残基を表す。
Figure JPOXMLDOC01-appb-C000010
 　ただし、前記一般式（ＩＶ）中、Ｚは、前記一般式（ＩＩＩ－１）中のＺと同じである。
　＜１０＞　窒素原子含有樹脂が、一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂と、ｐＫａが１４以下である官能基を一部に有する基の前駆体と、数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体とを反応させて得られる樹脂である前記＜１＞から＜９＞のいずれかに記載の感光性組成物である。
　＜１１＞　さらに、重合性化合物と、光重合開始剤とを含有する前記＜１＞から＜１０＞のいずれかに記載の感光性組成物である。
　＜１２＞　前記＜１＞から＜１１＞のいずれかに記載の感光性組成物からなる感光層を支持体上に有することを特徴とする感光性フィルムである。
　＜１３＞　基体上に、前記＜１＞から＜１１＞のいずれかに記載の感光性組成物を含む感光層を有することを特徴とする感光性積層体である。
　＜１４＞　前記＜１＞から＜１１＞のいずれかに記載の感光性組成物により形成された感光層に対して露光を行うことを少なくとも含むことを特徴とする永久パターン形成方法である。
　＜１５＞　前記＜１４＞に記載の永久パターン形成方法によって形成された永久パターンを備えることを特徴とするプリント基板である。 Means for solving the problems are as follows. That is,
<1> containing a nitrogen atom-containing resin, a resin other than the nitrogen atom-containing resin, a thermal crosslinking agent, and a filler,
The nitrogen atom-containing resin is bonded to the main chain having a nitrogen atom, a group having a functional group having a pKa of 14 or less, bonded to the main chain having a nitrogen atom, and the main chain. And a photosensitive composition having a graft chain having a number average molecular weight of 500 to 1,000,000.
<2> The photosensitive composition according to <1>, wherein the filler is silica.
<3> The photosensitive composition according to any one of <1> to <2>, wherein the filler content is 10 parts by mass to 97 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. It is.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the main chain having a nitrogen atom is a main chain composed of a polymer having an amino group.
<5> The main chain composed of a polymer having an amino group is composed of one or more selected from poly (alkyleneimine), polyallylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, and polyvinylamine. It is the photosensitive composition as described in said <4> which is a main chain.
<6> The above-mentioned <1> to <5, wherein the group partially having a functional group having a pKa of 14 or less is any of the groups represented by the following general formulas (V-1) to (V-3): > The photosensitive composition according to any one of the above.
Figure JPOXMLDOC01-appb-C000006
 However, in the general formula (V-1) and the general formula (V-2), U represents either a single bond or a divalent linking group. d and e each independently represents either 0 or 1;
In the general formula (V-3), W represents either an acyl group or an alkoxycarbonyl group.
<7> The above-mentioned <1> to <6>, wherein the nitrogen atom-containing resin has a repeating unit represented by the following general formula (I-1) and a repeating unit represented by the following general formula (I-2): It is the photosensitive composition in any one.
Figure JPOXMLDOC01-appb-C000007
 However, in the general formulas (I-1) and (I-2), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group. a represents each independently an integer of 1 to 5. “*” Represents a connecting portion between repeating units. X represents a group partially having a functional group having a pKa of 14 or less. Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
<8> The above-mentioned <1> to <6>, wherein the nitrogen atom-containing resin has a repeating unit represented by the following general formula (II-1) and a repeating unit represented by the following general formula (II-2) It is the photosensitive composition in any one.
Figure JPOXMLDOC01-appb-C000008
 However, in the general formulas (II-1) and (II-2), R 3 , R 4 , R 5 and R 6 each independently represent any of a hydrogen atom, a halogen atom and an alkyl group. “*” Represents a connecting portion between repeating units. X represents a group partially having a functional group having a pKa of 14 or less. Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
<9> The photosensitive film according to any one of <1> to <8>, wherein the graft chain having a number average molecular weight of 500 to 1,000,000 is a graft chain represented by the following general formula (III-1): Composition.
Figure JPOXMLDOC01-appb-C000009
 However, in the general formula (III-1), Z is a polymer residue having at least a polyester chain as a partial structure, and from a polyester having a free carboxylic acid represented by the following general formula (IV) to a carboxyl It represents a polymer residue excluding a group.
Figure JPOXMLDOC01-appb-C000010
 However, in the general formula (IV), Z is the same as Z in the general formula (III-1).
<10> A resin having a nitrogen atom-containing resin having at least one of a primary amino group and a secondary amino group, a precursor of a group partially having a functional group having a pKa of 14 or less, and a number average molecular weight of 500 The photosensitive composition according to any one of <1> to <9>, wherein the photosensitive composition is a resin obtained by reacting with a precursor of ˜1,000,000 graft chain.
<11> The photosensitive composition according to any one of <1> to <10>, further including a polymerizable compound and a photopolymerization initiator.
<12> A photosensitive film having a photosensitive layer made of the photosensitive composition according to any one of <1> to <11> on a support.
<13> A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <11> on a substrate.
<14> A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <11>.
<15> A printed circuit board comprising a permanent pattern formed by the method for forming a permanent pattern according to <14>.
　本発明によると、従来における前記諸問題を解決することができ、フィラーの含有量が多い場合においても粘度が高くならず、かつ解像性が高く、現像残渣がなく、さらに、耐熱性、強靭性、絶縁性に優れる感光性組成物、並びに該感光性組成物を用いた感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板を提供することができる。 According to the present invention, the conventional problems can be solved, and even when the filler content is high, the viscosity is not high, the resolution is high, there is no development residue, and the heat resistance, toughness is further improved. And a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed circuit board using the photosensitive composition can be provided.
（感光性組成物）
　本発明の感光性組成物は、窒素原子含有樹脂と、該窒素原子含有樹脂以外の樹脂と、熱架橋剤と、フィラーとを少なくとも含有し、重合性化合物、光重合開始剤、さらに必要に応じて、その他の成分を含有する。 (Photosensitive composition)
The photosensitive composition of the present invention contains at least a nitrogen atom-containing resin, a resin other than the nitrogen atom-containing resin, a thermal crosslinking agent, and a filler, a polymerizable compound, a photopolymerization initiator, and further if necessary. And other ingredients.
＜窒素原子含有樹脂＞
　前記窒素原子含有樹脂は、窒素原子を有する主鎖と、ｐＫａが１４以下である官能基を一部に有する基と、数平均分子量が５００～１，０００，０００のグラフト鎖とを少なくとも有し、更に必要に応じて、その他の構成を有する。 <Nitrogen-containing resin>
The nitrogen atom-containing resin has at least a main chain having a nitrogen atom, a group partially having a functional group having a pKa of 14 or less, and a graft chain having a number average molecular weight of 500 to 1,000,000. Furthermore, it has other configurations as required.
－窒素原子を有する主鎖－
　前記窒素原子含有樹脂は、前記窒素原子を有する主鎖を有する。前記窒素原子含有樹脂が、前記窒素原子を有する主鎖を有することにより、前記窒素原子含有樹脂のフィラーへの吸着性が向上し、前記感光性組成物におけるフィラー間の相互作用が低減できる。これにより、前記感光性組成物においてフィラーの含有量が多い場合においても、粘度が高くなるのを抑えることができる。 -Main chain with nitrogen atoms-
The nitrogen atom-containing resin has a main chain having the nitrogen atom. When the nitrogen atom-containing resin has a main chain having the nitrogen atom, the adsorptivity of the nitrogen atom-containing resin to the filler is improved, and the interaction between the fillers in the photosensitive composition can be reduced. Thereby, even when there is much content of a filler in the said photosensitive composition, it can suppress that a viscosity becomes high.
　前記窒素原子を有する主鎖としては、窒素原子を有するものであれば、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、アミノ基を有する重合体から構成される主鎖であることが好ましい。
　前記アミノ基を有する重合体から構成される主鎖としては、ポリ（アルキレンイミン）、ポリアリルアミン、ポリジアリルアミン、メタキシレンジアミン－エピクロルヒドリン重縮合物、及びポリビニルアミンから選択される１種以上で構成される主鎖であることが好ましく、ポリ（アルキレンイミン）で構成される主鎖、ポリアリルアミンで構成される主鎖であることがより好ましい。前記より好ましい態様であると、フィラーの分散性能が向上し、感光性組成物において粘度が高くなるのを抑えることができる点で有利である。
　前記ポリ（アルキレンイミン）のアルキレンとしては、例えば、炭素数１～５のアルキレンが挙げられる。
　前記ポリアリルアミンのアリルは、置換基を有していてもよい。前記置換基としては、例えば、ハロゲン原子、アルキル基などが挙げられる。
　前記ポリ（アルキレンイミン）は、鎖状であってもよく網目状であってもよい。網目状であることが、分散安定性及び素材供給性の点で好ましい。 The main chain having a nitrogen atom is not particularly limited as long as it has a nitrogen atom, and can be appropriately selected according to the purpose, but is a main chain composed of a polymer having an amino group. It is preferable.
The main chain composed of the polymer having an amino group is composed of at least one selected from poly (alkyleneimine), polyallylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, and polyvinylamine. The main chain is preferably a main chain composed of poly (alkyleneimine) and a main chain composed of polyallylamine. The more preferable embodiment is advantageous in that the dispersibility of the filler is improved and the viscosity of the photosensitive composition can be suppressed from increasing.
Examples of the alkylene of the poly (alkyleneimine) include alkylene having 1 to 5 carbon atoms.
Allyl of the polyallylamine may have a substituent. Examples of the substituent include a halogen atom and an alkyl group.
The poly (alkyleneimine) may be a chain or a network. A network shape is preferable in terms of dispersion stability and material supply.
　前記窒素原子を有する主鎖がポリ（アルキレンイミン）で構成される主鎖である場合の前記窒素原子含有樹脂としては、下記一般式（Ｉ－１）で表される繰返し単位、及び下記一般式（Ｉ－２）で表される繰返し単位を有する構造が好ましい。 The nitrogen atom-containing resin in the case where the main chain having a nitrogen atom is a main chain composed of poly (alkyleneimine) includes a repeating unit represented by the following general formula (I-1), and the following general formula A structure having a repeating unit represented by (I-2) is preferred.
－－下記一般式（Ｉ－１）で表される繰り返し単位、及び下記一般式（Ｉ－２）で表される繰り返し単位を有する構造－－
Figure JPOXMLDOC01-appb-C000011
 　ただし、前記一般式（Ｉ－１）及び（Ｉ－２）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子、ハロゲン原子、及びアルキル基のいずれかを表す。ａは、それぞれ独立に、１～５の整数のいずれかを表す。「＊」は、繰返し単位間の連結部を表す。Ｘは、ｐＫａが１４以下である官能基を一部に有する基を表す。Ｙは、数平均分子量が５００～１，０００，０００のグラフト鎖を表す。 --A structure having a repeating unit represented by the following general formula (I-1) and a repeating unit represented by the following general formula (I-2)-
Figure JPOXMLDOC01-appb-C000011
 However, in the general formulas (I-1) and (I-2), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group. a represents each independently an integer of 1 to 5. “*” Represents a connecting portion between repeating units. X represents a group partially having a functional group having a pKa of 14 or less. Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
　なお、前記一般式（Ｉ－１）において、前記一般式（Ｉ－１）からＸを除いた部分が前記窒素原子を有する主鎖に該当する。
　前記一般式（Ｉ－２）において、前記一般式（Ｉ－２）からＹを除いた部分が前記窒素原子を有する主鎖に該当する。 In the general formula (I-1), a portion excluding X from the general formula (I-1) corresponds to the main chain having the nitrogen atom.
In the general formula (I-2), the portion excluding Y from the general formula (I-2) corresponds to the main chain having a nitrogen atom.
　前記一般式（Ｉ－１）及び（Ｉ－２）のＲ１及びＲ２のアルキル基としては、例えば、置換基を有していてもよい炭素数１～５のアルキル基が挙げられる。前記置換基としては、例えば、ハロゲン原子が挙げられる。
　前記一般式（Ｉ－１）及び（Ｉ－２）のＸとしては、ｐＫａが１４以下である官能基を一部に有する基であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、後述するｐＫａが１４以下である官能基を一部に有する基が挙げられる。
　前記一般式（Ｉ－１）及び（Ｉ－２）のＹとしては、数平均分子量が５００～１，０００，０００のグラフト鎖であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、後述する数平均分子量が５００～１，０００，０００のグラフト鎖が挙げられる。 Examples of the alkyl group of R 1 and R 2 in the general formulas (I-1) and (I-2) include an alkyl group having 1 to 5 carbon atoms which may have a substituent. Examples of the substituent include a halogen atom.
X in the general formulas (I-1) and (I-2) is not particularly limited as long as it is a group partially having a functional group having a pKa of 14 or less, and is appropriately selected depending on the purpose. Examples thereof include a group partially having a functional group having a pKa of 14 or less, which will be described later.
Y in the general formulas (I-1) and (I-2) is not particularly limited as long as it is a graft chain having a number average molecular weight of 500 to 1,000,000, and is appropriately selected according to the purpose. Examples thereof include a graft chain having a number average molecular weight of 500 to 1,000,000, which will be described later.
　前記窒素原子含有樹脂は、前記一般式（Ｉ－１）及び前記一般式（Ｉ－２）で表される繰返し単位に加えて、さらに下記一般式（Ｉ－３）で表される繰返し単位を共重合成分として有していてもよい。このような繰返し単位を併用することで、フィラーの分散性能が向上し、感光性組成物において粘度が高くなるのを抑えることができる。
Figure JPOXMLDOC01-appb-C000012
 　ただし、前記一般式（Ｉ－３）中、Ｒ１、Ｒ２及びａは、それぞれ、前記一般式（Ｉ－１）のＲ１、Ｒ２及びａと同じである。「＊」は、繰返し単位間の連結部を表す。Ｙ’は、アニオン基を有する数平均分子量が５００～１，０００，０００のグラフト鎖を表す。 The nitrogen atom-containing resin includes a repeating unit represented by the following general formula (I-3) in addition to the repeating unit represented by the general formula (I-1) and the general formula (I-2). You may have as a copolymerization component. By using such a repeating unit in combination, the dispersion performance of the filler can be improved, and the viscosity of the photosensitive composition can be suppressed from increasing.
Figure JPOXMLDOC01-appb-C000012
 In the general formula (I-3), R 1, R 2 and a are respectively the same as R 1, R 2 and a in the general formula (I-1). “*” Represents a connecting portion between repeating units. Y ′ represents a graft chain having an anionic group and a number average molecular weight of 500 to 1,000,000.
　なお、前記一般式（Ｉ－３）において、前記一般式（Ｉ－３）からＹ－を除いた部分が前記窒素原子を有する主鎖に該当する。 In the general formula (I-3), the portion excluding Y − from the general formula (I-3) corresponds to the main chain having the nitrogen atom.
　前記一般式（Ｉ－３）で表される繰返し単位は、一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂に、アミンと反応して塩を形成する基を有する重合体を添加して反応させることで形成することが可能である。ここで、前記アニオン基としては、ＣＯ２ －、ＳＯ３ －が好ましく、ＣＯ２ －がより好ましい。前記アニオン基は、Ｙ’が有する数平均分子量が５００～１，０００，０００のグラフト鎖の末端位にあることが好ましい。 The repeating unit represented by the general formula (I-3) is obtained by adding a polymer having a group that reacts with an amine to form a salt to a resin having at least one of a primary amino group and a secondary amino group. It can be formed by reacting. Here, as the anionic group, CO 2 - and SO 3 - are preferable, and CO 2 - is more preferable. The anionic group is preferably at the terminal position of the graft chain having a number average molecular weight of 500 to 1,000,000.
　前記一般式（Ｉ－１）、一般式（Ｉ－２）及び一般式（Ｉ－３）において、Ｒ１及びＲ２は水素原子であることが好ましい。ａは、原料入手が容易である点から２であることが好ましい。 In the general formula (I-1), general formula (I-2) and general formula (I-3), R 1 and R 2 are preferably hydrogen atoms. a is preferably 2 in view of easy availability of raw materials.
　前記窒素原子含有樹脂は、前記一般式（Ｉ－１）、一般式（Ｉ－２）及び一般式（Ｉ－３）で表される繰返し単位以外に、一級又は三級のアミノ基を含有するアルキレンイミンを繰返し単位として含んでいてもよい。なお、そのようなアルキレンイミン繰返し単位における窒素原子には、さらに、前記Ｘ、Ｙ又はＹ’で示される基が結合していてもよい。アルキレンイミン繰返し構造に、前記Ｘで示される基が結合した繰返し単位と前記Ｙが結合した繰返し単位の双方を含む樹脂もまた、前記窒素原子含有樹脂に包含される。 The nitrogen atom-containing resin contains a primary or tertiary amino group in addition to the repeating units represented by the general formula (I-1), general formula (I-2) and general formula (I-3). An alkyleneimine may be contained as a repeating unit. In addition, the group shown by said X, Y, or Y 'may couple | bond with the nitrogen atom in such an alkyleneimine repeating unit. Resins containing both a repeating unit in which the group represented by X and a repeating unit to which Y are bonded to an alkyleneimine repeating structure are also included in the nitrogen atom-containing resin.
　前記一般式（Ｉ－１）で表される繰返し単位は、ｐＫａが１４以下である官能基を一部に有する基Ｘを有する繰返し単位であり、このような繰り返し単位は、現像時の残渣及び解像性の点から、前記窒素原子含有樹脂の全繰返し単位中、１モル％～８０モル％含有することが好ましく、３％～５０モル％含有することがより好ましい。 The repeating unit represented by the general formula (I-1) is a repeating unit having a group X partially having a functional group having a pKa of 14 or less. Such a repeating unit includes a residue during development, From the viewpoint of resolution, it is preferably contained in an amount of 1 mol% to 80 mol%, more preferably 3% to 50 mol% in all repeating units of the nitrogen atom-containing resin.
　前記一般式（Ｉ－２）で表される繰返し単位は、数平均分子量が５００～１，０００，０００のグラフト鎖Ｙを有する繰返し単位であり、このような繰返し単位は、保存安定性の点から、前記窒素原子含有樹脂の全繰返し単位中、１０モル％～９０モル％含有することが好ましく、３０モル％～７０モル％含有することがより好ましい。 The repeating unit represented by the general formula (I-2) is a repeating unit having a graft chain Y having a number average molecular weight of 500 to 1,000,000. Therefore, the content is preferably 10 mol% to 90 mol%, more preferably 30 mol% to 70 mol%, in all the repeating units of the nitrogen atom-containing resin.
　前記一般式（Ｉ－１）で表される繰返し単位と前記一般式（Ｉ－２）で表される繰返し単位の前記窒素原子含有樹脂における含有比としては、分散安定性、及び親疎水性のバランスの点から、繰返し単位（Ｉ－１）：（Ｉ－２）がモル比で１０：１～１：１００の範囲であることが好ましく、１：１～１：１０の範囲であることがより好ましい。 The content ratio of the repeating unit represented by the general formula (I-1) to the repeating unit represented by the general formula (I-2) in the nitrogen atom-containing resin is a balance between dispersion stability and hydrophilicity / hydrophobicity. In view of the above, the repeating unit (I-1) :( I-2) is preferably in the range of 10: 1 to 1: 100, more preferably in the range of 1: 1 to 1:10. preferable.
　なお、所望により併用される前記一般式（Ｉ－３）で表される繰返し単位は、数平均分子量が５００～１，０００，０００のグラフト鎖が、前記窒素原子を有する主鎖の窒素原子にイオン的に結合しているものであり、前記窒素原子含有樹脂の全繰返し単位中、効果の観点からは、０．５モル％～２０モル％含有することが好ましく、１モル％～１０モル％含有することがより好ましい。
　なお、イオン的に結合していることは、赤外分光法、酸価滴定、塩基滴定などにより確認できる。 The repeating unit represented by the general formula (I-3) used in combination, if desired, has a graft chain having a number average molecular weight of 500 to 1,000,000 as a nitrogen atom of the main chain having the nitrogen atom. In terms of the effect, it is preferably contained in an amount of 0.5 mol% to 20 mol% in all repeating units of the nitrogen atom-containing resin, and 1 mol% to 10 mol%. It is more preferable to contain.
The ion binding can be confirmed by infrared spectroscopy, acid value titration, base titration and the like.
　前記窒素原子を有する主鎖がポリアリルアミンで構成される鎖部である場合の前記窒素原子含有樹脂としては、下記一般式（ＩＩ－１）で表される繰返し単位、及び下記一般式（ＩＩ－２）で表される繰返し単位を有する構造が好ましい。 Examples of the nitrogen atom-containing resin in the case where the main chain having a nitrogen atom is a chain part composed of polyallylamine include a repeating unit represented by the following general formula (II-1), and a general formula (II- A structure having a repeating unit represented by 2) is preferred.
－－下記一般式（ＩＩ－１）で表される繰り返し単位、及び下記一般式（ＩＩ－２）で表される繰り返し単位を有する構造－－
Figure JPOXMLDOC01-appb-C000013
 　ただし、前記一般式（ＩＩ－１）及び（ＩＩ－２）中、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子、及びアルキル基のいずれかを表す。「＊」は、繰返し単位間の連結部を表す。Ｘは、ｐＫａが１４以下である官能基を一部に有する基を表す。Ｙは、数平均分子量が５００～１，０００，０００のグラフト鎖を表す。 --A structure having a repeating unit represented by the following general formula (II-1) and a repeating unit represented by the following general formula (II-2)-
Figure JPOXMLDOC01-appb-C000013
 However, in the general formulas (II-1) and (II-2), R 3 , R 4 , R 5 and R 6 each independently represent any of a hydrogen atom, a halogen atom and an alkyl group. “*” Represents a connecting portion between repeating units. X represents a group partially having a functional group having a pKa of 14 or less. Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
　なお、前記一般式（ＩＩ－１）において、前記一般式（ＩＩ－１）からＸを除いた部分が前記窒素原子を有する主鎖に該当する。
　前記一般式（ＩＩ－２）において、前記一般式（ＩＩ－１）からＹを除いた部分が前記窒素原子を有する主鎖に該当する。 In the general formula (II-1), the portion excluding X from the general formula (II-1) corresponds to the main chain having the nitrogen atom.
In the general formula (II-2), a portion excluding Y from the general formula (II-1) corresponds to the main chain having the nitrogen atom.
　前記一般式（ＩＩ－１）及び（ＩＩ－２）のＲ３、Ｒ４、Ｒ５及びＲ６のアルキル基としては、例えば、置換基を有していてもよい炭素数１～５のアルキル基が挙げられる。前記置換基としては、例えば、ハロゲン原子が挙げられる。
　前記一般式（ＩＩ－１）及び（ＩＩ－２）のＸとしては、ｐＫａが１４以下である官能基を一部に有する基であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、後述するｐＫａが１４以下である官能基を一部に有する基が挙げられる。
　前記一般式（ＩＩ－１）及び（ＩＩ－２）のＹとしては、数平均分子量が５００～１，０００，０００のグラフト鎖であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、後述する数平均分子量が５００～１，０００，０００のグラフト鎖が挙げられる。 Examples of the alkyl group of R 3 , R 4 , R 5 and R 6 in the general formulas (II-1) and (II-2) include an alkyl having 1 to 5 carbon atoms which may have a substituent. Groups. Examples of the substituent include a halogen atom.
X in the general formulas (II-1) and (II-2) is not particularly limited as long as it is a group partially having a functional group having a pKa of 14 or less, and is appropriately selected depending on the purpose. Examples thereof include a group partially having a functional group having a pKa of 14 or less, which will be described later.
Y in the general formulas (II-1) and (II-2) is not particularly limited as long as it is a graft chain having a number average molecular weight of 500 to 1,000,000, and is appropriately selected according to the purpose. Examples thereof include a graft chain having a number average molecular weight of 500 to 1,000,000, which will be described later.
　前記窒素原子含有樹脂は、前記一般式（ＩＩ－１）及び前記一般式（ＩＩ－２）で表される繰返し単位に加えて、さらに下記一般式（ＩＩ－３）で表される繰返し単位を共重合成分として有することが好ましい。このような繰返し単位を併用することで、フィラーの分散性能が向上し、感光性組成物において粘度が高くなるのを抑えることができる。
Figure JPOXMLDOC01-appb-C000014
 　ただし、前記一般式（ＩＩ－３）中、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ、前記一般式（ＩＩ－１）のＲ３、Ｒ４、Ｒ５及びＲ６と同じである。「＊」は、繰返し単位間の連結部を表す。Ｙ’は、アニオン基を有する数平均分子量が５００～１，０００，０００のグラフト鎖を表す。 The nitrogen atom-containing resin includes a repeating unit represented by the following general formula (II-3) in addition to the repeating unit represented by the general formula (II-1) and the general formula (II-2). It is preferable to have it as a copolymerization component. By using such a repeating unit in combination, the dispersion performance of the filler can be improved, and the viscosity of the photosensitive composition can be suppressed from increasing.
Figure JPOXMLDOC01-appb-C000014
 In the general formula (II-3), R 3, R 4, R 5 and R 6 are each the same as R 3, R 4, R 5 and R 6 in the general formula (II-1) is there. “*” Represents a connecting portion between repeating units. Y ′ represents a graft chain having an anionic group and a number average molecular weight of 500 to 1,000,000.
　なお、前記一般式（ＩＩ－３）において、前記一般式（ＩＩ－３）からＹ－を除いた部分が前記窒素原子を有する主鎖に該当する。 In the general formula (II-3), the portion excluding Y − from the general formula (II-3) corresponds to the main chain having the nitrogen atom.
　前記一般式（ＩＩ－３）で表される繰返し単位は、一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂に、アミンと反応して塩を形成する基を有する重合体を添加して反応させることで形成することが可能である。ここで、前記アニオン基としては、ＣＯ２ －、ＳＯ３ －が好ましく、ＣＯ２ －がより好ましい。前記アニオン基は、Ｙ’が有する数平均分子量が５００～１，０００，０００のグラフト鎖の末端位にあることが好ましい。 In the repeating unit represented by the general formula (II-3), a polymer having a group that reacts with an amine to form a salt is added to a resin having at least one of a primary amino group and a secondary amino group. It can be formed by reacting. Here, as the anionic group, CO 2 - and SO 3 - are preferable, and CO 2 - is more preferable. The anionic group is preferably at the terminal position of the graft chain having a number average molecular weight of 500 to 1,000,000.
　前記一般式（ＩＩ－１）、一般式（ＩＩ－２）及び一般式（ＩＩ－３）において、Ｒ３、Ｒ４、Ｒ５及びＲ６は原料入手が容易である点から水素原子であることが好ましい。 In the general formula (II-1), general formula (II-2), and general formula (II-3), R 3 , R 4 , R 5, and R 6 are hydrogen atoms because raw materials are easily available. It is preferable.
　前記一般式（ＩＩ－１）で表される繰返し単位は、ｐＫａが１４以下である官能基を一部に有する基Ｘを有する繰返し単位であり、このような繰り返し単位は、現像時の残渣及び解像性の観点から、前記窒素原子含有樹脂の全繰返し単位中、１モル％～８０モル％含有することが好ましく、３％～５０モル％含有することがより好ましい。 The repeating unit represented by the general formula (II-1) is a repeating unit having a group X partially having a functional group having a pKa of 14 or less. Such a repeating unit includes a residue during development, From the viewpoint of resolution, it is preferably contained in an amount of 1 mol% to 80 mol%, more preferably 3% to 50 mol% in all repeating units of the nitrogen atom-containing resin.
　前記一般式（ＩＩ－２）で表される繰返し単位は、数平均分子量が５００～１，０００，０００のグラフト鎖Ｙを有する繰返し単位であり、このような繰返し単位は、保存安定性の点から、前記窒素原子含有樹脂の全繰返し単位中、１０モル％～９０モル％含有することが好ましく、３０モル％～７０モル％含有することがより好ましい。 The repeating unit represented by the general formula (II-2) is a repeating unit having a graft chain Y having a number average molecular weight of 500 to 1,000,000. Therefore, the content is preferably 10 mol% to 90 mol%, more preferably 30 mol% to 70 mol%, in all the repeating units of the nitrogen atom-containing resin.
　前記一般式（ＩＩ－１）で表される繰返し単位と前記一般式（ＩＩ－２）で表される繰返し単位の前記窒素原子含有樹脂における含有比としては、分散安定性、及び親疎水性のバランスの点から、繰返し単位（ＩＩ－１）：（ＩＩ－２）がモル比で１０：１～１：１００の範囲であることが好ましく、１：１～１：１０の範囲であることがより好ましい。 The content ratio of the repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2) in the nitrogen atom-containing resin is a balance between dispersion stability and hydrophilicity / hydrophobicity. In view of the above, the repeating unit (II-1) :( II-2) is preferably in the range of 10: 1 to 1: 100, and more preferably in the range of 1: 1 to 1:10. preferable.
　なお、所望により併用される前記一般式（ＩＩ－３）で表される繰返し単位は、数平均分子量が５００～１，０００，０００のグラフト鎖が、前記窒素原子を有する主鎖の窒素原子にイオン的に結合しているものであり、前記窒素原子含有樹脂の全繰返し単位中、効果の観点からは、０．５モル％～２０モル％含有することが好ましく、１モル％～１０モル％含有することがより好ましい。
　なお、イオン的に結合していることは、赤外分光法、酸価滴定、塩基滴定などにより確認できる。 The repeating unit represented by the general formula (II-3) used in combination, if desired, has a graft chain having a number average molecular weight of 500 to 1,000,000 as a nitrogen atom of the main chain having the nitrogen atom. In terms of the effect, it is preferably contained in an amount of 0.5 mol% to 20 mol% in all repeating units of the nitrogen atom-containing resin, and 1 mol% to 10 mol%. It is more preferable to contain.
The ion binding can be confirmed by infrared spectroscopy, acid value titration, base titration and the like.
　前記窒素原子を有する主鎖の数平均分子量としては、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、１００～１０，０００が好ましく、２００～５，０００がより好ましく、５００～１，５００が特に好ましい。前記数平均分子量が、前記特に好ましい範囲であると、感光性組成物の粘度及び現像性の両立の点で有利である。前記窒素原子を有する主鎖の分子量は、核磁気共鳴分光法で測定した末端基と鎖部の水素原子積分値の比率から求めることができる。また、例えば、アミノ基を有する重合体を前記窒素原子含有樹脂の原料とする場合には、前記アミノ基を有する重合体の分子量の測定により求めることができる。 The number average molecular weight of the main chain having a nitrogen atom is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 to 10,000, more preferably 200 to 5,000, and more preferably 500 to 1,500 is particularly preferred. When the number average molecular weight is in the particularly preferred range, it is advantageous in terms of both the viscosity and developability of the photosensitive composition. The molecular weight of the main chain having a nitrogen atom can be determined from the ratio of the hydrogen atom integral value of the terminal group and the chain portion measured by nuclear magnetic resonance spectroscopy. Further, for example, when a polymer having an amino group is used as a raw material for the nitrogen atom-containing resin, it can be determined by measuring the molecular weight of the polymer having an amino group.
－ｐＫａが１４以下である官能基を一部に有する基－
　前記ｐＫａが１４以下である官能基を一部に有する基は、前記窒素原子を有する主鎖に存在する窒素原子と結合する基であって水温２５℃でのｐＫａが１４以下である官能基を含有する基である。
　ここで、「ｐＫａ」は、化学便覧（ＩＩ）（改訂４版、１９９３年、日本化学会編、丸善株式会社）に記載されている定義のものである。 -A group partially having a functional group having a pKa of 14 or less-
The group partially having a functional group having a pKa of 14 or less is a group bonded to a nitrogen atom present in the main chain having a nitrogen atom, and a functional group having a pKa at a water temperature of 25 ° C. of 14 or less. It is a group to contain.
Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
　前記ｐＫａが１４以下である官能基としては、物性がこの条件を満たすものであれば、特に制限はなく、目的に応じて適宜選択することができ、公知の官能基でｐＫａが上記範囲を満たすものが挙げられ、具体的には、例えば、カルボン酸（ｐＫａ３～５程度）、スルホン酸（ｐＫａ－３～－２程度）、りん酸（ｐＫａ２程度）、－ＣＯＣＨ２ＣＯ－（ｐＫａ８～１０程度）、－ＣＯＣＨ２ＣＮ（ｐＫａ８～１１程度）、－ＣＯＮＨＣＯ－、フェノール性水酸基、－ＲＦＣＨ２ＯＨ又は－（ＲＦ）２ＣＨＯＨ（ＲＦはペルフルオロアルキル基を表す。（ｐＫａ９～１１程度））、スルホンアミド基（ｐＫａ９～１１程度）などが挙げられる。これらの中でも、カルボン酸（ｐＫａ３～５程度）、スルホン酸（ｐＫａ－３～－２程度）、－ＣＯＣＨ２ＣＯ－（ｐＫａ８～１０程度）が好ましい。 The functional group having a pKa of 14 or less is not particularly limited as long as the physical properties satisfy this condition, and can be appropriately selected according to the purpose. The pKa satisfies the above range with known functional groups. Specifically, for example, carboxylic acid (about pKa 3 to 5), sulfonic acid (about pKa-3 to -2), phosphoric acid (about pKa2), —COCH 2 CO— (about pKa 8 to 10). ), —COCH 2 CN (about pKa 8 to 11), —CONHCO—, phenolic hydroxyl group, —R F CH 2 OH or — (R F ) 2 CHOH (R F represents a perfluoroalkyl group (about pKa 9 to 11) )), Sulfonamide groups (about pKa 9 to 11) and the like. Among these, carboxylic acids (about pKa 3 to 5), sulfonic acids (about pKa-3 to -2), and —COCH 2 CO— (about pKa 8 to 10) are preferable.
　前記ｐＫａが１４以下である官能基を一部に有する基は、通常、前記窒素原子を有する主鎖に存在する窒素原子に直接結合するものであるが、前記窒素原子を有する主鎖の窒素原子と前記ｐＫａが１４以下である官能基を一部に有する基とは、共有結合のみならず、イオン結合して塩を形成する態様で連結していてもよい。 The group partially having a functional group having a pKa of 14 or less is usually bonded directly to a nitrogen atom present in the main chain having the nitrogen atom, but the main chain nitrogen atom having the nitrogen atom. And a group having a functional group having a pKa of 14 or less in part may be linked not only by a covalent bond but also by an ionic bond to form a salt.
　前記窒素原子含有樹脂は、分子内に２種以上の互いに異なる前記ｐＫａが１４以下である官能基を一部に有する基を有していてもよい。 The nitrogen atom-containing resin may have a group partially containing a functional group having two or more different pKa values of 14 or less in the molecule.
　前記ｐＫａが１４以下である官能基を一部に有する基の分子量としては、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、５０～１，０００であることが好ましく、５０～５００であることがより好ましい。この分子量の範囲であることにより、現像性、分散性が良好となる。 The molecular weight of the group partially having a functional group having a pKa of 14 or less is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 1,000, More preferably, it is 500. When the molecular weight is within this range, developability and dispersibility are improved.
　前記ｐＫａが１４以下である官能基を一部に有する基としては、下記一般式（Ｖ－１）で表される基、下記前記一般式（Ｖ－２）で表される基、下記一般式（Ｖ－３）で表される基が好ましい。
Figure JPOXMLDOC01-appb-C000015
 　ただし、前記一般式（Ｖ－１）、及び前記一般式（Ｖ－２）中、Ｕは単結合及び二価の連結基のいずれかを表す。ｄ及びｅは、それぞれ独立に、０及び１のいずれかを表す。
　前記一般式（Ｖ－３）中、Ｗは、アシル基及びアルコキシカルボニル基のいずれかを表す。 Examples of the group partially having a functional group having a pKa of 14 or less include a group represented by the following general formula (V-1), a group represented by the following general formula (V-2), and the following general formula A group represented by (V-3) is preferred.
Figure JPOXMLDOC01-appb-C000015
 However, in the general formula (V-1) and the general formula (V-2), U represents either a single bond or a divalent linking group. d and e each independently represents either 0 or 1;
In the general formula (V-3), W represents either an acyl group or an alkoxycarbonyl group.
　前記Ｕで表される二価の連結基としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、アルキレン基、酸素を含有するアルキレン基、シクロアルキレン基、アリーレン基、アルキレンオキシ基が挙げられる。
　前記アルキレン基としては、例えば、－ＣＨ２－、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）－、－（ＣＨ２）５－、－ＣＨ２ＣＨ（ｎ－Ｃ１０Ｈ２１）－などが挙げられる。
　前記酸素を含有するアルキレン基としては、例えば、－ＣＨ２ＯＣＨ２－、－ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２－などが挙げられる。
　前記シクロアルキレン基としては、例えば、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロオクチレン基などが挙げられる。
　前記アリーレン基としては、例えば、フェニレン基、トリレン基、ビフェニレン基、ナフチレン基、フラニレン基、ピロリレン基などが挙げられる。
　前記アルキレンオキシ基としては、例えば、エチレンオキシ基、プロピレンオキシ基、フェニレンオキシ基などが挙げられる。
　これらの中でも、炭素数１～３０のアルキレン基、炭素数５～２０のシクロアルキレン基、炭素数６～２０のアリーレン基が好ましく、炭素数１～２０のアルキレン基、炭素数５～１０のシクロアルキレン基、炭素数６～１５のアリーレン基がより好ましい。 The divalent linking group represented by U is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkylene group, an oxygen-containing alkylene group, a cycloalkylene group, an arylene group, and an alkylene group. An oxy group is mentioned.
Examples of the alkylene group include, -CH 2 -, - CH 2 CH 2 -, - CH 2 CH (CH 3) -, - (CH 2) 5 -, - CH 2 CH (n-C 10 H 21) -And the like.
Examples of the oxygen-containing alkylene group include —CH 2 OCH 2 —, —CH 2 CH 2 OCH 2 CH 2 —, and the like.
Examples of the cycloalkylene group include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.
Examples of the arylene group include a phenylene group, a tolylene group, a biphenylene group, a naphthylene group, a furylene group, and a pyrrolylene group.
Examples of the alkyleneoxy group include an ethyleneoxy group, a propyleneoxy group, and a phenyleneoxy group.
Among these, an alkylene group having 1 to 30 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms are preferable, an alkylene group having 1 to 20 carbon atoms, and a cyclohexane having 5 to 10 carbon atoms. An alkylene group and an arylene group having 6 to 15 carbon atoms are more preferable.
　前記ｄとしては、生産性の点から１が好ましい。
　前記ｅとしては、０が好ましい。 The d is preferably 1 from the viewpoint of productivity.
The e is preferably 0.
　前記Ｗにおけるアシル基としては、例えば、炭素数１～３０のアシル基が挙げられる。前記炭素数１～３０のアシル基の中でも、製造のし易さ、及び原料の入手の容易性の点か、ホルミル基、アセチル基、ｎ－プロパノイル基、ベンゾイル基が好ましく、アセチル基がより好ましい。
　前記Ｗにおけるアルコキシカルボニル基としては、例えば、メトキシカルボニル基、エトキシカルボニル基、プロピルオキシカルボニル基、イソプロピルオキシカルボニル基、ブトキシカルボニル基、イソブトキシカルボニル基、ｓ－ブトキシカルボニル基、ｔ－ブトキシカルボニル基、ペンチルオキシカルボニル基、ヘキシルオキシカルボニル基、ヘプチルオキシカルボニル基、オクチルオキシカルボニル基、２－エチルヘキシルオキシカルボニル基、ノニルオキシカルボニル基、デシルオキシカルボニル基、３，７－ジメチルオクチルオキシカルボニル基、ドデシルオキシカルボニル基などが挙げられる。 Examples of the acyl group for W include an acyl group having 1 to 30 carbon atoms. Among the acyl groups having 1 to 30 carbon atoms, a formyl group, an acetyl group, an n-propanoyl group, and a benzoyl group are preferable, and an acetyl group is more preferable, from the viewpoint of ease of production and availability of raw materials. .
Examples of the alkoxycarbonyl group in W include, for example, methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, Pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Group and the like.
　前記ｐＫａが１４以下の官能基の前記窒素原子含有樹脂における含有量としては、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、前記窒素原子含有樹脂１ｇに対し、０．０１ｍｍｏｌ～５ｍｍｏｌであることが好ましく、０．０５ｍｍｏｌ～１ｍｍｏｌであることがより好ましい。前記含有量が前記より好ましい範囲であると、フィラーの分散性、分散安定性が向上し、且つ、前記感光性組成物において、未硬化部の現像性が優れる。
　また、前記窒素含有樹脂の酸価は、５ｍｇＫＯＨ／ｇ～５０ｍｇＫＯＨ／ｇであることが、前記感光性組成物の現像性の点から好ましい。
　ここで、酸価滴定は、公知の方法により行うことができ、例えば指示薬法（中和点を指示薬により見極める方法）、電位差測定法などを用いて行うことができる。また、酸価滴定に用いる滴定液は市販の水酸化ナトリウム水溶液を用いることができるが、比較的高いｐＫａを有する官能基（例えば、－ＣＯＣＨ２ＣＯ－、フェノール性水酸基等）のように、この水酸化ナトリウム水溶液によって酸価が測定しにくい場合は、ナトリウムメトキシド－ジオキサン溶液等の非水系滴定液を調製し、非水系溶媒系で酸価測定することが可能である。 The content of the functional group having a pKa of 14 or less in the nitrogen atom-containing resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.01 mmol to 1 g of the nitrogen atom-containing resin. 5 mmol is preferable, and 0.05 mmol to 1 mmol is more preferable. When the content is in the more preferable range, the dispersibility and dispersion stability of the filler are improved, and the developability of the uncured portion is excellent in the photosensitive composition.
The acid value of the nitrogen-containing resin is preferably 5 mgKOH / g to 50 mgKOH / g from the viewpoint of developability of the photosensitive composition.
Here, the acid value titration can be performed by a known method, for example, using an indicator method (a method for determining a neutralization point with an indicator), a potentiometric method, or the like. Although titrant used in acid value titration can be used a commercially available aqueous sodium hydroxide, a functional group having a relatively high pKa (e.g., -COCH 2 CO-, phenolic hydroxyl group) as this When it is difficult to measure the acid value with an aqueous sodium hydroxide solution, it is possible to prepare a nonaqueous titrant such as a sodium methoxide-dioxane solution and measure the acid value in a nonaqueous solvent system.
　前記ｐＫａが１４以下である官能基を一部に有する基は、前記窒素原子を有する主鎖に存在する窒素原子と結合していることを特徴としている。これにより、フィラーの分散性、分散安定性が飛躍的に向上し、感光性組成物においてフィラーの含有量が多い場合にも、粘度が高くなるのを抑えることができる。この理由は不明であるが、次のように推測される。すなわち、前記窒素原子を有する主鎖の窒素原子はアミノ基、アンモニウム基又はアミド基の構造で存在しており、アミノ基、アンモニウム基又はアミド基は、フィラー表面の酸性部と、水素結合、イオン結合等の相互作用によりフィラーに吸着していると考えられる。さらに、前記ｐＫａが１４以下である官能基を一部に有する基は酸基として機能するため、フィラーの塩基性部（窒素原子等）や金属原子と相互作用することができる。つまり、前記窒素原子含有樹脂は、窒素原子と前記ｐＫａが１４以下である官能基を含有する基とで、フィラーの塩基性部と酸性部の双方を吸着することができるため、吸着能が高まり、分散性、分散安定性が飛躍的に向上し、その結果として感光性組成物においてフィラーの含有量が多い場合にも、粘度が高くなるのを抑えることができるものと考えられる。 The group having a functional group having a pKa of 14 or less in part is bonded to a nitrogen atom present in the main chain having the nitrogen atom. Thereby, the dispersibility and dispersion stability of a filler improve dramatically, and even when there is much content of a filler in a photosensitive composition, it can suppress that a viscosity becomes high. The reason is unknown, but is presumed as follows. That is, the nitrogen atom of the main chain having the nitrogen atom exists in the structure of an amino group, an ammonium group or an amide group, and the amino group, the ammonium group or the amide group has an acidic part on the filler surface, a hydrogen bond, an ion It is considered that the filler is adsorbed by the interaction such as bonding. Furthermore, since the group having a functional group having a pKa of 14 or less in part functions as an acid group, it can interact with a basic part of the filler (such as a nitrogen atom) or a metal atom. That is, since the nitrogen atom-containing resin can adsorb both the basic part and the acidic part of the filler with a nitrogen atom and a group containing a functional group having a pKa of 14 or less, the adsorption ability is increased. Thus, it is considered that the dispersibility and dispersion stability are dramatically improved, and as a result, it is possible to suppress an increase in viscosity even when the content of the filler in the photosensitive composition is large.
　さらに、ｐＫａが１４以下である官能基を一部に有する基は、該基に部分構造としてｐＫａが１４以下の官能基を含むものであるため、アルカリ可溶性基としても機能する。それにより、前記窒素原子含有樹脂を感光性組成物に用い、塗膜にエネルギーを付与して部分的に硬化させ、未露光部を溶解除去してパターンを形成する如き用途に使用する場合、未硬化領域のアルカリ現像液への現像性が向上するものと考えられる。 Furthermore, a group having a functional group having a pKa of 14 or less in part also includes a functional group having a pKa of 14 or less as a partial structure, and thus functions as an alkali-soluble group. Accordingly, when the nitrogen atom-containing resin is used in a photosensitive composition, energy is applied to the coating film to be partially cured, and the unexposed portion is dissolved and removed to form a pattern. It is considered that the developability of the cured region into an alkaline developer is improved.
　そして、前記窒素原子含有樹脂により、フィラーの分散性、分散安定性の向上及び感光性組成物の現像性の向上が複合的に寄与して、解像性が高く、現像残渣がない感光性組成物が得られるものと考えられる。 Further, the nitrogen atom-containing resin contributes to the composite dispersibility of the filler, the improvement of the dispersion stability and the improvement of the developability of the photosensitive composition, and the photosensitive composition has high resolution and no development residue. It is thought that a thing is obtained.
－数平均分子量が５００～１，０００，０００のグラフト鎖－
　前記数平均分子量が５００～１，０００，０００のグラフト鎖としては、前記窒素原子を有する主鎖と結合する鎖部であって数平均分子量５００～１００，０００のグラフト鎖であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記窒素原子含有樹脂の窒素原子を有する主鎖と連結できるポリエステル、ポリアミド、ポリイミド、ポリ（メタ）アクリル酸エステルなどの公知の重合体鎖が挙げられる。前記数平均分子量が５００～１，０００，０００のグラフト鎖の前記窒素原子を有する主鎖との結合部位は、前記数平均分子量が５００～１，０００，０００のグラフト鎖の末端であることが好ましい。
　なお、前記窒素原子含有樹脂は、分子内に互いに構造の異なる２種以上の前記数平均分子量が５００～１，０００，０００のグラフト鎖を有していてもよい。 -Graft chain with a number average molecular weight of 500-1,000,000-
The graft chain having a number average molecular weight of 500 to 1,000,000 is not particularly limited as long as it is a chain part bonded to the main chain having a nitrogen atom and has a number average molecular weight of 500 to 100,000. For example, known polymers such as polyesters, polyamides, polyimides, poly (meth) acrylates and the like that can be connected to the main chain having a nitrogen atom of the nitrogen atom-containing resin. A chain. The binding site of the graft chain having the number average molecular weight of 500 to 1,000,000 and the main chain having a nitrogen atom is the end of the graft chain having the number average molecular weight of 500 to 1,000,000. preferable.
The nitrogen atom-containing resin may have two or more types of graft chains having a number average molecular weight of 500 to 1,000,000 having different structures in the molecule.
　前記数平均分子量が５００～１，０００，０００のグラフト鎖は、前記窒素原子を有する主鎖の窒素原子と結合していることが好ましい。前記数平均分子量が５００～１，０００，０００のグラフト鎖と前記窒素原子を有する主鎖の窒素原子との結合様式は、共有結合、イオン結合、並びに共有結合及びイオン結合の混合のいずれかである。前記数平均分子量が５００～１，０００，０００のグラフト鎖と前記窒素原子を有する主鎖の窒素原子との結合様式の比率は、共有結合：イオン結合＝１００：０～０：１００であるが、９５：５～５：９５が好ましく、９０：１０～１０：９０がより好ましく、９５：５～８０：２０が特に好ましい。共有結合とイオン結合との結合様式をこの好ましい範囲とすることで、フィラーの分散性、分散安定性が向上し、かつ前記窒素原子含有樹脂の溶剤溶解性が良好となる。 The graft chain having a number average molecular weight of 500 to 1,000,000 is preferably bonded to the nitrogen atom of the main chain having the nitrogen atom. The bonding mode of the graft chain having a number average molecular weight of 500 to 1,000,000 and the nitrogen atom of the main chain having a nitrogen atom is any one of a covalent bond, an ionic bond, and a mixture of a covalent bond and an ionic bond. is there. The ratio of the bonding mode between the graft chain having a number average molecular weight of 500 to 1,000,000 and the nitrogen atom of the main chain having a nitrogen atom is covalent bond: ionic bond = 100: 0 to 0: 100. 95: 5 to 5:95 is preferable, 90:10 to 10:90 is more preferable, and 95: 5 to 80:20 is particularly preferable. By setting the bonding mode between the covalent bond and the ionic bond within this preferable range, the dispersibility and dispersion stability of the filler are improved, and the solvent solubility of the nitrogen atom-containing resin is improved.
　前記数平均分子量が５００～１，０００，０００のグラフト鎖は、前記窒素原子を有する主鎖の窒素原子とアミド結合していること、カルボン酸塩としてイオン結合していることが好ましい。 The graft chain having a number average molecular weight of 500 to 1,000,000 is preferably an amide bond with a nitrogen atom of the main chain having the nitrogen atom or an ionic bond as a carboxylate.
　前記数平均分子量が５００～１，０００，０００のグラフト鎖の数平均分子量はＧＰＣ法によるポリスチレン換算値により測定することができる。前記グラフト鎖の数平均分子量は、１，０００～５０，０００が好ましく、１，０００～３０，０００がより好ましい。前記数平均分子量がより好ましい範囲であると、フィラーの分散性、分散安定性、及び前記感光性組成物の現像性の点で有利である。 The number average molecular weight of the graft chain having the number average molecular weight of 500 to 1,000,000 can be measured by polystyrene conversion value by GPC method. The number average molecular weight of the graft chain is preferably 1,000 to 50,000, and more preferably 1,000 to 30,000. When the number average molecular weight is in a more preferable range, it is advantageous in terms of dispersibility of the filler, dispersion stability, and developability of the photosensitive composition.
　前記数平均分子量が５００～１，０００，０００のグラフト鎖は、前記窒素原子を有する主鎖に２つ以上連結していることが好ましく、５つ以上連結していることがより最も好ましい。 The graft chain having a number average molecular weight of 500 to 1,000,000 is preferably connected to the main chain having a nitrogen atom by 2 or more, more preferably 5 or more.
　前記数平均分子量が５００～１，０００，０００のグラフト鎖は、下記一般式（ＩＩＩ－１）で表されるグラフト鎖であることが好ましい。
Figure JPOXMLDOC01-appb-C000016
 　ただし、前記一般式（ＩＩＩ－１）中、Ｚは、ポリエステル鎖を部分構造として少なくとも有する重合体残基であって、下記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルからカルボキシル基を除いた重合体残基を表す。
Figure JPOXMLDOC01-appb-C000017
 　ただし、前記一般式（ＩＶ）中、Ｚは、前記一般式（ＩＩＩ－１）中のＺと同じである。 The graft chain having a number average molecular weight of 500 to 1,000,000 is preferably a graft chain represented by the following general formula (III-1).
Figure JPOXMLDOC01-appb-C000016
 However, in the general formula (III-1), Z is a polymer residue having at least a polyester chain as a partial structure, and from a polyester having a free carboxylic acid represented by the following general formula (IV) to a carboxyl It represents a polymer residue excluding a group.
Figure JPOXMLDOC01-appb-C000017
 However, in the general formula (IV), Z is the same as Z in the general formula (III-1).
　前記窒素原子含有樹脂が前記一般式（Ｉ－３）で表される繰返し単位及び前記（ＩＩ－３）で表される繰返し単位の少なくともいずれかを含有する場合、前記Ｙ’が一般式（ＩＩＩ－２）であることが好ましい。 When the nitrogen atom-containing resin contains at least one of the repeating unit represented by the general formula (I-3) and the repeating unit represented by the (II-3), Y ′ is represented by the general formula (III -2).
Figure JPOXMLDOC01-appb-C000018
 　ただし、前記一般式（ＩＩＩ－２）中、Ｚは前記一般式（ＩＩＩ－１）のＺと同じである。
Figure JPOXMLDOC01-appb-C000018
 However, in the general formula (III-2), Z is the same as Z in the general formula (III-1).
　前記一般式（ＩＶ）で表わされる遊離のカルボン酸を有するポリエステル（片末端にカルボキシル基を有するポリエステル）は、例えば、（ＩＶ－１）カルボン酸とラクトンの重縮合、（ＩＶ－２）ヒドロキシ基含有カルボン酸の重縮合、（ＩＶ－３）二価アルコールと二価カルボン酸（又は環状酸無水物）の重縮合、により得ることができる。 Polyester having a free carboxylic acid represented by the general formula (IV) (polyester having a carboxyl group at one end) is, for example, (IV-1) polycondensation of carboxylic acid and lactone, (IV-2) hydroxy group (IV-3) polycondensation of dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride).
－－（ＩＶ－１）カルボン酸とラクトンの重縮合－－
　前記カルボン酸とラクトンの重縮合に用いるカルボン酸としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、脂肪族カルボン酸、ヒドロキシ基含有カルボン酸などが挙げられる。
　前記脂肪族カルボン酸としては、炭素数１～３０の直鎖のカルボン酸、炭素数１～３０の分岐のカルボン酸が好ましく、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、ｎ－ヘキサン酸、ｎ－オクタン酸、ｎ－デカン酸、ｎ－ドデカン酸、パルミチン酸、２－エチルヘキサン酸、シクロヘキサン酸がより好ましい。
　前記ヒドロキシ基含有カルボン酸としては、炭素数１～３０の直鎖のヒドロキシ基含有カルボン酸、炭素数１～３０の分岐のヒドロキシ基含有カルボン酸が好ましく、グリコール酸、乳酸、３－ヒドロキシプロピオン酸、４－ヒドロキシドデカン酸、５－ヒドロキシドデカン酸、リシノール酸、１２－ヒドロキシドデカン酸、１２－ヒドロキシステアリン酸、２，２－ビス（ヒロドキシメチル）酪酸がより好ましい。
　これらの中でも、炭素数６～２０の直鎖脂肪族カルボン酸、炭素数１～２０のヒドロキシ基含有カルボン酸が特に好ましい。
　これらのカルボン酸は、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。 -(IV-1) Polycondensation of carboxylic acid and lactone--
There is no restriction | limiting in particular as carboxylic acid used for the polycondensation of the said carboxylic acid and lactone, According to the objective, it can select suitably, For example, aliphatic carboxylic acid, hydroxy group containing carboxylic acid, etc. are mentioned.
As the aliphatic carboxylic acid, a linear carboxylic acid having 1 to 30 carbon atoms and a branched carboxylic acid having 1 to 30 carbon atoms are preferable. Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid and cyclohexane acid are more preferred.
The hydroxy group-containing carboxylic acid is preferably a straight-chain hydroxy group-containing carboxylic acid having 1 to 30 carbon atoms or a branched hydroxy group-containing carboxylic acid having 1 to 30 carbon atoms, such as glycolic acid, lactic acid, or 3-hydroxypropionic acid. 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, and 2,2-bis (hydroxymethyl) butyric acid are more preferable.
Among these, linear aliphatic carboxylic acids having 6 to 20 carbon atoms and hydroxy group-containing carboxylic acids having 1 to 20 carbon atoms are particularly preferable.
These carboxylic acids may be used alone or in combination of two or more.
　前記カルボン酸とラクトンの重縮合に用いるラクトンとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、β－プロピオラクトン、β－ブチロラクトン、γ－ブチロラクトン、γ－ヘキサノラクトン、γ－オクタノラクトン、δ－バレロラクトン、δ－ヘキサラノラクトン、δ－オクタノラクトン、ε－カプロラクトン、δ－ドデカノラクトン、α－メチル－γ－ブチロラクトンなどが挙げられる。これらの中でも、ε－カプロラクトンが反応性、入手性の点から好ましい。
　これらのラクトンは、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 lactone used for the polycondensation of carboxylic acid and lactone is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone Examples include lactone, γ-octanolactone, δ-valerolactone, δ-hexalanolactone, δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, and the like. Among these, ε-caprolactone is preferable from the viewpoint of reactivity and availability.
These lactones may be used alone or in combination of two or more.
　前記カルボン酸と前記ラクトンの反応時の仕込み比率としては、目的のポリエステル鎖の分子量によるため一義的に決定できないが、モル比でカルボン酸：ラクトン＝１：１～１：１，０００が好ましく、１：３～１：５００がより好ましい。 The charge ratio at the time of reaction of the carboxylic acid and the lactone cannot be uniquely determined because of the molecular weight of the target polyester chain, but is preferably carboxylic acid: lactone = 1: 1 to 1: 1,000 in terms of molar ratio. A ratio of 1: 3 to 1: 500 is more preferable.
－－（ＩＶ－２）ヒドロキシ基含有カルボン酸の重縮合－－
　前記ヒドロキシ基含有カルボン酸の重縮合に用いるヒドロキシ基含有カルボン酸としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記（ＩＶ－１）におけるヒドロキシ基含有カルボン酸と同様であり、好ましい範囲も同様である。 -(IV-2) Polycondensation of hydroxy group-containing carboxylic acid--
The hydroxy group-containing carboxylic acid used for the polycondensation of the hydroxy group-containing carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the hydroxy group-containing carboxylic acid in the above (IV-1) The same is true for the preferred range.
－－（ＩＶ－３）二価アルコールと二価カルボン酸（又は環状酸無水物）の重縮合－－
　前記二価アルコールと二価カルボン酸（又は環状酸無水物）の重縮合に用いる二価アルコールとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、直鎖の脂肪族ジオール、分岐の脂肪族ジオールが挙げられる。
　前記直鎖の脂肪族ジオール、及び前記分岐の脂肪族ジオールとしては、炭素数２～３０のジオールが好ましく、炭素数２～２０の脂肪族ジオールがより好ましい。前記炭素数２～２０の脂肪族ジオールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，８－オクタンジオールなどが挙げられる。 -(IV-3) Polycondensation of dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride)-
The dihydric alcohol used for the polycondensation of the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a linear aliphatic Examples include diols and branched aliphatic diols.
As the linear aliphatic diol and the branched aliphatic diol, a diol having 2 to 30 carbon atoms is preferable, and an aliphatic diol having 2 to 20 carbon atoms is more preferable. Examples of the aliphatic diol having 2 to 20 carbon atoms include ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 1,8-octanediol and the like.
　前記二価アルコールと二価カルボン酸（又は環状酸無水物）の重縮合に用いる二価カルボン酸としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、直鎖の二価の脂肪族カルボン酸、分岐の二価の脂肪族カルボン酸が挙げられる。
　前記直鎖の二価の脂肪族カルボン酸、及び分岐の二価の脂肪族カルボン酸としては、炭素数１～３０の二価の脂肪族カルボン酸が好ましく、炭素数３～２０の二価の脂肪族カルボン酸がより好ましい。前記炭素数３～２０の二価カルボン酸としては、例えば、コハク酸、マレイン酸、アジピン酸、セバシン酸、ドデカン二酸、グルタル酸、スベリン酸、酒石酸、シュウ酸、マロン酸などが挙げられる。 The divalent carboxylic acid used for the polycondensation of the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride) is not particularly limited and may be appropriately selected depending on the intended purpose. Valent aliphatic carboxylic acid and branched divalent aliphatic carboxylic acid.
As the linear divalent aliphatic carboxylic acid and the branched divalent aliphatic carboxylic acid, a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms is preferable, and a divalent aliphatic carboxylic acid having 3 to 20 carbon atoms is preferable. Aliphatic carboxylic acids are more preferred. Examples of the divalent carboxylic acid having 3 to 20 carbon atoms include succinic acid, maleic acid, adipic acid, sebacic acid, dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid and malonic acid.
　前記二価アルコールと二価カルボン酸（又は環状酸無水物）の重縮合には、前記二価カルボン酸と等価な酸無水物（例えば、無水コハク酸、無水グルタル酸等）を用いてもよい。 For polycondensation of the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride), an acid anhydride equivalent to the divalent carboxylic acid (for example, succinic anhydride, glutaric anhydride, etc.) may be used. .
　前記二価カルボン酸と前記二価アルコールは、モル比１：１で仕込むことが好ましい。これにより、前記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルの末端にカルボン酸を導入することが可能となる。 The divalent carboxylic acid and the dihydric alcohol are preferably charged at a molar ratio of 1: 1. Thereby, it becomes possible to introduce the carboxylic acid into the terminal of the polyester having the free carboxylic acid represented by the general formula (IV).
　前記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルを製造する際の重縮合は、触媒を添加して行うことが好ましい。前記触媒としては、ルイス酸として機能する触媒が好ましい。前記ルイス酸として機能する触媒としては、例えば、Ｔｉ化合物、Ｓｎ化合物、プロトン酸などが挙げられる。前記Ｔｉ化合物としは、例えば、Ｔｉ（Ｏ－Ｃ４Ｈ９）４、Ｔｉ（Ｏ－Ｃ３Ｈ７）４などが挙げられる。前記Ｓｎ化合物としては、例えば、オクチル酸スズ、ジブチルスズオキシド、ジブチルスズラウレート、モノブチルスズヒドロキシブチルオキシド、塩化第二スズ、ブチルスズジオキシドなどが挙げられる。前記プロトン酸としては、例えば、硫酸、パラトルエンスルホン酸などが挙げられる。
　前記重縮合における触媒量としては、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、全モノマーのモル数に対し、０．０１モル％～１０モル％が好ましく、０．１モル％～５モル％がより好ましい。
　前記重縮合における反応温度としては、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、８０℃～２５０℃が好ましく、１００℃～１８０℃がより好ましい。
　前記重縮合における反応時間としては、反応条件により異なるが、通常、１時間～２４時間である。 The polycondensation in producing the polyester having the free carboxylic acid represented by the general formula (IV) is preferably performed by adding a catalyst. As the catalyst, a catalyst that functions as a Lewis acid is preferable. Examples of the catalyst that functions as the Lewis acid include Ti compounds, Sn compounds, and protonic acids. Examples of the Ti compound include Ti (O—C 4 H 9 ) 4 and Ti (O—C 3 H 7 ) 4 . Examples of the Sn compound include tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, stannic chloride, and butyltin dioxide. Examples of the protonic acid include sulfuric acid and paratoluenesulfonic acid.
The amount of the catalyst in the polycondensation is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 mol% to 10 mol%, preferably 0.1 % To 5 mol% is more preferable.
The reaction temperature in the polycondensation is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 80 ° C to 250 ° C, more preferably 100 ° C to 180 ° C.
The reaction time in the polycondensation is usually 1 to 24 hours, although it varies depending on the reaction conditions.
　前記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルの数平均分子量としては、１，０００～１，０００，０００が好ましく、２，０００～１００，０００がより好ましく、３，０００～５０，０００が特に好ましい。数平均分子量が前記範囲にある場合、分散性、及び現像性の両立ができる点で有利である。
　前記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルの数平均分子量は、ＧＰＣ法によるポリスチレン換算値として測定することができる。 The number average molecular weight of the polyester having a free carboxylic acid represented by the general formula (IV) is preferably 1,000 to 1,000,000, more preferably 2,000 to 100,000, and 3,000. ˜50,000 is particularly preferred. When the number average molecular weight is in the above range, it is advantageous in that both dispersibility and developability can be achieved.
The number average molecular weight of the polyester having a free carboxylic acid represented by the general formula (IV) can be measured as a polystyrene converted value by the GPC method.
　前記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルとしては、（ＩＶ－１）カルボン酸とラクトンの重縮合、及び、（ＩＶ－２）ヒドロキシ基含有カルボン酸の重縮合の少なくともいずれかにより得られるポリエステルであることが、製造容易性の点から好ましい。 Examples of the polyester having a free carboxylic acid represented by the general formula (IV) include (IV-1) polycondensation of carboxylic acid and lactone, and (IV-2) polycondensation of hydroxy group-containing carboxylic acid. A polyester obtained by any of these is preferable from the viewpoint of ease of production.
　前記窒素原子含有樹脂の具体例〔（Ａ－１）～（Ａ－６０）〕を、樹脂が有する繰返し単位の具体的構造とその組合せにより以下に示すが、前記窒素原子含有樹脂はこれに限定されるものではない。下記式中、ｋ、ｌ、ｍ、及びｎはそれぞれ繰返し単位の重合モル比を示し、ｋは１～８０、ｌは１０～９０、ｍは０～８０、ｎは０～７０であり、且つｋ＋ｌ＋ｍ＋ｎ＝１００である。ｐ及びｑはポリエステル鎖の連結数を示し、それぞれ独立に５～１００，０００を表す。Ｒ’は水素原子、アルコキシカルボニル基のいずれかを表す。
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
 Specific examples of the nitrogen atom-containing resin [(A-1) to (A-60)] are shown below by the specific structure of the repeating unit of the resin and the combination thereof, but the nitrogen atom-containing resin is not limited to this. It is not done. In the following formula, k, l, m, and n each represent a polymerization molar ratio of repeating units, k is 1 to 80, l is 10 to 90, m is 0 to 80, n is 0 to 70, and k + l + m + n = 100. p and q represent the number of linked polyester chains, and each independently represents 5 to 100,000. R ′ represents either a hydrogen atom or an alkoxycarbonyl group.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
－窒素原子含有樹脂の製造方法－
　前記窒素原子含有樹脂の製造方法としては、例えば、（１）一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂と、前記ｐＫａが１４以下である官能基を一部に有する基の前駆体と、前記数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体とを反応させる方法、（２）窒素原子を含有するモノマーと、前記ｐＫａが１４以下である官能基を一部に有する基を含有するモノマーと、前記数平均分子量が５００～１，０００，０００のグラフト鎖を含有するモノマーとの重合による方法、などが挙げられる。これらの中でも、前記（１）により製造する方法が好ましい。 -Manufacturing method of nitrogen atom-containing resin-
Examples of the method for producing the nitrogen atom-containing resin include: (1) a resin having at least one of a primary amino group and a secondary amino group, and a precursor of a group partially having a functional group having a pKa of 14 or less. And a graft chain precursor having a number average molecular weight of 500 to 1,000,000, (2) a monomer containing a nitrogen atom, and a part of the functional group having a pKa of 14 or less And a method of polymerizing a monomer containing a group having the above and a monomer containing a graft chain having a number average molecular weight of 500 to 1,000,000. Among these, the method produced by (1) is preferable.
－－（１）の製造方法－－
　前記（１）の製造方法としては、（ａ）一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂と、前記ｐＫａが１４以下である官能基を一部に有する基の前駆体と、前記数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体とを同時に反応させる方法、（ｂ）一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂と、前記ｐＫａが１４以下である官能基を一部に有する基の前駆体とを反応させた後、該反応の生成物と前記数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体とを反応させる方法、（ｃ）一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂と、前記数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体とを反応させた後、該反応の生成物と前記ｐＫａが１４以下である官能基を一部に有する基の前駆体とを反応させる方法、などが挙げられる。これらの中でも、前記（ｃ）の製造方法が好ましい。 -Manufacturing method (1)-
The production method of (1) includes (a) a resin having at least one of a primary amino group and a secondary amino group, and a precursor of a group partially having a functional group having a pKa of 14 or less, A method of simultaneously reacting a precursor of a graft chain having a number average molecular weight of 500 to 1,000,000, (b) a resin having at least one of a primary amino group and a secondary amino group, and the pKa of 14 or less A method of reacting a precursor of a group partially having a functional group with a product of the reaction and a precursor of a graft chain having a number average molecular weight of 500 to 1,000,000, (C) After reacting a resin having at least one of a primary amino group and a secondary amino group with a precursor of a graft chain having a number average molecular weight of 500 to 1,000,000, a product of the reaction And said A method of reacting a precursor of a group having a part Ka of 14 or less functional groups, and the like. Among these, the production method (c) is preferable.
－－－一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂－－－
　前記一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂としては、前記窒素原子を有する主鎖を構成するアミノ基を有する重合体が挙げられる。前記アミノ基を有する重合体としては、例えば、ポリ（アルキレンイミン）、ポリアリルアミン、ポリジアリルアミン、メタキシレンジアミン－エピクロルヒドリン重縮合物、ポリビニルアミン、３－ジアルキルアミノプロピル（メタ）アクリル酸アミドを共重合成分として有する共重合体、及び（メタ）アクリル酸２－ジアルキルアミノエチルを共重合成分として有する共重合体などが挙げられる。これらの中でも、ポリ（アルキレンイミン）、ポリアリルアミンが好ましい。 --- Resin having at least one of primary amino group and secondary amino group ---
Examples of the resin having at least one of the primary amino group and the secondary amino group include a polymer having an amino group constituting the main chain having the nitrogen atom. Examples of the polymer having an amino group include poly (alkyleneimine), polyallylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, polyvinylamine, and 3-dialkylaminopropyl (meth) acrylic acid amide. Examples thereof include a copolymer having as a component and a copolymer having 2-dialkylaminoethyl (meth) acrylate as a copolymer component. Among these, poly (alkyleneimine) and polyallylamine are preferable.
－－－ｐＫａが１４以下である官能基を一部に有する基の前駆体－－－
　前記ｐＫａが１４以下である官能基を一部に有する基の前駆体とは、前記一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂と反応し、前記窒素原子含有樹脂における前記窒素原子を有する主鎖に存在する窒素原子に、前記ｐＫａが１４以下である官能基を一部に有する基を結合させることのできる化合物を表す。 --- a precursor of a group partially having a functional group with a pKa of 14 or less ---
The precursor of a group partially having a functional group having a pKa of 14 or less reacts with a resin having at least one of the primary amino group and the secondary amino group, and the nitrogen atom in the nitrogen atom-containing resin The compound which can couple | bond the group which has the functional group in which said pKa is 14 or less in part to the nitrogen atom which exists in the principal chain which has this.
　前記ｐＫａが１４以下である官能基を一部に有する基の前駆体としては、例えば、環状カルボン酸無水物、ハロゲン原子含有カルボン酸、スルトン、ジケテン、環状スルホカルボン酸無水物、－ＣＯＣＨ２ＣＯＣｌを含有する化合物、シアノ酢酸クロリドなどが挙げられる。これらの中でも、環状カルボン酸無水物、スルトン、ジケテンが、生産性の点から好ましい。 Examples of the precursor of a group partially having a functional group having a pKa of 14 or less include a cyclic carboxylic acid anhydride, a halogen atom-containing carboxylic acid, a sultone, a diketene, a cyclic sulfocarboxylic acid anhydride, —COCH 2 COCl And cyanoacetic acid chloride. Among these, cyclic carboxylic acid anhydride, sultone, and diketene are preferable from the viewpoint of productivity.
　前記環状カルボン酸無水物としては、炭素数４～３０の環状カルボン酸無水物が好ましい。前記炭素数４～３０の環状カルボン酸無水物としては、例えば、コハク酸無水物、グルタル酸無水物、イタコン酸無水物、マレイン酸無水物、アリルコハク酸無水物、ブチルコハク酸無水物、ｎ－オクチルコハク酸無水物、ｎ－デシルコハク酸無水物、ｎ－ドデシルコハク酸無水物、ｎ－テトラデシルコハク酸無水物、ｎ－ドコセニルコハク酸無水物、（２－ヘキセン－１－イル）コハク酸無水物、（２－メチルプロペン－１－イル）コハク酸無水物、（２－ドデセン－１－イル）コハク酸無水物、ｎ－オクテニルコハク酸無水物、（２，７－オクタンジエン－１－イル）コハク酸無水物、アセチルリンゴ酸無水物、ジアセチル酒石酸無水物、ヘット酸無水物、シクロヘキサン－１，２－ジカルボン酸無水物、３又は４－メチルシクロヘキサン－１，２－ジカルボン酸無水物、テトラフルオロコハク酸無水物、３又は４－シクロヘキセン－１，２－ジカルボン酸無水物、４－メチル－４－シクロヘキセン－１，２－ジカルボン酸無水物、フタル酸無水物、テトラクロロフタル酸無水物、ナフタル酸無水物、ナフタル酸無水物、ビシクロ［２．２．２］オクト－７－エン－２，３，５，６－テトラカルボン酸二無水物、ピロメリット酸二無水物、ｍｅｓｏ－ブタン－１，２，３，４－テトラカルボン酸二無水物、１，２，３，４－シクロペンタンカルボン酸二無水物などが挙げられる。
　前記ハロゲン原子含有カルボン酸としては、例えば、クロロ酢酸、ブロモ酢酸、ヨード酢酸、４－クロロ－ｎ－酪酸などが挙げられる。
　前記スルトンとしては、例えば、プロパンスルトン、１，４－ブタンスルトンなどが挙げられる。
　前記環状スルホカルボン酸無水物としては、例えば、２－スルホ安息香酸無水物が挙げられる。
　前記－ＣＯＣＨ２ＣＯＣｌを含有する化合物としては、例えば、エチルマロニルクロリドが挙げられる。 The cyclic carboxylic acid anhydride is preferably a cyclic carboxylic acid anhydride having 4 to 30 carbon atoms. Examples of the cyclic carboxylic acid anhydride having 4 to 30 carbon atoms include succinic anhydride, glutaric anhydride, itaconic anhydride, maleic anhydride, allyl succinic anhydride, butyl succinic anhydride, and n-octyl. Succinic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-docosenyl succinic anhydride, (2-hexen-1-yl) succinic anhydride, (2-Methylpropen-1-yl) succinic anhydride, (2-dodecene-1-yl) succinic anhydride, n-octenyl succinic anhydride, (2,7-octanedien-1-yl) succinic acid Anhydride, acetylmalic anhydride, diacetyltartaric anhydride, het acid anhydride, cyclohexane-1,2-dicarboxylic anhydride, 3 or 4-methylcyclohexa -1,2-dicarboxylic acid anhydride, tetrafluorosuccinic acid anhydride, 3 or 4-cyclohexene-1,2-dicarboxylic acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, phthalate Acid anhydride, tetrachlorophthalic anhydride, naphthalic anhydride, naphthalic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Examples include pyromellitic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanecarboxylic dianhydride, and the like.
Examples of the halogen atom-containing carboxylic acid include chloroacetic acid, bromoacetic acid, iodoacetic acid, 4-chloro-n-butyric acid, and the like.
Examples of the sultone include propane sultone and 1,4-butane sultone.
Examples of the cyclic sulfocarboxylic acid anhydride include 2-sulfobenzoic acid anhydride.
Examples of the compound containing —COCH 2 COCl include ethyl malonyl chloride.
－－－数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体－－－
　前記数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体とは、前記一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂と反応し、前記窒素原子含有樹脂における前記窒素原子を有する主鎖に、前記数平均分子量が５００～１，０００，０００のグラフト鎖を結合させることのできる化合物を表す。 --- Precursor of graft chain having a number average molecular weight of 500 to 1,000,000 ---
The graft chain precursor having a number average molecular weight of 500 to 1,000,000 reacts with a resin having at least one of the primary amino group and secondary amino group, and the nitrogen atom in the nitrogen atom-containing resin. Represents a compound capable of binding a graft chain having a number average molecular weight of 500 to 1,000,000 to the main chain having
　前記数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体は、前記窒素原子含有樹脂における前記窒素原子を有する主鎖と共有結合及びイオン結合のいずれかができる基を末端に有する数平均分子量５００～１，０００，０００の重合体が好ましく、片末端に遊離のカルボキシル基を有する数平均分子量５００～１，０００，０００の重合体がより好ましい。
　前記数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体としては、例えば、前記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステル（片末端にカルボキシル基を有するポリエステル）、片末端に遊離のカルボン酸を有するポリアミド、片末端に遊離のカルボン酸を有するポリ（メタ）アクリル酸系樹脂などが挙げられる。これらの中でも、前記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルがより好ましい。 The graft chain precursor having a number average molecular weight of 500 to 1,000,000 is a number having a terminal group capable of either a covalent bond or an ionic bond with the main chain having a nitrogen atom in the nitrogen atom-containing resin. A polymer having an average molecular weight of 500 to 1,000,000 is preferred, and a polymer having a number average molecular weight of 500 to 1,000,000 having a free carboxyl group at one end is more preferred.
Examples of the precursor of the graft chain having a number average molecular weight of 500 to 1,000,000 include, for example, a polyester having a free carboxylic acid represented by the general formula (IV) (polyester having a carboxyl group at one end) And a polyamide having a free carboxylic acid at one end, and a poly (meth) acrylic acid resin having a free carboxylic acid at one end. Among these, a polyester having a free carboxylic acid represented by the general formula (IV) is more preferable.
　前記数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体は、公知の方法で合成することができ、例えば、前記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルは、前記（ＩＶ－１）カルボン酸とラクトンの重縮合、前記（ＩＶ－２）ヒドロキシ基含有カルボン酸の重縮合、前記（ＩＶ－３）二価アルコールと二価カルボン酸（又は環状酸無水物）の重縮合などより製造することができる。
　前記片末端に遊離のカルボン酸を含有するポリアミドは、アミノ基含有カルボン酸（例えば、グリシン、アラニン、β－アラニン、２－アミノ酪酸等）の自己縮合等により製造することができる。
　前記片末端に遊離のカルボン酸を有するポリ（メタ）アクリル酸エステルはカルボキシル基含有連鎖移動剤（例えば、３－メルカプトプロピオン酸等）の存在下、（メタ）アクリル酸系モノマーをラジカル重合することにより製造することができる。 The graft chain precursor having a number average molecular weight of 500 to 1,000,000 can be synthesized by a known method. For example, a polyester having a free carboxylic acid represented by the general formula (IV) (IV-1) polycondensation of carboxylic acid and lactone, (IV-2) polycondensation of hydroxy group-containing carboxylic acid, (IV-3) dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride) ) Polycondensation or the like.
The polyamide containing a free carboxylic acid at one end can be produced by self-condensation of an amino group-containing carboxylic acid (for example, glycine, alanine, β-alanine, 2-aminobutyric acid, etc.).
The poly (meth) acrylic acid ester having a free carboxylic acid at one end is obtained by radical polymerization of a (meth) acrylic acid monomer in the presence of a carboxyl group-containing chain transfer agent (for example, 3-mercaptopropionic acid). Can be manufactured.
　前記窒素原子含有樹脂の製造における反応温度としては、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、２０℃～２００℃が好ましく、４０℃～１５０℃がより好ましい。
　前記製造における反応時間としては、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、生産性の点から、１時間～４８時間が好ましく、１時間～２４時間がより好ましい。 The reaction temperature in the production of the nitrogen atom-containing resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C.
The reaction time in the production is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 hour to 48 hours, more preferably 1 hour to 24 hours from the viewpoint of productivity.
　前記製造における反応は溶媒存在下で行ってもよい。前記溶媒としては、水、スルホキシド化合物（例えば、ジメチルスルホキシド等）、ケトン化合物（例えば、アセトン、メチルエチルケトン、シクロヘキサノン等）、エステル化合物（例えば、酢酸エチル、酢酸ブチル、プロピオン酸エチル、プロピレングリコール１－モノメチルエーテル２－アセテート等）、エーテル化合物（例えば、ジエチルエーテル、ジブチルエーテル、テトラヒドロフラン等）、脂肪族炭化水素化合物（例えば、ペンタン、ヘキサン等）、芳香族炭化水素化合物（例えば、トルエン、キシレン、メシチレン等）、二トリル化合物（例えば、アセトニトリル、プロピオンニトリル等）、アミド化合物（例えば、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン等）、カルボン酸化合物（例えば、酢酸、プロピオン酸等）、アルコール化合物（例えば、メタノール、エタノール、イソプロパノール、ｎ－ブタノール、３－メチルブタノール、１－メトキシ－２－プロパノール等）、ハロゲン系溶媒（例えば、クロロホルム、１，２－ジクロロエタン等）などが挙げられる。
　前記溶媒を用いる場合、反応原料に対し、０．１質量倍～１００質量倍用いることが好ましく、０．５質量倍～１０質量倍用いることがより好ましい。 The reaction in the production may be performed in the presence of a solvent. Examples of the solvent include water, sulfoxide compounds (for example, dimethyl sulfoxide), ketone compounds (for example, acetone, methyl ethyl ketone, cyclohexanone, etc.), ester compounds (for example, ethyl acetate, butyl acetate, ethyl propionate, propylene glycol 1-monomethyl). Ether 2-acetate, etc.), ether compounds (eg, diethyl ether, dibutyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbon compounds (eg, pentane, hexane, etc.), aromatic hydrocarbon compounds (eg, toluene, xylene, mesitylene, etc.) ), Nitrile compounds (eg, acetonitrile, propiononitrile, etc.), amide compounds (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), carboxylic acids Compounds (eg, acetic acid, propionic acid, etc.), alcohol compounds (eg, methanol, ethanol, isopropanol, n-butanol, 3-methylbutanol, 1-methoxy-2-propanol, etc.), halogenated solvents (eg, chloroform, 1,2-dichloroethane, etc.).
When the solvent is used, it is preferably used in an amount of 0.1 to 100 times by mass, more preferably 0.5 to 10 times by mass with respect to the reaction raw material.
　前記製造における前記窒素原子含有樹脂の精製方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、再沈法が挙げられる。前記再沈法により低分子量成分を除去することにより、得られた前記窒素原子含有樹脂をフィラーの分散剤として使用した場合の分散性能が向上する。
　再沈には、ヘキサン等の炭化水素系溶媒、メタノールなどのアルコール系溶媒を用いることが好ましい。 There is no restriction | limiting in particular as the purification method of the said nitrogen atom containing resin in the said manufacture, According to the objective, it can select suitably, For example, the reprecipitation method is mentioned. By removing the low molecular weight component by the reprecipitation method, the dispersion performance when the obtained nitrogen atom-containing resin is used as a dispersant for the filler is improved.
For reprecipitation, it is preferable to use a hydrocarbon solvent such as hexane and an alcohol solvent such as methanol.
－－（２）の製造方法－－
　前記（２）の製造方法に用いる、窒素原子を含有するモノマーとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、（メタ）アクリル酸２－ジアルキルアミノエチル、３－ジアルキルアミノプロピル（メタ）アクリルアミド、ビニルピリジン、Ｎ－ビニルイミダゾールなどが挙げられる。これらの中でも、三級アミノ基を含有するモノマーが好ましく、（メタ）アクリル酸２－ジアルキルアミノエチル、３－ジアルキルアミノプロピル（メタ）アクリルアミドがより好ましい。 -Manufacturing method of (2)-
The nitrogen atom-containing monomer used in the production method (2) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2-dialkylaminoethyl (meth) acrylate, 3- Examples thereof include dialkylaminopropyl (meth) acrylamide, vinylpyridine, N-vinylimidazole and the like. Among these, a monomer containing a tertiary amino group is preferable, and 2-dialkylaminoethyl (meth) acrylate and 3-dialkylaminopropyl (meth) acrylamide are more preferable.
　前記（２）の製造方法に用いる、前記ｐＫａが１４以下である官能基を一部に有する基を含有するモノマーとしては、前記ｐＫａが１４以下である官能基を一部に有する基を含有する（メタ）アクリル酸アミドが好ましく、例えば、Ｎ－（メタ）アクリロイルグリシン、Ｎ－（メタ）アクリロイルアラニン等の（メタ）アクリロイル基を含有するアミノ酸がより好ましい。 The monomer containing a group partially having a functional group having a pKa of 14 or less used in the production method of (2) includes a group partially having a functional group having a pKa of 14 or less. (Meth) acrylic acid amides are preferred, and amino acids containing a (meth) acryloyl group such as N- (meth) acryloylglycine and N- (meth) acryloylalanine are more preferred.
　前記（２）の製造方法に用いる、前記数平均分子量が５００～１，０００，０００のグラフト鎖を含有するモノマーとしては、公知のモノマーが挙げられるが、ポリ（メタ）アクリル酸エステル、ポリスチレン又はポリエステルの片末端に重合性基を有しているマクロモノマーが好ましい。また、このようなモノマーとしては、東亜合成社製マクロモノマーＡＡ－６（末端基がメタクリロイル基であるポリメタクリル酸メチル）、ＡＳ－６（末端基がメタクリロイル基であるポリスチレン）、ＡＮ－６Ｓ（末端基がメタクリロイル基であるスチレンとアクリロニトリルの共重合体）、ＡＢ－６（末端基がメタクリロイル基であるポリアクリル酸ブチル）、ダイセル化学社製プラクセルＦＭ５（メタクリル酸２－ヒドロキシエチルのε－カプロラクトン５モル当量付加品）、ＦＡ１０Ｌ（アクリル酸２－ヒドロキシエチルのε－カプロラクトン１０モル当量付加品）、特開平２－２７２００９号公報に記載のポリエステル系マクロマーが好ましい。 Examples of the monomer containing a graft chain having a number average molecular weight of 500 to 1,000,000 used in the production method of (2) include known monomers, such as poly (meth) acrylate, polystyrene or A macromonomer having a polymerizable group at one end of the polyester is preferred. Examples of such a monomer include macromonomers AA-6 (polymethyl methacrylate having a methacryloyl group at the end group), AS-6 (polystyrene having a methacryloyl group at the end group), AN-6S (manufactured by Toa Gosei Co., Ltd.). Copolymer of styrene and acrylonitrile whose end groups are methacryloyl groups), AB-6 (polybutyl acrylate whose end groups are methacryloyl groups), Plaxel FM5 (epsilon-caprolactone of 2-hydroxyethyl methacrylate) 5 mol equivalent addition product), FA10L (10 mol equivalent addition product of ε-caprolactone of 2-hydroxyethyl acrylate) and polyester macromer described in JP-A-2-272009 are preferred.
　前記（２）の製造方法における重合は、窒素雰囲気下、ラジカル重合開始剤を用いて行うことが好ましい。
　前記ラジカル重合開始剤としては、公知のラジカル重合開始剤を用いることができるが、アゾビスイソブチロニトリル、２，２’－アゾビスイソ酪酸メチルが、分子量の調整や取り扱いの点から好ましい。
　前記ラジカル重合開始剤は、全モノマーのモル数に対し、０．０１モル％～１０モル％用いることが好ましく、０．１モル％～５モル％用いることがより好ましい。
　前記重合において分子量を調整するために、連鎖移動剤を添加しても良い。前記連鎖移動剤としては、オール化合物が好ましく、炭素数５～２０のアルカンチオール、２－メルカプトエタノール、２－メルカプトプロピオン酸がより好ましい。
　前記連鎖移動剤は、全モノマーのモル数に対し、０．０１モル％～１０モル％用いることが好ましく、０．１モル％～５モル％用いることがより好ましい。 The polymerization in the production method (2) is preferably performed using a radical polymerization initiator in a nitrogen atmosphere.
As the radical polymerization initiator, known radical polymerization initiators can be used, but azobisisobutyronitrile and methyl 2,2′-azobisisobutyrate are preferable from the viewpoint of adjustment of molecular weight and handling.
The radical polymerization initiator is preferably used in an amount of 0.01 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, based on the number of moles of all monomers.
In order to adjust the molecular weight in the polymerization, a chain transfer agent may be added. The chain transfer agent is preferably an all compound, more preferably an alkanethiol having 5 to 20 carbon atoms, 2-mercaptoethanol, or 2-mercaptopropionic acid.
The chain transfer agent is preferably used in an amount of 0.01 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, based on the number of moles of all monomers.
　前記重合における反応温度としては、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、６０℃～１００℃が好ましく、７０℃～９０℃がより好ましい。
　前記重合における反応溶媒としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記（１）の製造方法で例示した溶媒が挙げられる。 The reaction temperature in the polymerization is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 100 ° C, more preferably 70 ° C to 90 ° C.
There is no restriction | limiting in particular as a reaction solvent in the said superposition | polymerization, According to the objective, it can select suitably, For example, the solvent illustrated by the manufacturing method of said (1) is mentioned.
　このようにして得られた前記窒素原子含有樹脂の重量平均分子量としては、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、３，０００～１，０００，０００であることが好ましく、５，０００～５００，０００であることがより好ましい。前記重量平均分子量が前記範囲であると、高現像性、及び保存安定性の点で有利である。 The weight average molecular weight of the nitrogen atom-containing resin thus obtained is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3,000 to 1,000,000. 5,000 to 500,000 is more preferable. When the weight average molecular weight is in the above range, it is advantageous in terms of high developability and storage stability.
　前記窒素原子含有樹脂の含有量としては、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、前記感光性組成物の固形分１００質量部に対して、０．１質量部～７０質量部が好ましく、１．０質量部～５０質量部がより好ましく、２．０質量部～３０質量部が特に好ましい。前記含有量が、０．１質量部未満であると、フィラーの分散性が低下し、粘度が上がることがあり、７０質量部を超えると、フィラーの分散時に粒子間架橋し、保存安定性が低下することがある。前記含有量が、前記特に好ましい範囲であると、フィラー分散後の安定性の点で有利である。 The content of the nitrogen atom-containing resin is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.1 to 70 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Part by mass is preferable, 1.0 part by mass to 50 parts by mass is more preferable, and 2.0 part by mass to 30 parts by mass is particularly preferable. When the content is less than 0.1 parts by mass, the dispersibility of the filler may decrease and the viscosity may increase. When the content exceeds 70 parts by mass, the particles are cross-linked during dispersion of the filler, and the storage stability is improved. May decrease. When the content is within the particularly preferable range, it is advantageous in terms of stability after dispersing the filler.
　前記窒素原子含有樹脂の前記窒素原子を有する主鎖における窒素原子の存在は、酸滴定などの方法により確認することができる。
　前記窒素原子含有樹脂の前記ｐＫａが１４以下である官能基の存在、及び、その官能基を有する基が前記窒素原子を有する主鎖に存在する窒素原子と結合していることは塩基滴定、核磁気共鳴分光法、赤外分光法などの方法により確認することができる。
　前記窒素原子含有樹脂の前記数平均分子量が５００～１，０００，０００のグラフト鎖が前記窒素原子を有する主鎖と結合していることは、核磁気共鳴分光法、ＧＰＣ法などの方法で確認することができる。 The presence of nitrogen atoms in the main chain having nitrogen atoms of the nitrogen atom-containing resin can be confirmed by a method such as acid titration.
The presence of a functional group having a pKa of 14 or less in the nitrogen atom-containing resin, and that the group having the functional group is bonded to the nitrogen atom present in the main chain having the nitrogen atom is determined by base titration, nucleus This can be confirmed by methods such as magnetic resonance spectroscopy and infrared spectroscopy.
It is confirmed by a method such as nuclear magnetic resonance spectroscopy or GPC that the graft chain having the number average molecular weight of 500 to 1,000,000 of the nitrogen atom-containing resin is bonded to the main chain having the nitrogen atom. can do.
　以下に、前記窒素原子含有樹脂の具体例をその分子量とともに記載する。
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
 Below, the specific example of the said nitrogen atom containing resin is described with the molecular weight.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
＜樹脂＞
　前記樹脂としては、前記窒素原子含有樹脂以外の樹脂であり、かつ感光性基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であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、感光性基及び酸基を導入したポリ（メタ）アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリアミック酸樹脂、ポリエーテル樹脂、ポリ尿素樹脂、ポリカーボネート樹脂などが挙げられる。さらに、２個以上のエポキシ基を有するエポキシ樹脂とビニル基含有有機酸とを反応させた後、更に多塩基酸無水物を反応させて得られる重合体；カルボキシル基含有樹脂の少なくとも一部の酸基にグリシジル基乃至脂環式エポキシ基を有するビニル化合物を付加させた変性共重合体；ヒドロキシル基含有樹脂の少なくとも一部のヒドロキシル基にイソシアナト基乃至酸無水物基を有するビニル化合物を付加させた変性共重合体；アミノ基含有樹脂の少なくとも一部のアミノ基にイソシアナト基乃至酸無水物基を有するビニル化合物を付加させた変性共重合体；ビニル基含有ジオール乃至ジアミンの共重合体；グリシジル基乃至オキセタニル基乃至脂環式エポキシ基を有するビニル化合物の開環重合体などが挙げられる。 <Resin>
The resin is not particularly limited as long as it is a resin other than the nitrogen atom-containing resin and is a compound into which an acid group for imparting a photosensitive group and alkali developability is introduced, and is appropriately selected depending on the purpose. For example, a poly (meth) acrylic resin, a polyester resin, a polyurethane resin, a polyamide resin, a polyamic acid resin, a polyether resin, a polyurea resin, a polycarbonate resin and the like into which a photosensitive group and an acid group have been introduced may be mentioned. . Further, a polymer obtained by reacting an epoxy resin having two or more epoxy groups with a vinyl group-containing organic acid, and further reacting with a polybasic acid anhydride; at least a part of the acid of the carboxyl group-containing resin Modified copolymer in which a vinyl compound having a glycidyl group or an alicyclic epoxy group is added to a group; a vinyl compound having an isocyanato group or an acid anhydride group is added to at least a part of hydroxyl groups of a hydroxyl group-containing resin Modified copolymer; modified copolymer obtained by adding a vinyl compound having an isocyanate group or an acid anhydride group to at least a part of amino groups of an amino group-containing resin; a copolymer of a vinyl group-containing diol or a diamine; a glycidyl group Or a ring-opening polymer of a vinyl compound having an oxetanyl group or an alicyclic epoxy group.
　これらの中でも、２個以上のエポキシ基を有するエポキシ樹脂とビニル基含有有機酸とを反応させた後、更に多塩基酸無水物を反応させて得られる重合体、ポリイソシアネートとポリイソシアネートからなるポリウレタン樹脂が好ましい。 Among these, a polymer obtained by reacting an epoxy resin having two or more epoxy groups with a vinyl group-containing organic acid and further reacting with a polybasic acid anhydride, a polyurethane comprising polyisocyanate and polyisocyanate Resins are preferred.
　前記ポリウレタン樹脂としては、ポリイソシアネートとポリイソシアネートに由来する構造を有しており、前記ポリウレタン樹脂としては、アルカリ現像性と硬化膜の強靭性という点から酸変性ビニル基含有ポリウレタン樹脂を使用することが好ましい。 The polyurethane resin has a structure derived from polyisocyanate and polyisocyanate, and as the polyurethane resin, an acid-modified vinyl group-containing polyurethane resin is used in terms of alkali developability and toughness of a cured film. Is preferred.
－酸変性ビニル基含有ポリウレタン樹脂－
　前記酸変性ビニル基含有ポリウレタン樹脂としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、（ｉ）側鎖にエチレン性不飽和結合を有するポリウレタン樹脂、（ｉｉ）カルボキシル基含有ポリウレタンと分子中にエポキシ基とビニル基を有する化合物とを反応して得られるポリウレタン樹脂、などが挙げられる。 -Acid-modified vinyl group-containing polyurethane resin-
The acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (i) a polyurethane resin having an ethylenically unsaturated bond in the side chain, (ii) a carboxyl group Examples thereof include a polyurethane resin obtained by reacting a containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule.
－－（ｉ）側鎖にエチレン性不飽和結合を有するポリウレタン樹脂－－
　前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、その側鎖に、下記一般式（１）～（３）で表される官能基のうち少なくとも１つを有するものが挙げられる。 -(I) Polyurethane resin having an ethylenically unsaturated bond in the side chain--
The polyurethane resin having an ethylenically unsaturated bond in the side chain is not particularly limited and may be appropriately selected depending on the purpose. For example, the side chain may be represented by the following general formulas (1) to (3). What has at least 1 among the functional groups represented is mentioned.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　前記一般式（１）中、Ｒ１～Ｒ３は、それぞれ独立に、水素原子及び１価の有機基のいずれかを表す。前記Ｒ1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、例えば、水素原子、置換基を有してもよいアルキル基、などが挙げられる。これらの中でも、ラジカル反応性が高い点で、水素原子、メチル基が好ましい。また、前記Ｒ２及びＲ３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、それぞれ独立に、例えば、水素原子、ハロゲン原子、アミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、置換基を有してもよいアリールスルホニル基、などが挙げられる。これらの中でも、ラジカル反応性が高い点で、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基が好ましい。
　前記一般式（１）中、Ｘは、酸素原子、硫黄原子、及び－Ｎ（Ｒ１２）－のいずれかを表し、前記Ｒ１２は、水素原子及び１価の有機基のいずれかを表す。前記Ｒ１２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、例えば、置換基を有してもよいアルキル基、などが挙げられる。これらの中でも、ラジカル反応性が高い点で、水素原子、メチル基、エチル基、イソプロピル基が好ましい。
　ここで、導入し得る前記置換基としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、アルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、ハロゲン原子、アミノ基、アルキルアミノ基、アリールアミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、アミド基、アルキルスルホニル基、アリールスルホニル基、などが挙げられる。 In the general formula (1), R 1 to R 3 each independently represents either a hydrogen atom or a monovalent organic group. R 1 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity. The R 2 and R 3 are not particularly limited and may be appropriately selected depending on the purpose. For example, each of R 2 and R 3 is independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group. Group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryl which may have a substituent An oxy group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent , Etc. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.
In the general formula (1), X represents an oxygen atom, a sulfur atom, and -N (R 12) - represents one of the R 12 represents a hydrogen atom or a monovalent organic group. R 12 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group which may have a substituent. Among these, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
Here, the substituent that can be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom. Amino group, alkylamino group, arylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group, and the like.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　前記一般式（２）中、Ｒ４～Ｒ８は、それぞれ独立に、水素原子及び１価の有機基のいずれかを表す。前記Ｒ４～Ｒ８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、水素原子、ハロゲン原子、アミノ基、ジアルキルアミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、置換基を有してもよいアリールスルホニル基、などが挙げられる。これらの中でも、ラジカル反応性が高い点で、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基が好ましい。 In the general formula (2), R 4 to R 8 each independently represents either a hydrogen atom or a monovalent organic group. R 4 to R 8 are not particularly limited and may be appropriately selected depending on the intended purpose. Hydrogen atoms, halogen atoms, amino groups, dialkylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, nitro groups , A cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, substituted An alkylamino group which may have a group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. It is done. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.
　導入し得る置換基としては、前記一般式（１）と同様のものが挙げられる。また、Ｙは、酸素原子、硫黄原子、及び－Ｎ（Ｒ１２）－のいずれかを表す。前記Ｒ12は、前記一般式（１）のＲ１２の場合と同義であり、好ましい例も同様である。 Examples of the substituent that can be introduced include the same as those in the general formula (1). Y represents any of an oxygen atom, a sulfur atom, and —N (R 12 ) —. Wherein R 12 has the same meaning as R 12 in the general formula (1), and preferred examples are also the same.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　前記一般式（３）中、Ｒ９～Ｒ１１は、それぞれ独立に、水素原子及び１価の有機基のいずれかを表す。前記一般式（３）中、前記Ｒ９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、水素原子、置換基を有してもよいアルキル基などが挙げられる。これらの中でも、ラジカル反応性が高い点で、水素原子、メチル基が好ましい。前記一般式（３）中、前記Ｒ１０及びＲ１１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、水素原子、ハロゲン原子、アミノ基、ジアルキルアミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、置換基を有してもよいアリールスルホニル基、などが挙げられる。これらの中でも、ラジカル反応性が高い点で、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基が好ましい。 In the general formula (3), R 9 to R 11 each independently represents a hydrogen atom or a monovalent organic group. In the general formula (3), R 9 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity. In the general formula (3), the R 10 and R 11 are not particularly limited and may be appropriately selected depending on the intended purpose. A hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxy group A carbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent An aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. A good arylsulfonyl group, and the like. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.
　ここで、導入し得る置換基としては、前記一般式（１）と同様のものが例示される。また、Ｚは、酸素原子、硫黄原子、－Ｎ（Ｒ１３）－、又は置換基を有してもよいフェニレン基を表す。前記Ｒ１３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、置換基を有してもよいアルキル基、などが挙げられる。これらの中でも、ラジカル反応性が高い点で、メチル基、エチル基、イソプロピル基が好ましい。 Here, examples of the substituent that can be introduced are the same as those in the general formula (1). Z represents an oxygen atom, a sulfur atom, —N (R 13 ) —, or an optionally substituted phenylene group. There is no restriction | limiting in particular as said R < 13 >, According to the objective, it can select suitably, The alkyl group etc. which may have a substituent are mentioned. Among these, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
　前記側鎖にエチレン性不飽和結合を有するウレタン樹脂は、下記一般式（４）で表されるジイソシアネート化合物の少なくとも１種と、下記一般式（５）で表されるジオール化合物の少なくとも１種と、の反応生成物で表される構造単位を基本骨格とするポリウレタン樹脂である。 The urethane resin having an ethylenically unsaturated bond in the side chain includes at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the following general formula (5): A polyurethane resin having a structural unit represented by the reaction product as a basic skeleton.
ＯＣＮ－Ｘ０－ＮＣＯ（４）
ＨＯ－Ｙ０－ＯＨ（５） OCN-X 0 -NCO (4)
HO—Y 0 —OH (5)
　前記一般式（４）及び（５）中、Ｘ０、Ｙ０は、それぞれ独立に２価の有機残基を表す。 In the general formulas (4) and (5), X 0 and Y 0 each independently represent a divalent organic residue.
　前記一般式（４）で表されるジイソシアネート化合物、又は、前記一般式（５）で表されるジオール化合物の少なくともどちらか一方が、前記一般式（１）～（３）で表される基のうち少なくとも１つを有していれば、当該ジイソシアネート化合物と当該ジオール化合物との反応生成物として、側鎖に前記一般式（１）～（３）で表される基が導入されたポリウレタン樹脂が生成される。かかる方法によれば、ポリウレタン樹脂の反応生成後に所望の側鎖を置換、導入するよりも、側鎖に前記一般式（１）～（３）で表される基が導入されたポリウレタン樹脂を容易に製造することができる。 At least one of the diisocyanate compound represented by the general formula (4) and the diol compound represented by the general formula (5) is a group represented by the general formulas (1) to (3). If at least one of them is present, a polyurethane resin in which the groups represented by the above general formulas (1) to (3) are introduced into the side chain as a reaction product of the diisocyanate compound and the diol compound is provided. Generated. According to such a method, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain can be easily used, rather than replacing and introducing a desired side chain after the reaction of the polyurethane resin. Can be manufactured.
　前記一般式（４）で表されるジイソシアネート化合物としては、特に制限されるものではなく、目的に応じて適宜選択することができ、例えば、トリイソシアネート化合物と、不飽和基を有する単官能のアルコール又は単官能のアミン化合物１当量とを付加反応させて得られる生成物などが挙げられる。
　前記トリイソシアネート化合物としては、特に制限されるものではなく、目的に応じて適宜選択することができ、例えば、特開２００５－２５０４３８号公報の段落「００３４」～「００３５」に記載された化合物、などが挙げられる。 The diisocyanate compound represented by the general formula (4) is not particularly limited and can be appropriately selected depending on the purpose. For example, a triisocyanate compound and a monofunctional alcohol having an unsaturated group Or the product obtained by addition-reacting with 1 equivalent of monofunctional amine compounds is mentioned.
The triisocyanate compound is not particularly limited and may be appropriately selected depending on the purpose. For example, the compounds described in paragraphs “0034” to “0035” of JP-A-2005-250438, Etc.
　前記不飽和基を有する単官能のアルコール又は前記単官能のアミン化合物としては、特に制限されるものではなく、目的に応じて適宜選択することができ、例えば、特開２００５－２５０４３８号公報の段落「００３７」～「００４０」に記載された化合物、などが挙げられる。 The monofunctional alcohol having an unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs of JP-A-2005-250438 And compounds described in “0037” to “0040”.
　ここで、前記ポリウレタン樹脂の側鎖に不飽和基を導入する方法としては、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、ポリウレタン樹脂製造の原料として、側鎖に不飽和基を含有するジイソシアネート化合物を用いる方法が好ましい。前記ジイソシアネート化合物としては、特に制限はなく、目的に応じて適宜選択することができ、トリイソシアネート化合物と不飽和基を有する単官能のアルコール又は単官能のアミン化合物１当量とを付加反応させることにより得ることできるジイソシアネート化合物であって、例えば、特開２００５－２５０４３８号公報の段落「００４２」～「００４９」に記載された側鎖に不飽和基を有する化合物などが挙げられる。 Here, the method for introducing an unsaturated group into the side chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. A method using a diisocyanate compound containing is preferable. There is no restriction | limiting in particular as said diisocyanate compound, According to the objective, it can select suitably, By carrying out addition reaction of the monoisocyanate which has a triisocyanate compound, and a monofunctional amine compound or monofunctional amine compound. Examples of the diisocyanate compound that can be obtained include compounds having an unsaturated group in the side chain described in paragraphs “0042” to “0049” of JP-A-2005-250438.
　前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂は、重合性組成物中の他の成分との相溶性を向上させ、保存安定性を向上させるといった観点から、前記不飽和基を含有するジイソシアネート化合物以外のジイソシアネート化合物を共重合させることもできる。 The polyurethane resin having an ethylenically unsaturated bond in the side chain is a diisocyanate containing the unsaturated group from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. Diisocyanate compounds other than the compounds can also be copolymerized.
　前記共重合させるジイソシアネート化合物としては、特に制限はなく、目的に応じて適宜選択することでき、例えば、下記一般式（６）で表されるジイソシアネート化合物である。 The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a diisocyanate compound represented by the following general formula (6).
ＯＣＮ－Ｌ１－ＮＣＯ（６） OCN-L 1 -NCO (6)
　前記一般式（６）中、Ｌ１は、置換基を有していてもよい２価の脂肪族又は芳香族炭化水素基を表す。必要に応じ、Ｌ１は、イソシアネート基と反応しない他の官能基、例えば、エステル、ウレタン、アミド、ウレイド基を有していてもよい。 In the general formula (6), L 1 represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L 1 may have another functional group that does not react with an isocyanate group, for example, an ester, urethane, amide, or ureido group.
　前記一般式（６）で表されるジイソシアネート化合物としては、特に制限はなく、目的に応じて適宜選択することでき、例えば、２，４－トリレンジイソシアネート、２，４－トリレンジイソシアネートの二量体、２，６－トリレンジレンジイソシアネート、ｐ－キシリレンジイソシアネート、ｍ－キシリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、１，５－ナフチレンジイソシアネート、３，３’－ジメチルビフェニル－４，４’－ジイソシアネート等のような芳香族ジイソシアネート化合物；ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、ダイマー酸ジイソシアネート等の脂肪族ジイソシアネート化合物；イソホロンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、メチルシクロヘキサン－２，４（又は２，６）ジイソシアネート、１，３－（イソシアネートメチル）シクロヘキサン等の脂環族ジイソシアネート化合物；１，３－ブチレングリコール１モルとトリレンジイソシアネート２モルとの付加体等のジオールとジイソシアネートとの反応物であるジイソシアネート化合物；などが挙げられる。 The diisocyanate compound represented by the general formula (6) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, dimer of 2,4-tolylene diisocyanate and 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4 Aromatic diisocyanate compounds such as' -diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate; isophorone diisocyanate, 4,4 -Alicyclic diisocyanate compounds such as methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate And a diisocyanate compound that is a reaction product of a diol such as an adduct with 2 mol and a diisocyanate.
　前記一般式（５）で表されるジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリエーテルジオール化合物、ポリエステルジオール化合物、ポリカーボネートジオール化合物、などが挙げられる。 There is no restriction | limiting in particular as a diol compound represented by the said General formula (5), According to the objective, it can select suitably, For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound etc. are mentioned. .
　ここで、ポリウレタン樹脂の側鎖に不飽和基を導入する方法としては、前述の方法の他に、ポリウレタン樹脂製造の原料として、側鎖に不飽和基を含有するジオール化合物を用いる方法も好ましい。前記側鎖に不飽和基を含有するジオール化合物は、例えば、トリメチロールプロパンモノアリルエーテルのように市販されているものでもよいし、ハロゲン化ジオール化合物、トリオール化合物、アミノジオール化合物等の化合物と、不飽和基を含有する、カルボン酸、酸塩化物、イソシアネート、アルコール、アミン、チオール、ハロゲン化アルキル化合物等の化合物との反応により容易に製造される化合物であってもよい。前記側鎖に不飽和基を含有するジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００５－２５０４３８号公報の段落「００５７」～「００６０」に記載された化合物、下記一般式（Ｇ）で表される特開２００５－２５０４３８号公報の段落「００６４」～「００６６」に記載された化合物、などが挙げられる。これらの中でも、下記一般式（Ｇ）で表される特開２００５－２５０４３８号公報の段落「００６４」～「００６６」に記載された化合物が好ましい。
Figure JPOXMLDOC01-appb-C000038
 　前記一般式（Ｇ）中、Ｒ１～Ｒ３は、それぞれ独立に水素原子又は１価の有機基を表し、Ａは２価の有機残基を表し、Ｘは、酸素原子、硫黄原子、又は－Ｎ（Ｒ１２）－を表し、前記Ｒ１２は、水素原子、又は１価の有機基を表す。
　なお、前記一般式（Ｇ）におけるＲ１～Ｒ３及びＸは、前記一般式（１）におけるＲ１～Ｒ３及びＸと同義であり、好ましい態様もまた同様である。
　前記一般式（Ｇ）で表されるジオール化合物に由来するポリウレタン樹脂を用いることにより、立体障害の大きい２級アルコールに起因するポリマー主鎖の過剰な分子運動を抑制効果により、層の被膜強度の向上が達成できるものと考えられる。 Here, as a method for introducing an unsaturated group into the side chain of the polyurethane resin, in addition to the above-described method, a method using a diol compound containing an unsaturated group in the side chain as a raw material for producing the polyurethane resin is also preferable. The diol compound containing an unsaturated group in the side chain may be, for example, a commercially available product such as trimethylolpropane monoallyl ether, and a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound; The compound which is easily manufactured by reaction with compounds, such as a carboxylic acid, an acid chloride, an isocyanate, alcohol, an amine, a thiol, and a halogenated alkyl compound containing an unsaturated group, may be sufficient. The diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0057” to “0060” of JP-A-2005-250438 And the compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438 represented by the following general formula (G). Among these, compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438 represented by the following general formula (G) are preferable.
Figure JPOXMLDOC01-appb-C000038
 In the general formula (G), R 1 to R 3 each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or —N (R 12 ) —, wherein R 12 represents a hydrogen atom or a monovalent organic group.
Incidentally, R 1 ~ R 3 and X in the general formula (G), said a general formula (1) the same meaning as R 1 ~ R 3 and X in preferred embodiments versa.
By using the polyurethane resin derived from the diol compound represented by the general formula (G), the effect of suppressing the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance can be reduced. It is thought that improvement can be achieved.
　前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂は、例えば、感光性組成物中の他の成分との相溶性を向上させ、保存安定性を向上させるといった観点から、前記側鎖に不飽和基を含有するジオール化合物以外のジオール化合物を共重合させることができる。
　前記側鎖に不飽和基を含有するジオール化合物以外のジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリエーテルジオール化合物、ポリエステルジオール化合物、ポリカーボネートジオール化合物、などが挙げられる。 The polyurethane resin having an ethylenically unsaturated bond in the side chain is unsaturated in the side chain from the viewpoint of, for example, improving compatibility with other components in the photosensitive composition and improving storage stability. A diol compound other than a diol compound containing a group can be copolymerized.
The diol compound other than the diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the purpose. For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, Etc.
　前記ポリエーテルジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００５－２５０４３８号公報の段落「００６８」～「００７６」に記載された化合物などが挙げられる。 The polyether diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs “0068” to “0076” of JP-A-2005-250438. It is done.
　前記ポリエステルジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００５－２５０４３８号公報の段落「００７７」～「００７９」、段落「００８３」～「００８５」におけるＮｏ．１～Ｎｏ．８及びＮｏ．１３～Ｎｏ．１８に記載された化合物などが挙げられる。 The polyester diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paragraphs “0077” to “0079” and paragraphs “0083” to “0085” of JP-A-2005-250438. No. 1-No. 8 and no. 13-No. 18 and the like.
　前記ポリカーボネートジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００５－２５０４３８号公報の段落「００８０」～「００８１」及び段落「００８４」におけるＮｏ．９～Ｎｏ．１２記載された化合物などが挙げられる。 The polycarbonate diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the paragraphs “0080” to “0081” and paragraph “0084” of JP-A-2005-250438, No. 9-No. 12 listed compounds.
　また、前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂の合成には、上述したジオール化合物の他に、イソシアネート基と反応しない置換基を有するジオール化合物を併用することもできる。
　前記イソシアネート基と反応しない置換基を有するジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００５－２５０４３８号公報の段落「００８７」～「００８８」に記載された化合物などが挙げられる。 Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in the said side chain, the diol compound which has a substituent which does not react with an isocyanate group other than the diol compound mentioned above can also be used together.
The diol compound having a substituent that does not react with the isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0087” to “0088” of JP-A-2005-250438 And the compounds described.
　さらに、前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂の合成には、上述したジオール化合物の他に、カルボキシル基を有するジオール化合物を併用することもできる。前記カルボキシル基を有するジオール化合物としては、例えば、以下の一般式（１７）～（１９）に示すものが含まれる。 Furthermore, in the synthesis of the polyurethane resin having an ethylenically unsaturated bond in the side chain, a diol compound having a carboxyl group can be used in combination with the diol compound described above. Examples of the diol compound having a carboxyl group include those represented by the following general formulas (17) to (19).
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　前記一般式（１７）～（１９）中、Ｒ１５としては、水素原子、置換基（例えば、シアノ基、ニトロ基、－Ｆ、－Ｃｌ、－Ｂｒ、－Ｉ等のハロゲン原子、－ＣＯＮＨ２、－ＣＯＯＲ１６、－ＯＲ１６、－ＮＨＣＯＮＨＲ１６、－ＮＨＣＯＯＲ１６、－ＮＨＣＯＲ１６、－ＯＣＯＮＨＲ１６（ここで、前記Ｒ１６は、炭素数１～１０のアルキル基、又は炭素数７～１５のアラルキル基を表す。）などの各基が含まれる。）を有していてもよいアルキル基、アラルキル基、アリール基、アルコキシ基、アリーロキシ基を表すものである限り、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、水素原子、炭素数１～８個のアルキル基、炭素数６～１５個のアリール基が好ましい。前記一般式（１７）～（１９）中、Ｌ９、Ｌ１０、Ｌ１１は、それぞれ同一でもよいし、相違していてもよく、単結合、置換基（例えば、アルキル、アラルキル、アリール、アルコキシ、ハロゲノの各基が好ましい。）を有していてもよい２価の脂肪族又は芳香族炭化水素基を表すものである限り、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、炭素数１～２０個のアルキレン基、炭素数６～１５個のアリーレン基が好ましく、炭素数１～８個のアルキレン基がより好ましい。また必要に応じ、前記Ｌ９～Ｌ１１中にイソシアネート基と反応しない他の官能基、例えば、カルボニル、エステル、ウレタン、アミド、ウレイド、エーテル基を有していてもよい。なお、前記Ｒ１５、Ｌ７、Ｌ８、Ｌ９のうちの２個又は３個で環を形成してもよい。
　前記一般式（１８）中、Ａｒとしては、置換基を有していてもよい三価の芳香族炭化水素基を表すものである限り、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、炭素数６～１５個の芳香族基が好ましい。 In the general formulas (17) to (19), R 15 represents a hydrogen atom, a substituent (for example, a cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc.), —CONH 2 , —COOR 16 , —OR 16 , —NHCONHR 16 , —NHCOOR 16 , —NHCOR 16 , —OCONHR 16 (wherein R 16 is an alkyl group having 1 to 10 carbon atoms, or aralkyl having 7 to 15 carbon atoms) Each group such as a group represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group, which may have a group, and is not particularly limited. A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable. In the general formulas (17) to (19), L 9 , L 10 and L 11 may be the same or different from each other, and may be a single bond, a substituent (for example, alkyl, aralkyl, aryl, alkoxy). And each group of halogeno are preferred.), As long as they represent a divalent aliphatic or aromatic hydrocarbon group which may have a substituent, and can be appropriately selected according to the purpose. An alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. If necessary, the L 9 to L 11 may have other functional groups that do not react with isocyanate groups, such as carbonyl, ester, urethane, amide, ureido, and ether groups. In addition, you may form a ring by two or three of said R < 15 >, L < 7 >, L < 8 >, L < 9 >.
In the general formula (18), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and may be appropriately selected according to the purpose. An aromatic group having 6 to 15 carbon atoms is preferable.
　上記一般式（１７）～（１９）で表されるカルボキシル基を有するジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、３，５－ジヒドロキシ安息香酸、２，２－ビス（ヒドロキシメチル）プロピオン酸、２，２－ビス（２－ヒドロキシエチル）プロピオン酸、２，２－ビス（３－ヒドロキシプロピル）プロピオン酸、ビス（ヒドロキシメチル）酢酸、ビス（４－ヒドロキシフェニル）酢酸、２，２－ビス（ヒドロキシメチル）酪酸、４，４－ビス（４－ヒドロキシフェニル）ペンタン酸、酒石酸、Ｎ，Ｎ－ジヒドロキシエチルグリシン、Ｎ，Ｎ―ビス（２－ヒドロキシエチル）－３－カルボキシ－プロピオンアミドなどが挙げられる。 The diol compound having a carboxyl group represented by the general formulas (17) to (19) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3,5-dihydroxybenzoic acid, 2 , 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4- Hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) ) -3-carboxy-propionamide and the like.
　このようなカルボキシル基の存在により、ポリウレタン樹脂に水素結合性とアルカリ可溶性といった特性を付与できるため好ましい。より具体的には、前記側鎖にエチレン性不飽和結合基を有するポリウレタン樹脂が、さらに側鎖にカルボキシル基を有する樹脂であり、より具体的には、側鎖のビニル基が、０．０５ｍｍｏｌ／ｇ～３．０ｍｍｏｌ／ｇであることが好ましく、０．５ｍｍｏｌ／ｇ～２．７ｍｍｏｌ／ｇであることがより好ましく、０．７５ｍｍｏｌ／ｇ～２．４ｍｍｏｌ／ｇであることが特に好ましく、且つ、側鎖にカルボキシル基を有することが好ましく、酸価が、２０ｍｇＫＯＨ／ｇ～１２０ｍｇＫＯＨ／ｇであることが好ましく、３０ｍｇＫＯＨ／ｇ～１１０ｍｇＫＯＨ／ｇであることがより好ましく、３５ｍｇＫＯＨ／ｇ～１００ｍｇＫＯＨ／ｇが特に好ましい。 It is preferable because the presence of such a carboxyl group can impart properties such as hydrogen bonding and alkali solubility to the polyurethane resin. More specifically, the polyurethane resin having an ethylenically unsaturated bond group in the side chain is a resin further having a carboxyl group in the side chain, and more specifically, the vinyl group in the side chain is 0.05 mmol. / G to 3.0 mmol / g, preferably 0.5 mmol / g to 2.7 mmol / g, more preferably 0.75 mmol / g to 2.4 mmol / g, The side chain preferably has a carboxyl group, and the acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and 35 mgKOH / g to 100 mgKOH / g. g is particularly preferred.
　また、側鎖にエチレン性不飽和結合を有するポリウレタン樹脂の合成には、上述したジオール化合物の他に、テトラカルボン酸二無水物をジオール化合物で開環させた化合物を併用することもできる。
　前記テトラカルボン酸二無水物をジオール化合物で開環させた化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００５－２５０４３８号公報の段落「００９５」～「０１０１」に記載された化合物などが挙げられる。 Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in a side chain, the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
The compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs “0095” to “2005” of JP-A-2005-250438 can be selected. And the compounds described in “0101”.
　前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂は、上記ジイソシアネート化合物及びジオール化合物を、非プロトン性溶媒中、それぞれの反応性に応じた活性の公知の触媒を添加し、加熱することにより合成される。合成に使用されるジイソシアネート及びジオール化合物のモル比（Ｍａ：Ｍｂ）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、１：１～１．２：１が好ましく、アルコール類又はアミン類等で処理することにより、分子量あるいは粘度といった所望の物性の生成物が、最終的にイソシアネート基が残存しない形で合成される。 The polyurethane resin having an ethylenically unsaturated bond in the side chain is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. Is done. The molar ratio (M a : M b ) of the diisocyanate and diol compound used in the synthesis is not particularly limited and can be appropriately selected according to the purpose, and is preferably 1: 1 to 1.2: 1. By treating with alcohols or amines, a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.
　前記エチレン性不飽和結合基の前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂における導入量としては、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、ビニル基当量としては、０．０５ｍｍｏｌ／ｇ～３．０ｍｍｏｌ／ｇが好ましく、０．５ｍｍｏｌ／ｇ～２．７ｍｍｏｌ／ｇがより好ましく、０．７５ｍｍｏｌ／ｇ～２．４ｍｍｏｌ／ｇが特に好ましい。さらに、前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂には、前記エチレン性不飽和結合基とともに、側鎖にカルボキシル基が導入されていることが好ましい。酸価としては、２０ｍｇＫＯＨ／ｇ～１２０ｍｇＫＯＨ／ｇが好ましく、３０ｍｇＫＯＨ／ｇ～１１０ｍｇＫＯＨ／ｇがより好ましく、３５ｍｇＫＯＨ／ｇ～１００ｍｇＫＯＨ／ｇが特に好ましい。 The amount of introduction in the polyurethane resin having an ethylenically unsaturated bond in the side chain of the ethylenically unsaturated bond group is not particularly limited and can be appropriately selected according to the purpose. 0.05 mmol / g to 3.0 mmol / g is preferable, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable. Furthermore, in the polyurethane resin having an ethylenically unsaturated bond in the side chain, it is preferable that a carboxyl group is introduced into the side chain together with the ethylenically unsaturated bond group. The acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and particularly preferably 35 mgKOH / g to 100 mgKOH / g.
　前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂の分子量としては、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、重量平均分子量で２，０００～５０，０００が好ましく、３，０００～３０，０００がより好ましい。特に、前記感光性組成物を感光性ソルダーレジストに用いた場合には、クラック耐性、耐熱性に優れ、アルカリ性現像液による非画像部の現像性に優れる。 The molecular weight of the polyurethane resin having an ethylenically unsaturated bond in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2,000 to 50,000 in terms of weight average molecular weight. 30,000 to 30,000 is more preferable. In particular, when the photosensitive composition is used for a photosensitive solder resist, it is excellent in crack resistance and heat resistance, and is excellent in developability of non-image areas with an alkaline developer.
　また、前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂としては、ポリマー末端、主鎖に不飽和基を有するものも好適に使用される。ポリマー末端、主鎖に不飽和基を有することにより、さらに、感光性組成物と側鎖にエチレン性不飽和結合を有するポリウレタン樹脂との間、又は側鎖にエチレン性不飽和結合を有するポリウレタン樹脂間で架橋反応性が向上し、光硬化物強度が増す。その結果、側鎖にエチレン性不飽和結合を有するポリウレタン樹脂をプリント配線板材料に使用した際、強靭性に優れる材料を与えることができる。ここで、不飽和基としては、架橋反応の起こり易さから、炭素－炭素二重結合を有することが特に好ましい。 Further, as the polyurethane resin having an ethylenically unsaturated bond in the side chain, those having an unsaturated group in the polymer terminal and main chain are also preferably used. Polyurethane resin having an ethylenically unsaturated bond in the side chain, or between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated bond in the side chain, by having an unsaturated group at the polymer terminal and main chain Crosslinking reactivity is improved, and the strength of the photocured product is increased. As a result, when a polyurethane resin having an ethylenically unsaturated bond in the side chain is used for the printed wiring board material, a material having excellent toughness can be provided. Here, it is particularly preferable that the unsaturated group has a carbon-carbon double bond from the viewpoint of easy occurrence of a crosslinking reaction.
　ポリマー末端に不飽和基を導入する方法としては、以下に示す方法がある。すなわち、上述した側鎖にエチレン性不飽和結合を有するポリウレタン樹脂の合成の工程での、ポリマー末端の残存イソシアネート基と、アルコール類又はアミン類等で処理する工程において、不飽和基を有するアルコール類又はアミン類等を用いればよい。このような化合物としては、具体的には、先に、不飽和基を有する単官能のアルコール又は単官能のアミン化合物として挙げられた例示化合物と同様のものを挙げることができる。
　なお、不飽和基は、導入量の制御が容易で導入量を増やすことができ、また、架橋反応効率が向上するといった観点から、ポリマー末端よりもポリマー側鎖に導入されることが好ましい。
　導入されるエチレン性不飽和結合基としては、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、架橋硬化膜形成性の点で、メタクリロイル基、アクリロイル基、スチリル基が好ましく、メタクリロイル基、アクリロイル基がより好ましく、架橋硬化膜の形成性と生保存性との両立の点で、メタクリロイル基が特に好ましい。
　また、メタクリロイル基の導入量としては、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、ビニル基当量としては、０．０５ｍｍｏｌ／ｇ～３．０ｍｍｏｌ／ｇが好ましく、０．５ｍｍｏｌ／ｇ～２．７ｍｍｏｌ／ｇがより好ましく、０．７５ｍｍｏｌ／ｇ～２．４ｍｍｏｌ／ｇが特に好ましい。 Examples of the method for introducing an unsaturated group at the polymer terminal include the following methods. That is, in the process of synthesizing a polyurethane resin having an ethylenically unsaturated bond in the side chain described above, in the process of treating with a residual isocyanate group at the polymer terminal and an alcohol or an amine, an alcohol having an unsaturated group Alternatively, amines or the like may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
The unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.
The ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. The vinyl group equivalent is preferably 0.05 mmol / g to 3.0 mmol / g, preferably 0.5 mmol. / G to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.
　主鎖に不飽和基を導入する方法としては、主鎖方向に不飽和基を有するジオール化合物をポリウレタン樹脂の合成に用いる方法がある。前記主鎖方向に不飽和基を有するジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、ｃｉｓ－２－ブテン－１，４－ジオール、ｔｒａｎｓ－２－ブテン－１，４－ジオール、ポリブタジエンジオール、などが挙げられる。 As a method for introducing an unsaturated group into the main chain, there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin. The diol compound having an unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, cis-2-butene-1,4-diol, trans-2-butene-1 , 4-diol, polybutadiene diol, and the like.
　前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂は、該特定ポリウレタン樹脂とは異なる構造を有するポリウレタン樹脂を含むアルカリ可溶性高分子を併用することも可能である。例えば、前記側鎖にエチレン性不飽和結合を有するポリウレタン樹脂は、は、主鎖及び／又は側鎖に芳香族基を含有したポリウレタン樹脂を併用することが可能である。 The polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin. For example, the polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.
　前記（ｉ）側鎖にエチレン性不飽和結合を有するポリウレタン樹脂の具体例としては、例えば、特開２００５－２５０４３８号公報の段落「０２９３」～「０３１０」に示されたＰ－１～Ｐ－３１のポリマー、などが挙げられる。これらの中でも、段落「０３０８」及び「０３０９」に示されたＰ－２７及びＰ－２８のポリマーが好ましい。 Specific examples of the (i) polyurethane resin having an ethylenically unsaturated bond in the side chain include, for example, P-1 to P— shown in paragraphs “0293” to “0310” of JP-A-2005-250438. 31 polymers, and the like. Among these, polymers of P-27 and P-28 shown in paragraphs “0308” and “0309” are preferable.
－－（ｉｉ）カルボキシル基含有ポリウレタンと分子中にエポキシ基とビニル基を有する化合物とを反応して得られるポリウレタン樹脂－－
　前記カルボキシル基含有ポリウレタンと分子中にエポキシ基とビニル基を有する化合物とを反応して得られるポリウレタン樹脂は、ジイソシアネートと、カルボン酸基含有ジオールとを必須成分とするカルボキシル基含有ポリウレタンと、分子中にエポキシ基とビニル基を有する化合物とを反応して得られるポリウレタン樹脂である。このポリウレタン樹脂には、目的に応じて、ジオール成分として、重量平均分子量３００以下の低分子ジオールや重量平均分子量５００以上の低分子ジオールを共重合成分として加えてもよい。
　前記ポリウレタン樹脂を用いることにより、無機充填剤との安定した分散性や耐クラック性や耐衝撃性に優れることから、耐熱性、耐湿熱性、密着性、機械特性、電気特性が向上する。
　また、前記ポリウレタン樹脂としては、置換基を有していてもよい二価の脂肪族及び芳香族炭化水素のジイソシアネートと、Ｃ原子及びＮ原子のいずれかを介してＣＯＯＨ基と２つのＯＨ基を有するカルボン酸含有ジオールとを必須成分とした反応物であって、得られた反応物と、－ＣＯＯ－結合を介して分子中にエポキシ基とビニル基を有する化合物とを反応して得られるものであってもよい。
　また、前記ポリウレタン樹脂としては、下記一般式（ＸＩ）で示されるジイソシアネートと、下記一般式（ＸＩＩ－１）～（ＸＩＩ－３）で示されるカルボン酸基含有ジオールから選ばれた少なくとも１種とを必須成分とし、目的に応じて下記一般式（ＸＩＩＩ－１）～（ＸＩＩＩ－５）で示される重量平均分子量が８００～３，０００の範囲にある高分子ジオールから選ばれた少なくとも１種との反応物であって、得られた反応物と、下記一般式（ＸＩＶ－１）～（ＸＩＶ－１６）で示される分子中にエポキシ基とビニル基を有する化合物とを反応して得られるものであってもよい。
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
 　ただし、前記一般式（ＸＩ）中、Ｒ１は、置換基（例えば、アルキル基、アラルキル基、アリール基、アルコキシ基、ハロゲノ基のいずれかが好ましい）を有していてもよい二価の脂肪族又は芳香族炭化水素を表す。必要に応じ、前記Ｒ１は、イソシアネート基と反応しない他の官能基、例えば、エステル基、ウレタン基、アミド基、ウレイド基のいずれかを有していてもよい。前記一般式（ＸＩ）中、Ｒ２は、水素原子、置換基（例えば、シアノ基、二トロ基、ハロゲン原子（－Ｆ、－Ｃｌ、－Ｂｒ、－Ｉ）、－ＣＯＮＨ２、－ＣＯＯＲ６、－ＯＲ６、－ＮＨＣＯＮＨＲ６、－ＮＨＣＯＯＲ６、－ＮＨＣＯＲ６、－ＯＣＯＮＨＲ６、－ＣＯＮＨＲ６（ここで、Ｒ６は、炭素数１～１０のアルキル基、炭素数７～１５のアラルキル基のいずれかを表す）、などの各基が含まれる）を有していてもよいアルキル基、アラルキル基、アリール基、アルコキシ基、又はアリーロキシ基を表す。これらの中でも、水素原子、炭素数１個～３個のアルキル基、炭素数６個～１５個のアリール基が好ましい。前記一般式（ＸＩＩ－１）及び（ＸＩＩ－２）中、Ｒ３、Ｒ４及びＲ５は、それぞれ同一でも相異していてもよく、単結合、置換基（例えば、アルキル基、アラルキル基、アリール基、アルコキシ基、ハロゲノ基の各基が好ましい）を有していてもよい二価の脂肪族又は芳香族炭化水素を表す。これらの中でも、炭素数１～２０個のアルキレン基、炭素数６～１５個のアリーレン基が好ましく、炭素数１～８個のアルキレン基が更に好ましい。また、必要に応じ、前記Ｒ３、Ｒ４及びＲ５中にイソシアネート基と反応しない他の官能基、例えば、カルボニル基、エステル基、ウレタン基、アミド基、ウレイド基、エーテル基のいずれかを有していてもよい。なお、前記Ｒ２、Ｒ３、Ｒ４及びＲ５のうちの２個又は３個で環を形成してもよい。Ａｒは置換基を有していてもよい三価の芳香族炭化水素を表し、炭素数６個～１５個の芳香族基が好ましい。
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
 　ただし、前記一般式（ＸＩＩＩ－１）～（ＸＩＩＩ－３）中、Ｒ７、Ｒ８、Ｒ９、Ｒ１０及びＲ１１は、それぞれ同一でもよいし、相異していてもよく、二価の脂肪族又は芳香族炭化水素を表す。前記Ｒ７、Ｒ９、Ｒ１０及びＲ１１は、それぞれ炭素数２個～２０個のアルキレン基又は炭素数６個～１５個のアリーレン基が好ましく、炭素数２個～１０個のアルキレン又は炭素数６個～１０個のアリーレン基がより好ましい。前記Ｒ８は、炭素数１個～２０個のアルキレン基又は炭素数６個～１５個のアリーレン基を表し、炭素数１個～１０個のアルキレン又は炭素数６個～１０個のアリーレン基がより好ましい。また、前記Ｒ７、Ｒ８、Ｒ９、Ｒ１０及びＲ１１中には、イソシアネート基と反応しない他の官能基、例えば、エーテル基、カルボニル基、エステル基、シアノ基、オレフィン基、ウレタン基、アミド基、ウレイド基、又はハロゲン原子などがあってもよい。前記一般式（ＸＩＩＩ－４）中、Ｒ１２は、水素原子、アルキル基、アリール基、アラルキル基、シアノ基又はハロゲン原子を表す。水素原子、炭素数１個～１０個のアルキル基、炭素数６個～１５個のアリール基、炭素数７個～１５個のアラルキル、シアノ基又はハロゲン原子が好ましく、水素原子、炭素数１個～６個のアルキル及び炭素数６個～１０個のアリール基がより好ましい。また、前記Ｒ１２中には、イソシアネート基と反応しない他の官能基、例えば、アルコキシ基、カルボニル基、オレフィン基、エステル基又はハロゲン原子などがあってもよい。
　前記一般式（ＸＩＩＩ－５）中、Ｒ１３は、アリール基又はシアノ基を表し、炭素数６個～１０個のアリール基又はシアノ基が好ましい。前記一般式（ＸＩＩＩ－４）中、ｍは、２～４の整数を表す。前記一般式（ＸＩＩＩ－１）～（ＸＩＩＩ－５）中、ｎ１、ｎ２、ｎ３、ｎ４及びｎ５は、それぞれ２以上の整数を表し、２～１００の整数が好ましい。前記一般式（ＸＩＩＩ－５）中、ｎ６は、０又は２以上の整数を示し、０又は２～１００の整数が好ましい。
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000064
 　ただし、前記一般式（ＸＩＶ－１）～（ＸＩＶ－１６）中、Ｒ１４は、水素原子又はメチル基を表し、Ｒ１５は、炭素数１～１０のアルキレン基を表し、Ｒ１６は、炭素数１～１０の炭化水素基を表す。ｐは、０又は１～１０の整数を表す。 -(Ii) Polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule--
A polyurethane resin obtained by reacting the carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule includes a carboxyl group-containing polyurethane having a diisocyanate and a carboxylic acid group-containing diol as essential components; And a polyurethane resin obtained by reacting a compound having an epoxy group and a vinyl group. Depending on the purpose, a low molecular weight diol having a weight average molecular weight of 300 or less or a low molecular diol having a weight average molecular weight of 500 or more may be added as a copolymer component to the polyurethane resin.
By using the polyurethane resin, it is excellent in stable dispersibility with an inorganic filler, crack resistance and impact resistance, so that heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties are improved.
The polyurethane resin includes a divalent aliphatic or aromatic hydrocarbon diisocyanate which may have a substituent, a COOH group and two OH groups via any one of a C atom and an N atom. A reaction product comprising a carboxylic acid-containing diol as an essential component, which is obtained by reacting the obtained reaction product with a compound having an epoxy group and a vinyl group in the molecule via a —COO— bond It may be.
The polyurethane resin includes at least one selected from diisocyanates represented by the following general formula (XI) and carboxylic acid group-containing diols represented by the following general formulas (XII-1) to (XII-3): And at least one selected from polymer diols having a weight average molecular weight in the range of 800 to 3,000 represented by the following general formulas (XIII-1) to (XIII-5) according to the purpose: A reaction product obtained by reacting the obtained reaction product with a compound having an epoxy group and a vinyl group in a molecule represented by the following general formulas (XIV-1) to (XIV-16) It may be.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
 However, in the general formula (XI), R 1 may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Represents an aromatic or aromatic hydrocarbon. If necessary, R 1 may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group. In the general formula (XI), R 2 represents a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH 2 , —COOR 6 , —OR 6 , —NHCONHR 6 , —NHCOOR 6 , —NHCOR 6 , —OCONHR 6 , —CONHR 6 (wherein R 6 is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) Represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable. In the general formulas (XII-1) and (XII-2), R 3 , R 4 and R 5 may be the same or different, and each may be a single bond, a substituent (for example, an alkyl group or an aralkyl group). , An aryl group, an alkoxy group, and a halogeno group are preferable). Among these, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. Further, if necessary, in R 3 , R 4 and R 5 , any other functional group that does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. You may have. In addition, you may form a ring by 2 or 3 of said R < 2 >, R < 3 >, R < 4 > and R < 5 >. Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and is preferably an aromatic group having 6 to 15 carbon atoms.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
 However, in the general formulas (XIII-1) to (XIII-3), R 7 , R 8 , R 9 , R 10 and R 11 may be the same or different, respectively. Represents an aliphatic or aromatic hydrocarbon. R 7 , R 9 , R 10 and R 11 are each preferably an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene or carbon having 2 to 10 carbon atoms Several to 10 arylene groups are more preferred. R 8 represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms is More preferred. In addition, in R 7 , R 8 , R 9 , R 10 and R 11 , other functional groups that do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups , An amide group, a ureido group, or a halogen atom. In the general formula (XIII-4), R 12 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group, or a halogen atom. A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or one carbon atom is preferable. More preferred are ˜6 alkyl and aryl groups having 6 to 10 carbon atoms. R 12 may have other functional groups that do not react with isocyanate groups, such as alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms.
In the general formula (XIII-5), R 13 represents an aryl group or a cyano group, preferably an aryl group or a cyano group having 6 to 10 carbon atoms. In the general formula (XIII-4), m represents an integer of 2 to 4. In the general formulas (XIII-1) to (XIII-5), n 1 , n 2 , n 3 , n 4 and n 5 each represents an integer of 2 or more, and an integer of 2 to 100 is preferable. In the general formula (XIII-5), n 6 represents 0 or an integer of 2 or more, preferably 0 or an integer of 2 to 100.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000064
 In the general formulas (XIV-1) to (XIV-16), R 14 represents a hydrogen atom or a methyl group, R 15 represents an alkylene group having 1 to 10 carbon atoms, and R 16 represents a carbon atom. Represents a hydrocarbon group of 1 to 10. p represents 0 or an integer of 1 to 10.
　また、前記ポリウレタン樹脂は、更に第５成分として、カルボン酸基非含有の低分子量ジオールを共重合させてもよく、該低分子量ジオールとしては、前記一般式（ＸＩＩＩ－１）～（ＸＩＩＩ－５）で表され、重量平均分子量が５００以下のものである。該カルボン酸基非含有低分子量ジオールは、アルカリ溶解性が低下しない限り、また、硬化膜の弾性率が十分低く保つことができる範囲で添加することができる。 Further, the polyurethane resin may further be copolymerized with a low molecular weight diol containing no carboxylic acid group as a fifth component. Examples of the low molecular weight diol include those represented by the general formulas (XIII-1) to (XIII-5). The weight average molecular weight is 500 or less. The low molecular weight diol containing no carboxylic acid group can be added as long as the alkali solubility is not lowered and the elastic modulus of the cured film can be kept sufficiently low.
　前記ポリウレタン樹脂としては、特に、一般式（ＸＩ）で示されるジイソシアネートと、一般式（ＸＩＩ－１）～（ＸＩＩ－３）で示されるカルボン酸基含有ジオールから選ばれた少なくとも１種とを必須成分とし、目的に応じて、一般式（ＸＩＩＩ－１）～（ＸＩＩＩ－５）で示される重量平均分子量が８００～３，０００の範囲にある高分子ジオールから選ばれた少なくとも１種や、一般式（ＸＩＩＩ－１）～（ＸＩＩＩ－５）で示される重量平均分子量が５００以下のカルボン酸基非含有の低分子量ジオールとの反応物に、さらに一般式（ＸＩＶ－１）～（ＸＩＶ－１６）のいずれかで示される分子中に１個のエポキシ基と少なくとも１個の（メタ）アクリル基を有する化合物を反応して得られる、酸価が２０ｍｇＫＯＨ／ｇ～１２０ｍｇＫＯＨ／ｇであるアルカリ可溶性光架橋性ポリウレタン樹脂が好適である。 As the polyurethane resin, in particular, a diisocyanate represented by the general formula (XI) and at least one selected from carboxylic acid group-containing diols represented by the general formulas (XII-1) to (XII-3) are essential. As a component, depending on the purpose, at least one selected from polymer diols having a weight average molecular weight of 800 to 3,000, represented by general formulas (XIII-1) to (XIII-5), A reaction product with a low molecular weight diol containing no carboxylic acid group and having a weight average molecular weight of 500 or less represented by formulas (XIII-1) to (XIII-5) is further added to formulas (XIV-1) to (XIV-16). ) Obtained by reacting a compound having one epoxy group and at least one (meth) acryl group in the molecule represented by any of the above, the acid value is 20 mgKOH / g to 12 Alkali-soluble photocrosslinking polyurethane resin is mg KOH / g are preferred.
　これらの高分子化合物は、単独で用いてもよいし、２種以上を併用してもよい。 These polymer compounds may be used alone or in combination of two or more.
　前記酸変性ビニル基含有ポリウレタン樹脂の含有量としては、前記感光性組成物の固形分１００質量部に対して、２質量部～３０質量部が好ましく、５質量部～２５質量部がより好ましい。前記含有量が、２質量部未満では硬化膜の高温時の十分な低弾性率が得られないことがあり、３０質量部を超えると現像性劣化や硬化膜の強靱性低下が起きることがある。 The content of the acid-modified vinyl group-containing polyurethane resin is preferably 2 to 30 parts by mass and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. When the content is less than 2 parts by mass, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 30 parts by mass, the developability may deteriorate and the toughness of the cured film may decrease. .
－－カルボキシル基含有ポリウレタンと分子中にエポキシ基とビニル基を有する化合物とを反応して得られるポリウレタン樹脂の合成法－－
　前記ポリウレタン樹脂の合成方法としては、上記ジイソシアネート化合物及びジオール化合物を非プロトン性溶媒中、それぞれの反応性に応じた活性の公知な触媒を添加し、加熱することにより合成される。使用するジイソシアネート及びジオール化合物のモル比は好ましくは、０．８：１～１．２：１であり、ポリマー末端にイソシアネート基が残存した場合、アルコール類又はアミン類等で処理することにより、最絡的にイソシアネート基が残存しない形で合成される。 --Synthesis of polyurethane resin obtained by reacting carboxyl group-containing polyurethane with compound having epoxy group and vinyl group in molecule--
As a method for synthesizing the polyurethane resin, the diisocyanate compound and the diol compound are synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. If an isocyanate group remains at the end of the polymer, the molar ratio can be reduced by treatment with alcohols or amines. It is synthesized in such a way that no isocyanate groups remain entangled.
－－－ジイソシアネート－－－
　前記一般式（ＸＩ）で示されるジイソシアネート化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００７－２０３０号公報の段落「００２１」に記載された化合物、などが挙げられる。 --- Diisocyanate ---
The diisocyanate compound represented by the general formula (XI) is not particularly limited and may be appropriately selected depending on the purpose. For example, the compound described in paragraph “0021” of JP-A-2007-2030, Etc.
－－－高分子量ジオール－－－
　前記一般式（ＸＩＩＩ－１）～（ＸＩＩＩ－５）で示される高分子量ジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００７－２０３０号公報の段落「００２２」～「００４６」に記載された化合物、などが挙げられる。 --- High molecular weight diol ---
The high molecular weight diol compound represented by the general formulas (XIII-1) to (XIII-5) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as disclosed in JP-A-2007-2030 And compounds described in paragraphs “0022” to “0046”.
－－－カルボン酸基含有ジオール－－－
　また、前記一般式（ＸＩＩ－１）～（ＸＩＩ－３）で表されるカルボキシル基を有するジオール化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００７－２０３０号公報の段落「００４７」に記載された化合物、などが挙げられる。 --Carboxylic acid group-containing diol ---
In addition, the diol compound having a carboxyl group represented by the general formulas (XII-1) to (XII-3) is not particularly limited and may be appropriately selected depending on the intended purpose. And the compounds described in paragraph “0047” of the publication No. 2030.
－－－カルボン酸基非含有低分子量ジオール－－－
　前記カルボン酸基非含有低分子量ジオールとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、特開２００７－２０３０号公報の段落「００４８」に記載された化合物、などが挙げられる。
　前記カルボン酸基非含有ジオールの共重合量としては、低分子量ジオール中の９５モル％以下が好ましく、８０％以下がより好ましく、５０％以下が特に好ましい。前記共重合量が、９５モル％を超えると現像性のよいウレタン樹脂が得られないことがある。 --- Low molecular weight diol containing no carboxylic acid groups ---
The carboxylic acid group-free low molecular weight diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0048” of JP-A-2007-2030. Can be mentioned.
The copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80% or less, and particularly preferably 50% or less in the low molecular weight diol. When the copolymerization amount exceeds 95 mol%, a urethane resin having good developability may not be obtained.
　前記（ｉｉ）カルボキシル基含有ポリウレタンと分子中にエポキシ基とビニル基を有する化合物とを反応して得られるポリウレタン樹脂の具体例としては、例えば、特開２００７－２０３０号公報の段落「０３１４」～「０３１５」に示されたＵ１～Ｕ４、Ｕ６～Ｕ１１のポリマーにおけるエポキシ基及びビニル基含有化合物としてのグリシジルアクリレートを、グリシジルメタクリレート、３，４－エポキシシクロヘキシルメチルアクリレート（商品名：サイクロマーＡ４００（ダイセル化学製））、３，４－エポキシシクロヘキシルメチルメタクリレート（商品名：サイクロマーＭ４００（ダイセル化学製））に代えたポリマー、などが挙げられる。 Specific examples of the polyurethane resin obtained by reacting the above (ii) carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule include, for example, paragraphs “0314” to JP-A-2007-2030. Glycidyl acrylate as an epoxy group and vinyl group-containing compound in the polymers U1 to U4 and U6 to U11 shown in “0315” is converted to glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400 (Daicel). Chemical)), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400 (manufactured by Daicel Chemical)), and the like.
　前記酸変性ビニル基含有ポリウレタン樹脂の前記感光性組成物における含有量としては、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、５質量％～８０質量％が好ましく、２０質量％～７５質量％がより好ましく、３０質量％～７０質量％が特に好ましい。
　前記含有量が５質量％未満であると、耐クラック性が良好に保つことができないことがあり、８０質量％を超えると、耐熱性が破綻をきたすことがある。一方、前記含有量が、前記特に好ましい範囲内であると、良好な耐クラック性と耐熱性の両立の点で有利である。 The content of the acid-modified vinyl group-containing polyurethane resin in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% by mass to 80% by mass, and preferably 20% by mass. Is more preferably from 75 to 75% by weight, particularly preferably from 30 to 70% by weight.
If the content is less than 5% by mass, good crack resistance may not be maintained, and if it exceeds 80% by mass, the heat resistance may fail. On the other hand, when the content is within the particularly preferable range, it is advantageous in terms of both good crack resistance and heat resistance.
　前記酸変性ビニル基含有ポリウレタン樹脂の重量平均分子量としては、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、２，０００～６０，０００が好ましく、５，０００～５０，０００がより好ましく、３，０００～３０，０００が特に好ましい。前記重量平均分子量が２，０００未満であると、硬化膜の高温時の十分な低弾性率が得られないことがあり、６０，０００を超えると、塗布適性及び現像性が悪化することがある。
　なお、前記重量平均分子量は、例えば、高速ＧＰＣ装置（東洋曹達社製ＨＬＣ－８０２Ａ）を使用して、０．５質量％のＴＨＦ溶液を試料溶液とし、カラムはＴＳＫｇｅｌ　ＨＺＭ－Ｍ　１本を使用し、２００μＬの試料を注入し、前記ＴＨＦ溶液で溶離して、２５℃で屈折率検出器あるいはＵＶ検出器（検出波長２５４ｎｍ）により測定することができる。次に、標準ポリスチレンで較正した分子量分布曲線より重量平均分子量を求めた。 The weight average molecular weight of the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2,000 to 60,000, and preferably 5,000 to 50,000. More preferred is 3,000 to 30,000. When the weight average molecular weight is less than 2,000, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 60,000, coating suitability and developability may be deteriorated. .
The weight average molecular weight is determined using, for example, a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.), a 0.5 mass% THF solution as a sample solution, and a column using one TSKgel HZM-M. Then, 200 μL of sample is injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or a UV detector (detection wavelength 254 nm). Next, the weight average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
　前記酸変性ビニル基含有ポリウレタン樹脂の酸価としては、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、２０ｍｇＫＯＨ／ｇ～１２０ｍｇＫＯＨ／ｇが好ましく、３０ｍｇＫＯＨ／ｇ～１１０ｍｇＫＯＨ／ｇがより好ましく、３５ｍｇＫＯＨ／ｇ～１００ｍｇＫＯＨ／ｇが特に好ましい。前記酸価が、２０ｍｇＫＯＨ／ｇ未満であると現像性が不十分となることがあり、１２０ｍｇＫＯＨ／ｇを超えると現像速度が高すぎるため現像のコントロールが難しくなることがある。
　なお、前記酸価は、例えば、ＪＩＳ　Ｋ００７０に準拠して測定することができる。ただし、サンプルが溶解しない場合は、溶媒としてジオキサン又はテトラヒドロフランなどを使用する。 The acid value of the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. 35 mg KOH / g to 100 mg KOH / g is particularly preferable. If the acid value is less than 20 mgKOH / g, the developability may be insufficient, and if it exceeds 120 mgKOH / g, the development rate may be too high, and development control may be difficult.
In addition, the said acid value can be measured based on JISK0070, for example. However, if the sample does not dissolve, dioxane or tetrahydrofuran is used as the solvent.
　前記酸変性ビニル基含有ポリウレタン樹脂のビニル基当量としては、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、０．０５ｍｍｏｌ／ｇ～３．０ｍｍｏｌ／ｇが好ましく、０．５ｍｍｏｌ／ｇ～２．７ｍｍｏｌ／ｇがより好ましく、０．７５ｍｍｏｌ／ｇ～２．４ｍｍｏｌ／ｇが特に好ましい。前記ビニル基当量が、０．０５ｍｍｏｌ／ｇ未満であると、硬化膜の耐熱性が劣ることがあり、３．０ｍｍｏｌ／ｇを超えると、耐クラック性が悪化することがある。
　前記ビニル基当量は、例えば、臭素価を測定することにより求めることができる。なお、前記臭素価は、例えば、ＪＩＳ　Ｋ２６０５に準拠して測定することができる。 The vinyl group equivalent of the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 mmol / g to 3.0 mmol / g, preferably 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable. When the vinyl group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 3.0 mmol / g, the crack resistance may be deteriorated.
The vinyl group equivalent can be determined, for example, by measuring the bromine number. The bromine number can be measured according to, for example, JIS K2605.
　なお、本発明の感光性組成物には、前記ポリウレタン樹脂以外にも、更に必要に応じてその他の樹脂を前記ポリウレタン樹脂に対し５０質量％以下の量添加することが好ましい。前記その他の樹脂としては、例えば、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、アクリル樹脂、メタクリル樹脂、ポリスチレン樹脂、ノボラック型フェノール樹脂などが挙げられる。 In addition to the polyurethane resin, it is preferable to add another resin to the photosensitive composition of the present invention in an amount of 50% by mass or less based on the polyurethane resin as necessary. Examples of the other resin include polyamide resin, epoxy resin, polyacetal resin, acrylic resin, methacrylic resin, polystyrene resin, and novolac type phenol resin.
　前記樹脂の含有量としては、前記感光性組成物の固形分１００質量部に対して、５質量部～８０質量部が好ましく、３０質量部～７０質量部がより好ましい。前記含有量が、５質量部以上であれば、現像性、露光感度が良好となり、８０質量部以下であれば、感光層の粘着性が強くなりすぎることを防止できる。 The content of the resin is preferably 5 to 80 parts by mass, and more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. When the content is 5 parts by mass or more, developability and exposure sensitivity are good, and when the content is 80 parts by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.
＜熱架橋剤＞
　前記熱架橋剤としては、特に制限はなく、目的に応じて適宜選択することができ、現像性等に悪影響を与えない範囲で、例えば、エポキシ化合物（例えば、１分子内に少なくとも２つのオ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つのオキセタニル基を有するオキセタン化合物などを用いることができ、特開２００７－４７７２９号公報に記載されているようなオキシラン基を有するエポキシ化合物、β位にアルキル基を有するエポキシ化合物、オキセタニル基を有するオキセタン化合物、ポリイソシアネート化合物、ポリイソシアネート及びその誘導体のイソシアネート基にブロック剤を反応させて得られる化合物、メラミン誘導体などが挙げられる。 <Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. For example, an epoxy compound (for example, at least two oxirane groups in one molecule) may be selected as long as it does not adversely affect developability. An oxetane compound having at least two oxetanyl groups in one molecule, an epoxy compound having an oxirane group as described in JP-A-2007-47729, and a β-position Examples include an epoxy compound having an alkyl group, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a compound obtained by reacting an isocyanate group of a polyisocyanate and a derivative thereof with a blocking agent, and a melamine derivative.
　前記エポキシ化合物としては、例えば、１分子中に少なくとも２つのオキシラン基を有するエポキシ化合物、β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つ含むエポキシ化合物などが挙げられる。 Examples of the epoxy compound include an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound having at least two epoxy groups having an alkyl group at the β-position in one molecule.
　前記１分子中に少なくとも２つのオキシラン基を有するエポキシ化合物としては、例えば、ビキシレノール型若しくはビフェ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、イソシア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（株）製」、「アラルダイトＰＴ８１０；チバ・スペシャルティ・ケミカルズ社製」等）、ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾ－ルノボラック型エポキシ樹脂、ハロゲン化エポキシ樹脂（例えば低臭素化エポキシ樹脂、高ハロゲン化エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂など）、アリル基含有ビスフェノールＡ型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ジフェニルジメタノール型エポキシ樹脂、フェノールビフェニレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂（「ＨＰ－７２００，ＨＰ－７２００Ｈ；大日本インキ化学工業（株）製」等）、グリシジルアミン型エポキシ樹脂（ジアミノジフェニルメタン型エポキシ樹脂、ジグリシジルアニリン、トリグリシジルアミノフェノール等）、グリジジルエステル型エポキシ樹脂（フタル酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステル等）ヒダントイン型エポキシ樹脂、脂環式エポキシ樹脂（３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ジシクロペンタジエンジエポキシド、「ＧＴ－３００、ＧＴ－４００、ＺＥＨＰＥ３１５０；ダイセル化学工業製」等、）、イミド型脂環式エポキシ樹脂、トリヒドロキシフェニルメタン型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、テトラフェニロールエ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イルエタン樹脂、ナフタレン基含有エポキシ樹脂（ナフトールアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、４官能ナフタレン型エポキシ樹脂、市販品としては「ＥＳＮ－１９０，ＥＳＮ－３６０；新日鉄化学（株）製」、「ＨＰ－４０３２，ＥＸＡ－４７５０，ＥＸＡ－４７００；大日本インキ化学工業（株）製」等）、フェノール化合物とジビニルベンゼンやジシクロペンタジエン等のジオレフィン化合物との付加反応によって得られるポリフェノール化合物と、エピクロルヒドリンとの反応物、４－ビニルシクロヘキセン－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、線状含リン構造を有するエポキシ樹脂、環状含リン構造を有するエポキシ樹脂、α－メチルスチルベン型液晶エポキシ樹脂、ジベンゾイルオキシベンゼン型液晶エポキシ樹脂、アゾフェニル型液晶エポキシ樹脂、アゾメチンフェニル型液晶エポキシ樹脂、ビナフチル型液晶エポキシ樹脂、アジン型エポキシ樹脂、グリシジルメタアクリレート共重合系エポキシ樹脂（「ＣＰ－５０Ｓ，ＣＰ－５０Ｍ；日本油脂（株）製」等）、シクロヘキシルマレイミドとグリシジルメタアクリレートとの共重合エポキシ樹脂、ビス（グリシジルオキシフェニル）フルオレン型エポキシ樹脂、ビス（グリシジルオキシフェニル）アダマンタン型エポキシ樹脂などが挙げられるが、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。 Examples of the epoxy compound having at least two oxirane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resin (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, water Bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin) , Brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP- 7200, HP-7200H; manufactured by Dainippon Ink and Chemicals, Inc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (phthalic acid) Acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; Industrial-made "etc.), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidylxylenoylethane resin, Naphthalene group-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; "Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; Dainippon Ink and Chemicals Co., Ltd."), phenol compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene Reaction product of polyphenol compound obtained by reaction with epichlorohydrin, ring-opening polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid, epoxy resin having linear phosphorus-containing structure, cyclic phosphorus-containing Epoxy resin having structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl meta Acrylate copolymer system Xy-resin (“CP-50S, CP-50M; manufactured by NOF Corporation”, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxy) Phenyl) adamantane type epoxy resin and the like can be mentioned, but not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.
　また、１分子中に少なくとも２つのオキシラン基を有する前記エポキシ化合物以外に、β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つ含むエポキシ化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ル基など）を含む化合物が特に好ましい。
　前記β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β－アルキル置換グリシジル基であってもよい。 In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used, and the β-position is an alkyl group. Particularly preferred are compounds containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound including at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.
　前記オキセタン化合物としては、例えば、１分子内に少なくとも２つのオキセタニル基を有するオキセタン化合物が挙げられる。
　具体的には、例えば、ビス［（３－メチル－３－オキセタニルメトキシ）メチル］エーテル、ビス［（３－エチル－３－オ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－オキセタニルメトキシ）メチル］ベンゼン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、（３－メチル－３－オキセタニル）メチルアクリレート、（３－エチル－３－オキセタニル）メチルアクリレート、（３－メチル－３－オキセタニル）メチルメタクリレート、（３－エチル－３－オキセタニル）メチルメタク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オキセタン類の他、オキセタン基を有する化合物と、ノボラック樹脂、ポリ（ｐ－ヒドロキシスチレン）、カルド型ビスフェノール類、カリックスアレーン類、カリックスレゾルシンアレーン類、シルセスキオキサン等の水酸基を有する樹脂など、とのエーテル化合物が挙げられ、この他、オキセタン環を有する不飽和モノマーとアルキル（メタ）アクリレートとの共重合体なども挙げられる。 Examples of the oxetane compound include oxetane compounds having at least two oxetanyl groups in one molecule.
Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, compounds having an oxetane group; Novolac resin, poly (p-hydroxystyrene), cardo type bisphenol , Calixarenes, calixresorcinarenes, ether compounds such as silsesquioxanes and the like, and other compounds having an oxetane ring and alkyl (meth) acrylate. A polymer etc. are also mentioned.
　また、前記ポリイソシアネート化合物としては、特開平５－９４０７号公報記載のポリイソシアネート化合物を用いることができ、該ポリイソシアネート化合物は、少なくとも２つのイソシアネート基を含む脂肪族、環式脂肪族又は芳香族基置換脂肪族化合物から誘導されていてもよい。具体的には、２官能イソシアネート（例えば、１，３－フェニレンジイソシアネートと１，４－フェニレンジイソシアネートとの混合物、２，４－及び２，６－トルエンジイソシアネート、１，３－及び１，４－キシリレンジイソシアネート、ビス（４－イソシアネート－フェニル）メタン、ビス（４－イソシアネートシクロヘキシル）メタン、イソフォロンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等）、該２官能イソシアネートと、トリメチロールプロパン、ペンタリスルトール、グリセリン等との多官能アルコール；該多官能アルコールのアルキレンオキサイド付加体と、前記２官能イソシアネートとの付加体；ヘキサメチレンジイソシアネート、ヘキサメチレン－１，６－ジイソシアネート及びその誘導体等の環式三量体；などが挙げられる。 Further, as the polyisocyanate compound, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is an aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin and the like; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.
　前記ポリイソシアネート化合物にブロック剤を反応させて得られる化合物、すなわちポリイソシアネート及びその誘導体のイソシアネート基にブロック剤を反応させて得られる化合物における、イソシアネート基ブロック剤としては、アルコール類（例えば、イソプロパノール、ｔｅｒｔ－ブタノール等）、ラクタム類（例えば、ε－カプロラクタム等）、フェノール類（例えば、フェノール、クレゾール、ｐ－ｔｅｒｔ－ブチルフェノール、ｐ－ｓｅｃ－ブチルフェノール、ｐ－ｓｅｃ－アミルフェノール、ｐ－オクチルフェノール、ｐ－ノニルフェノール等）、複素環式ヒドロキシル化合物（例えば、３－ヒドロキシピリジン、８－ヒドロキシキノリン等）、活性メチレン化合物（例えば、ジアルキルマロネート、メチルエチルケトキシム、アセチルアセトン、アルキルアセトアセテートオキシム、アセトオキシム、シクロヘキサノンオキシム等）などが挙げられる。これらの他、特開平６－２９５０６０号公報記載の分子内に少なくとも１つの重合可能な二重結合及び少なくとも１つのブロックイソシアネート基のいずれかを有する化合物などを用いることができる。 As an isocyanate group blocking agent in a compound obtained by reacting a blocking agent with the polyisocyanate compound, that is, a compound obtained by reacting a blocking agent with an isocyanate group of polyisocyanate and derivatives thereof, alcohols (for example, isopropanol, tert-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol, p -Nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, methyl ethyl ketoxy) Arm, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.) and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.
　前記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、エチル、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く、ヘキサメチル化メチロールメラミンが特に好ましい。 Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.
　前記熱架橋剤の含有量としては、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、前記感光性組成物の固形分１００質量部に対して、１質量部～５０質量部が好ましく、３質量部～３０質量部がより好ましい。前記含有量が、１質量部以上であれば、硬化膜の膜強度が向上され、５０質量部以下であれば、現像性、露光感度が良好となる。 The content of the thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is 1 to 50 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Preferably, 3 parts by mass to 30 parts by mass is more preferable. If the said content is 1 mass part or more, the film | membrane intensity | strength of a cured film will be improved, and if it is 50 mass parts or less, developability and exposure sensitivity will become favorable.
＜フィラー＞
　前記フィラーとしては、例えば、無機フィラー、有機フィラーが挙げられる。 <Filler>
Examples of the filler include inorganic fillers and organic fillers.
　前記無機フィラーとしては、特に制限はなく、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、チタン酸バリウム、シリカ、タルク、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、マイカなどが挙げられる。これらの中でも、耐熱性、強靭性、絶縁性、誘電率の点から、シリカが好ましい。 The inorganic filler is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, water Examples thereof include aluminum oxide and mica. Among these, silica is preferable from the viewpoint of heat resistance, toughness, insulation, and dielectric constant.
　前記シリカとしては、例えば、酸化ケイ素粉、微粉状酸化ケイ素、気相法シリカ、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカなどが挙げられる。
　前記シリカとしては、市販品を用いることができ、例えば、アドマテックス社、龍森社などから市販されているシリカが挙げられる。 Examples of the silica include silicon oxide powder, finely divided silicon oxide, gas phase method silica, amorphous silica, crystalline silica, fused silica, and spherical silica.
A commercial item can be used as said silica, for example, the silica marketed from Admatex, Tatsumori, etc. is mentioned.
　前記有機フィラーとしては、特に制限はなく、目的に応じて適宜選択することができ、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。 The organic filler is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine resin, benzoguanamine resin, and cross-linked polystyrene resin.
　前記フィラーの平均粒子径としては、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、０．０１μｍ～２０μｍが好ましく、０．０２μｍ～１０μｍがより好ましく、０．０５μｍ～５μｍが特に好ましい。前記平均粒子径が、０．０１μｍ未満であると、充分な耐熱性が得られないことがあり、２０μｍを超えると、解像性が低下することがある。前記平均粒子径が、前記特に好ましい範囲であると、解像性と耐熱性が両立できる点で有利である。
　前記フィラーの平均粒子径は、レーザ回折・散乱法により測定することができる。 The average particle size of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 μm to 20 μm, more preferably 0.02 μm to 10 μm, and particularly preferably 0.05 μm to 5 μm. preferable. When the average particle diameter is less than 0.01 μm, sufficient heat resistance may not be obtained, and when it exceeds 20 μm, resolution may be deteriorated. When the average particle diameter is in the particularly preferred range, it is advantageous in that both resolution and heat resistance can be achieved.
The average particle diameter of the filler can be measured by a laser diffraction / scattering method.
　前記フィラーの含有量としては、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、前記感光性組成物の固形分１００質量部に対して、１０質量部～９７質量部が好ましく、１５質量部～９５質量部がより好ましく、２５質量部～９５質量部が特に好ましい。前記含有量が、１０質量部未満であると、充分な耐熱性が得られないことがあり、９７質量部を超えると、解像性が低下することがある。前記含有量が、前記特に好ましい範囲であると、解像性と耐熱性が両立できる点で有利である。 The content of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 parts by mass to 97 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition, 15 parts by mass to 95 parts by mass is more preferable, and 25 parts by mass to 95 parts by mass is particularly preferable. When the content is less than 10 parts by mass, sufficient heat resistance may not be obtained, and when it exceeds 97 parts by mass, resolution may be deteriorated. When the content is within the particularly preferable range, it is advantageous in that both resolution and heat resistance can be achieved.
＜重合性化合物＞
　前記重合性化合物としては、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、例えば、エチレン性不飽和結合を１つ以上有する化合物が好ましい。 <Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, For example, the compound which has one or more ethylenically unsaturated bonds is preferable.
　前記エチレン性不飽和結合としては、例えば、（メタ）アクリロイル基、（メタ）アクリルアミド基、ビニルフェニル基、ビニルエステルやビニルエーテル等のビニル基、アリルエーテルやアリルエステル等のアリル基、などが挙げられる。 Examples of the ethylenically unsaturated bond include (meth) acryloyl group, (meth) acrylamide group, vinylphenyl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester, and the like. .
　前記エチレン性不飽和結合を１つ以上有する化合物としては、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、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 compound having one or more ethylenically unsaturated bonds is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from monomers having a (meth) acryl group is Preferably mentioned.
　前記（メタ）アクリル基を有するモノマーとしては、特に制限はなく、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）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の単官能アクリレートや単官能メタクリレート；ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンジアクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリトリトールテトラ（メタ）アクリレート、ペンタエリトリトールトリ（メタ）アクリレート、ジペンタエリトリトールヘキサ（メタ）アクリレート、ジペンタエリトリトールペンタ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート、トリ（アクリロイルオキシエチル）シアヌレート、グリセリントリ（メタ）アクリレート、トリメチロールプロパンやグリセリン、ビスフェ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加反応した後で（メタ）アクリレート化したもの、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クリレート類；特開昭４８－６４１８３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クリレート類；エポキシ樹脂と（メタ）アクリル酸の反応生成物であるエポキシアクリレート類等の多官能アクリレートやメタク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）アクリレート、ペンタエリトリトールテトラ（メタ）アクリレート、ジペンタエリトリトールヘキサ（メタ）アクリレート、ジペンタエリトリトールペンタ（メタ）アクリレートが特に好ましい。 There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Polyfunctional alcohols such as glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, and the like, which are subjected to addition reaction of ethylene oxide and propylene oxide and then (meth) acrylated, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50 Urethane acrylates described in each publication such as JP-6034, JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, JP-B-52-3 Polyester acrylates described in each publication of such 490 No., such as epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.
　前記重合性化合物の含有量としては、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、前記感光性組成物の固形分１００質量部に対して、５質量部～５０質量部が好ましく、１０質量部～４０質量部がより好ましい。前記含有量が、５質量部以上であれば、現像性、露光感度が良好となり、５０質量部以下であれば、感光層の粘着性が強くなりすぎることを防止できる。 The content of the polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. It is 5 to 50 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Preferably, 10 parts by weight to 40 parts by weight is more preferable. When the content is 5 parts by mass or more, developability and exposure sensitivity are good, and when the content is 50 parts by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.
＜光重合開始剤＞
　前記光重合開始剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン化合物；アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－１－プロパノン、Ｎ，Ｎ－ジメチルアミノアセトフェノン等のアセトフェノン化合物；２－メチルアントラキノン、２－エチルアントラキノン、２－ｔｅｒｔ－ブチルアントラキノン、１－クロロアントラキノン、２－アミルアントラキノン、２－アミノアントラキノン等のアントラキノン化合物；２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン化合物；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール化合物；ベンゾフェノン、メチルベンゾフェノン、４，４′－ジクロロベンゾフェノン、４，４′－ビス（ジエチルアミノ）ベンゾフェノン、ミヒラーズケトン、４－ベンゾイル－４′－メチルジフェニルサルファイド等のベンゾフェノン化合物；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、アシルホスフィンオキシド化合物（ビスアシルホスフィンオキシド、モノアシルホスフィンオキシド、など）又はそのエステル化合物、オキシム誘導体化合物、有機過酸化物、チオ化合物、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。 <Photopolymerization initiator>
The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone Acetophenone compounds such as N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthra Anthraquinone compounds such as non; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, Benzophenone compounds such as methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenyl sulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide , Acylphosphine oxide compounds (bisacylphosphine oxide, monoacylphosphine oxide, etc.) or ester compounds thereof, oxy Derivative compounds, organic peroxides, thio compounds, and the like. These may be used individually by 1 type and may use 2 or more types together.
　前記光重合開始剤の含有量としては、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、前記感光性組成物の固形分１００質量部に対して、０．５質量部～２０質量部が好ましく、２質量部～１５質量部がより好ましい。前記含有量が０．５質量部以上であれば、露光部が現像中に溶出するのを防止することができ、２０質量部以下であれば、耐熱性が低下するのを防止することができる。 The content of the photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Mass parts are preferred, and 2 to 15 parts by mass are more preferred. If the content is 0.5 parts by mass or more, the exposed part can be prevented from eluting during development, and if it is 20 parts by mass or less, the heat resistance can be prevented from decreasing. .
＜その他の成分＞
　前記その他の成分としては、例えば、溶剤、増感剤、密着促進剤、熱重合禁止剤、着色剤、その他の添加剤などが挙げられ、更にその他の助剤類（例えば、導電性粒子、消泡剤、難燃剤、レベリング剤、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ィルムの安定性、写真性、膜物性などの性質を調整することができる。 <Other ingredients>
Examples of the other components include solvents, sensitizers, adhesion promoters, thermal polymerization inhibitors, colorants, other additives, and other auxiliary agents (for example, conductive particles, erasing agents, etc.). You may use together a foaming agent, a flame retardant, a leveling agent, a peeling accelerator, antioxidant, a fragrance | flavor, a surface tension regulator, a chain transfer agent, etc.). By appropriately containing these components, it is possible to adjust properties such as the stability, photographic properties, and film properties of the intended photosensitive composition or photosensitive film.
－溶剤－
　前記溶剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、メタノール、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－ヘキサノール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジイソブチルケトンなどのケトン類；酢酸エチル、酢酸ブチル、酢酸－ｎ－アミル、硫酸メチル、プロピオン酸エチル、フタル酸ジメチル、安息香酸エチル、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、エ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、クロロホルム、１，１，１－トリクロロエタン、塩化メチレン、モノクロロ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、ジエチルエーテル、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エチルエーテル、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、ジメチルアセトアミド、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く、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。 -solvent-
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.
－増感剤－
　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、酸発生剤など）と相互作用（例えば、エネルギー移動、電子移動など）することにより、ラジカルや酸などの有用基を発生することが可能である。
　前記増感剤としては、特に制限はなく、公知の増感剤の中から適宜選択することができ、例えば、公知の多核芳香族類（例えば、ピレン、ペリレン、トリフェニレン）、キサンテン類（例えば、フルオレセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、シアニン類（例えば、インドカルボシアニン、チアカルボシアニン、オキサカルボシアニン）、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、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アントラキノン類（例えば、アントラキノン）、スクアリウム類（例えば、スクアリウム）、アクリドン類（例えば、アクリドン、クロロアクリドン、Ｎ－メチルアクリドン、Ｎ－ブチルアクリドン、Ｎ－ブチル－クロロアクリドンなど）、クマリン類（例えば、３－（２－ベンゾフロイル）－７－ジエチルアミノクマリン、３－（２－ベンゾフロイル）－７－（１－ピロリジニル）クマリン、３－ベンゾイル－７－ジエチルアミノクマリン、３－（２－メトキシベンゾイル）－７－ジエチルアミノクマリン、３－（４－ジメチルアミノベンゾイル）－７－ジエチルアミノクマリン、３，３’－カルボニルビス（５，７－ジ－ｎ－プロポキシクマリン）、３，３’－カルボニルビス（７－ジエチルアミノクマリン）、３－ベンゾイル－７－メトキシクマリン、３－（２－フロイル）－７－ジエチルアミノクマリン、３－（４－ジエチルアミノシンナモイル）－７－ジエチルアミノクマリン、７－メトキシ－３－（３－ピリジルカルボニル）クマリン、３－ベンゾイル－５，７－ジプロポキシクマリンなどがあげられ、他に特開平５－１９４７５号公報、特開平７－２７１０２８号公報、特開２００２－３６３２０６号公報、特開２００２－３６３２０７号公報、特開２００２－３６３２０８号公報、特開２００２－３６３２０９号公報などの各公報に記載のクマリン化合物など）が挙げられる。 -Sensitizer-
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 generating radicals, acids, etc. It is possible to generate a useful group of
The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue) , Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrid) N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (eg 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7 -(1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 ′ -Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylamino Coumarin, 3- (4-Diethylaminocinnamoyl) -7-diethylaminocoumarin, 7 Examples include -methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, such as JP-A-5-19475, JP-A-7-271028, and JP2002. -363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like.
　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２００１－３０５７３４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。 Examples of the combination 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) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.
　前記増感剤の含有量としては、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、前記感光性組成物中の固形分１００質量部に対して、０．０５質量部～３０質量部が好ましく、０．１質量部～２０質量部がより好ましく、０．２質量部～１０質量部が特に好ましい。前記含有量が、０．０５質量部未満であると、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質量部を超えると、前記感光性組成物を感光性フィルムとした場合の保存時に、感光性フィルムにおける感光層から増感剤が析出することがある。 The content of the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.05 to 30 parts by mass with respect to 100 parts by mass of the solid content in the photosensitive composition. Part by mass is preferable, 0.1 to 20 parts by mass is more preferable, and 0.2 to 10 parts by mass is particularly preferable. When the content is less than 0.05 parts by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease. When the photosensitive composition is a photosensitive film, the sensitizer may be precipitated from the photosensitive layer in the photosensitive film during storage.
－密着促進剤－
　前記密着促進剤は、各層間の密着性、又は感光層と基材との密着性、電食性を向上させる機能がある。
　前記密着促進剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、メラミン、アセトグアナミン、ベンゾグアテミン、メラミン－フェノールホルマリン樹脂、エチルジアミノ－Ｓ－トリアジン、２，４－ジアミノ－Ｓ－トリアジン、２，４－ジアミノ－６－キシリル－Ｓ－トリアジンなどのトリアジン化合物が挙げられる。市販されているトリアジン化合物としては、下記構造式（Ｂ）～（Ｄ）に示す四国化成工業社製；２ＭＺ－ＡＺＩＮＥ（構造式（Ｂ）），２Ｅ４ＭＺ－ＡＺＩＮＥ（構造式（Ｃ）），ＣｌｌＺ－ＡＺＩＮＥ（構造式（Ｄ））などが挙げられる。
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000067
 　これらの化合物は、銅回路との密着性を高め、耐ＰＣＴ性を向上させ、電食性にも効果がある。これらは単独であるいは２種以上を組み合わせて用いることができる。
　前記密着促進剤の含有量としては、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、前記感光性組成物の固形分１００質量部に対して、０．１質量部～４０質量部が好ましく、０．１質量部～２０質量部がより好ましい。 -Adhesion promoter-
The adhesion promoter has a function of improving adhesion between layers, adhesion between the photosensitive layer and the substrate, and electrolytic corrosion.
The adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine, acetoguanamine, benzoguatemine, melamine-phenol formalin resin, ethyldiamino-S-triazine, 2,4-diamino. And triazine compounds such as -S-triazine and 2,4-diamino-6-xylyl-S-triazine. Commercially available triazine compounds include the following structural formulas (B) to (D) manufactured by Shikoku Chemical Industries; 2MZ-AZINE (structural formula (B)), 2E4MZ-AZINE (structural formula (C)), CllZ -AZINE (structural formula (D)) and the like.
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000067
 These compounds increase the adhesion to the copper circuit, improve the PCT resistance, and have an effect on electrolytic corrosion. These can be used alone or in combination of two or more.
The content of the adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.1 to 40 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Part is preferable, and 0.1 to 20 parts by mass is more preferable.
－熱重合禁止剤－
　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し、保存安定性を向上させるために添加することが好ましい。
　前記熱重合禁止剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、４－メトキシフェノール、ハイドロキノン、ハイドロキノンモノメチルエーテル、アルキル又はア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ェノン、４－メトキシ－２－ヒドロキシベンゾフェノン、塩化第一銅、フェノチアジン、クロラニル、ナフチルアミン、β－ナフトール、２，６－ジ－ｔ－ブチル－４－クレゾール、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、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、及びフェノチアジン、ニトロソ化合物、ニトロソ化合物とＡｌとのキレートなどが挙げられる。 -Thermal polymerization inhibitor-
The thermal polymerization inhibitor is preferably added to prevent thermal polymerization or temporal polymerization of the polymerizable compound and improve storage stability.
The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 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, phenothiazine, nitroso compound, nitroso compound Such as chelates with Al and the like.
　前記熱重合禁止剤の含有量としては、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、前記重合性化合物１００質量部に対して、０．００１質量部～５質量部が好ましく、０．００５質量部～２質量部がより好ましく、０．０１質量部～１質量部が特に好ましい。前記含有量が、０．００１質量部未満であると、保存時の安定性が低下することがあり、５質量部を超えると、活性エネルギー線に対する感度が低下することがある。 The content of the thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound. 0.005 to 2 parts by mass is more preferable, and 0.01 to 1 part by mass is particularly preferable. When the content is less than 0.001 part by mass, stability during storage may be reduced, and when it exceeds 5 parts by mass, sensitivity to active energy rays may be reduced.
－着色剤－
　前記着色剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、公知の染料の中から、適宜選択した着色顔料などの染料を使用することができる。 -Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, dyes, such as a coloring pigment suitably selected from well-known dyes, can be used.
　前記着色顔料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、フタロシアニングリーン、ビクトリア・ピュアーブルーＢＯ（Ｃ．Ｉ．４２５９５）、オーラミン（Ｃ．Ｉ．４１０００）、ファット・ブラックＨＢ（Ｃ．Ｉ．２６１５０）、モノライト・エローＧＴ（Ｃ．Ｉ．ピグメント・エロー１２）、パーマネント・エローＧＲ（Ｃ．Ｉ．ピグメント・エロー１７）、パーマネント・エローＨＲ（Ｃ．Ｉ．ピグメント・エロー８３）、パーマネント・カーミンＦＢＢ（Ｃ．Ｉ．ピグメント・レッド１４６）、ホスターバームレッドＥＳＢ（Ｃ．Ｉ．ピグメント・バイオレット１９）、パーマネント・ルビーＦＢＨ（Ｃ．Ｉ．ピグメント・レッド１１）ファステル・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．ピグメント・ブルー１５）、モノライト・ファースト・ブラックＢ（Ｃ．Ｉ．ピグメント・ブラック１）、カーボン、Ｃ．Ｉ．ピグメント・レッド９７、Ｃ．Ｉ．ピグメント・レッド１２２、Ｃ．Ｉ．ピグメント・レッド１４９、Ｃ．Ｉ．ピグメント・レッド１６８、Ｃ．Ｉ．ピグメント・レッド１７７、Ｃ．Ｉ．ピグメント・レッド１８０、Ｃ．Ｉ．ピグメント・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・ブルー１５：１、Ｃ．Ｉ．ピグメント・ブルー１５：４、Ｃ．Ｉ．ピグメント・ブルー１５：６、Ｃ．Ｉ．ピグメント・ブルー２２、Ｃ．Ｉ．ピグメント・ブルー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。 There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, phthalocyanine green, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat Black HB (C.I. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (C.I) 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) ) Fastel Pink B Supra (CI Pigment 81) Monasutoraru Fast Blue (C.I. Pigment Blue 15), Monolight Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more.
　前記着色顔料の含有量としては、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が、一般的には、前記感光性組成物の固形分１００質量部に対して、０．１質量部～１０質量部が好ましく、０．５質量部～８質量部がより好ましい。 The content of the color pigment can be determined in consideration of the exposure sensitivity and resolution of the photosensitive layer at the time of forming a permanent pattern, and varies depending on the type of the color pigment. 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the solid content of the composition.
－その他の添加剤－
　前記その他の添加剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ベントン、モンモリロナイト、エアロゾル、アミドワックスなどのチキソ性付与剤、シリコーン系、フッ素系、高分子系などの消泡剤、レベリング剤のような添加剤類を用いることができる。 -Other additives-
The other additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thixotropic agents such as benton, montmorillonite, aerosol, amide wax, silicone-based, fluorine-based, and polymer-based. Additives such as antifoaming agents and leveling agents can be used.
（感光性フィルム）
　本発明の感光性フィルムは、少なくとも支持体と、該支持体上に本発明の感光性組成物からなる感光層を有し、更に必要に応じてその他の層を有する。 (Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer comprising the photosensitive composition of the present invention on the support, and further has other layers as necessary.
－支持体－
　前記支持体としては、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、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ものが好ましく、更に表面の平滑性が良好であることがより好ましい。 -Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.
　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く、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、三酢酸セルロース、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）アクリル酸エステル共重合体、ポリ塩化ビニル、ポリビニルアルコール、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、塩化ビニル・酢酸ビニル共重合体、ポリテトラフロロエチレン、ポリトリフロロエチレン、セルロース系フィルム、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く、２種以上を併用してもよい。 The support is preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
　前記支持体の厚みは、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、例えば、２μｍ～１５０μｍが好ましく、５μｍ～１００μｍがより好ましく、８μｍ～５０μｍが特に好ましい。 The thickness of the support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 2 μm to 150 μm, more preferably 5 μm to 100 μm, and particularly preferably 8 μm to 50 μm.
　前記支持体の形状としては、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、長尺状が好ましい。前記長尺状の支持体の長さは、特に制限はなく、例えば、１０ｍ～２０，０００ｍの長さのものが挙げられる。 The shape of the support is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably long. The length of the long support is not particularly limited, and examples thereof include those having a length of 10 m to 20,000 m.
－感光層－
　前記感光層は、前記感光性組成物からなる層であれば、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。
　また、前記感光層の積層数としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、１層であってもよく、２層以上であってもよい。 -Photosensitive layer-
If the said photosensitive layer is a layer which consists of the said photosensitive composition, there will be no restriction | limiting in particular, According to the objective, it can select suitably.
Further, the number of laminated photosensitive layers is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be one layer or two or more layers.
　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。 Examples of the method for forming the photosensitive layer include a method in which the photosensitive composition of the present invention is directly applied on the support and laminated by drying.
　前記塗布の方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、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、カーテンコーター等を用いて、前記支持体に直接塗布する方法が挙げられる。
　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℃の温度で３０秒間～１５分間程度である。 The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually 60 ° C. to 110 ° C. for about 30 seconds to 15 minutes.
　前記感光層の厚みとしては、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、例えば、１μｍ～１００μｍが好ましく、２μｍ～５０μｍがより好ましく、４μｍ～３０μｍが特に好ましい。 The thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and particularly preferably 4 μm to 30 μm.
＜その他の層＞
　前記その他の層としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、保護フィルム、熱可塑性樹脂層、バリア層、剥離層、接着層、光吸収層、表面保護層等の層が挙げられる。前記感光性フィルムは、これらの層を１種単独で有していてもよく、２種以上を有していてもよい。 <Other layers>
The other layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a protective film, a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorption layer, a surface protective layer, etc. Layer. The said photosensitive film may have these layers individually by 1 type, and may have 2 or more types.
－保護フィルム－
　前記感光性フィルムは、前記感光層上に保護フィルムを有していてもよい。
　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、紙、ポリエチレン、ポリプロピレンがラミネートされた紙、などが挙げられ、これらの中でも、ポリエチレンフィルム、ポリプロピレンフィルムが好ましい。
　前記保護フィルムの厚みとしては、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、５μｍ～１００μｍが好ましく、８μｍ～５０μｍがより好ましく、１０μｍ～３０μｍが特に好ましい。
　前記支持体と前記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／ポリエチレン、ポリ塩化ビニル／セロフアン、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、層間接着力を調整することができる。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く、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、グロー放電照射処理、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。 -Protective film-
The photosensitive film may have a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
The thickness of the protective film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 μm to 100 μm, more preferably 8 μm to 50 μm, and particularly preferably 10 μm to 30 μm.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. It is done. Moreover, interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective film. 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, glow treatment Examples thereof include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.
　前記感光性フィルムは、例えば、円筒状の巻芯に巻き取って、長尺状でロール状に巻かれて保管されることが好ましい。前記長尺状の感光性フィルムの長さは、特に制限はなく、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～１，０００ｍ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巻き取られることが好ましい。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）を設置することが好ましく、また梱包も透湿性の低い素材を用いることが好ましい。 The photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape. The length of the long photosensitive film is not particularly limited, and can be appropriately selected from a range of, for example, 10 m to 20,000 m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. It is preferable.
　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、弗素化ポリオレフィン、ポリフルオロエチレン、ポリビニ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℃で１分間～３０分間乾燥させることにより形成させることができる。前記乾燥の際の温度は５０℃～１２０℃が特に好ましい。 The protective film may be surface-treated 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 polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 ° C. to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 ° C to 120 ° C.
（感光性積層体）
　前記感光性積層体は、少なくとも基体と、前記基体上に設けられた感光層と、有してなり、目的に応じて適宜選択されるその他の層を積層してなる。
　前記感光層は、上述の製造方法で作製された前記感光性フィルムから転写されたものであり、上述と同様の構成を有する。 (Photosensitive laminate)
The photosensitive laminate has at least a substrate and a photosensitive layer provided on the substrate, and is formed by laminating other layers appropriately selected according to the purpose.
The photosensitive layer is transferred from the photosensitive film produced by the manufacturing method described above, and has the same configuration as described above.
＜基体＞
　前記基体は、感光層が形成される被処理基体、又は本発明の感光性フィルムの少なくとも前記感光層が転写される被転写体となるもので、特に制限はなく、目的に応じて適宜選択することができ、例えば、表面平滑性の高いものから凸凹のある表面を持つものまで任意に選択できる。板状の基体が好ましく、いわゆる基板が使用される。具体的には、公知のプリント配線板製造用の基板（プリント基板）、ガラス板（ソーダガラス板など）、合成樹脂性のフィルム、紙、金属板などが挙げられる。 <Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited and is appropriately selected depending on the purpose. For example, it can be arbitrarily selected from those having a high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.
＜感光性積層体の製造方法＞
　前記感光性積層体の製造方法としては、例えば、本発明の感光性フィルムにおける少なくとも前記感光層を加熱及び加圧の少なくともいずれかを行いながら転写して積層する方法が挙げられる。 <Method for producing photosensitive laminate>
Examples of the method for producing the photosensitive laminate include a method in which at least the photosensitive layer in the photosensitive film of the present invention is transferred and laminated while performing at least one of heating and pressurization.
　前記感光性積層体の製造方法は、前記基体の表面に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を行いながら積層する。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、前記基体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。
　前記加熱温度は、特に制限はなく、目的に応じて適宜選択することができ、例えば、１５℃～１８０℃が好ましく、６０℃～１４０℃がより好ましい。
　前記加圧の圧力は、特に制限はなく、目的に応じて適宜選択することができ、例えば、０．１ＭＰａ～１．０ＭＰａが好ましく、０．２ＭＰａ～０．８ＭＰａがより好ましい。 In the method for producing the photosensitive laminate, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. 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 | substrate.
The heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 15 to 180 ° C. is preferable, and 60 to 140 ° C. is more preferable.
The pressurizing pressure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the pressure is preferably 0.1 MPa to 1.0 MPa, more preferably 0.2 MPa to 0.8 MPa.
　前記加熱の少なくともいずれかを行う装置としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ラミネーター（例えば、大成ラミネータ社製　ＶＰ－ＩＩ、ニチゴーモートン（株）製　ＶＰ１３０）などが好適に挙げられる。 An apparatus for performing at least one of the heating is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a laminator (for example, VP-II manufactured by Taisei Laminator Co., Ltd., VP130 manufactured by Nichigo Morton Co., Ltd.) Etc. are preferable.
　本発明の感光性フィルム及び前記感光性積層体は、現像後の基体上に不要な膜が残ることを抑制することができるため、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）を効率よく形成可能である。したがって、電子材料分野における高精細な永久パターンの形成用として広く用いることができ、特に、プリント基板の永久パターン形成用に好適に用いることができる。 Since the photosensitive film of the present invention and the photosensitive laminate can suppress the unnecessary film from remaining on the substrate after development, a high-definition permanent pattern (protective film, interlayer insulating film, and solder resist) Pattern etc.) can be formed efficiently. Therefore, it can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be suitably used particularly for forming a permanent pattern on a printed circuit board.
（永久パターン形成方法）
　本発明の永久パターン形成方法は、露光工程を少なくとも含み、更に、必要に応じて適宜選択した現像工程等のその他の工程を含む。 (Permanent pattern forming method)
The permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps such as a development step appropriately selected as necessary.
＜露光工程＞
　前記露光工程は、本発明の感光性組成物により形成された感光層に対し、露光を行う工程である。本発明の感光性組成物については上述の通りである。 <Exposure process>
The said exposure process is a process of exposing with respect to the photosensitive layer formed with the photosensitive composition of this invention. The photosensitive composition of the present invention is as described above.
　前記露光の対象としては、前記感光層である限り、特に制限はなく、目的に応じて適宜選択することができ、例えば、上述のように、基材上に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を行いながら積層して形成した積層体に対して行われることが好ましい。 The object of exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. For example, as described above, the photosensitive film of the present invention is heated on a substrate and heated. It is preferably performed on a laminate formed by laminating while performing at least one of pressurization.
　前記露光としては、特に制限はなく、目的に応じて適宜選択することができ、デジタル露光、アナログ露光等が挙げられるが、これらの中でもデジタル露光が好ましい。 The exposure is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include digital exposure and analog exposure. Of these, digital exposure is preferable.
＜その他の工程＞
　前記その他の工程としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、基材の表面処理工程、現像工程、硬化処理工程、ポスト露光工程などが挙げられる。 <Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a development process, a hardening process process, a post exposure process etc. are mentioned.
－現像工程－
　前記現像としては、前記感光層の未露光部分を除去することにより行われる。
　前記未硬化領域の除去方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、現像液を用いて除去する方法などが挙げられる。 -Development process-
The development is performed by removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.
　前記現像液としては、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、例えば、アルカリ性水溶液、水系現像液、有機溶剤などが挙げられ、これらの中でも、弱アルカリ性の水溶液が好ましい。該弱アルカリ水溶液の塩基成分としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、リン酸ナトリウム、リン酸カリウム、ピロリン酸ナトリウム、ピロリン酸カリウム、硼砂などが挙げられる。 The developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkaline aqueous solutions, aqueous developers and organic solvents, and among these, weakly alkaline aqueous solutions are preferred. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.
　前記弱アルカリ性の水溶液のｐＨは、例えば、約８～１２が好ましく、約９～１１がより好ましい。前記弱アルカリ性の水溶液としては、例えば、０．１質量％～５質量％の炭酸ナトリウム水溶液又は炭酸カリウム水溶液などが挙げられる。
　前記現像液の温度は、前記感光層の現像性に合わせて適宜選択することができるが、例えば、約２５℃～４０℃が好ましい。 The pH of the weak alkaline aqueous solution is preferably about 8 to 12, for example, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1% by mass to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.
　前記現像液は、界面活性剤、消泡剤、有機塩基（例えば、エチレンジアミン、エタノールアミン、テトラメチルアンモニウ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、ラクトン類等）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く、有機溶剤単独であってもよい。 The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.
－硬化処理工程－
　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。
　前記硬化処理工程としては、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、例えば、全面露光処理、全面加熱処理などが好適に挙げられる。 -Curing process-
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.
　前記全面露光処理の方法としては、例えば、前記現像後に、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。
　前記全面露光を行う装置としては、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、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。 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 development. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.
　前記全面加熱処理の方法としては、前記現像の後に、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。
　前記全面加熱における加熱温度は、１２０℃～２５０℃が好ましく、１２０℃～２００℃がより好ましい。該加熱温度が１２０℃以上であれば、加熱処理によって膜強度が向上し、２５０℃以下であれば、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を防止できる。
　前記全面加熱における加熱時間は、１０分～１２０分が好ましく、１５分～６０分がより好ましい。
　前記全面加熱を行う装置としては、特に制限はなく、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。 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 development. The entire surface heating increases the film strength of the surface of the permanent pattern.
The heating temperature in the entire surface heating is preferably 120 ° C. to 250 ° C., more preferably 120 ° C. to 200 ° C. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the resin in the photosensitive composition is decomposed to prevent the film quality from being weak and brittle.
The heating time in the entire surface heating is preferably 10 minutes to 120 minutes, more preferably 15 minutes to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.
　前記永久パターンの形成方法が、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永久パターン形成方法である場合には、プリント配線板上に前記永久パターン形成方法により、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。
　即ち、前記現像により、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）、ソルダーレジスト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。 When the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern is formed on the printed wiring board by the permanent pattern forming method. Further, soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, 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, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.
（プリント基板）
　本発明のプリント基板は、少なくとも基体と、前記永久パターン形成方法によって形成された永久パターンと、を有し、更に必要に応じて適宜選択した、その他の構成を有する。
　その他の構成としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、基材と前記永久パターン間に、更に絶縁層が設けられたビルドアップ基板などが挙げられる。 (Printed board)
The printed circuit board of the present invention has at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further has other configurations appropriately selected as necessary.
There is no restriction | limiting in particular as another structure, According to the objective, it can select suitably, For example, the buildup board | substrate etc. in which the insulating layer was further provided between the base material and the said permanent pattern are mentioned.
　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、実施例中、酸価及びアミン価は電位差法（溶媒テトラヒドロフラン／水＝１００／１０（体積比）、滴定液０．０１Ｎ水酸化ナトリウム水溶液（酸価）、滴定液０．０１Ｎ塩酸（アミン価））により決定した。 Examples of the present invention will be described below, but the present invention is not limited to the following examples.
In the examples, acid value and amine value are determined by potentiometric method (solvent tetrahydrofuran / water = 100/10 (volume ratio), titrant 0.01N aqueous sodium hydroxide solution (acid value), titrant 0.01N hydrochloric acid (amine Value)).
（合成例１）
＜ポリエステル（数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体）の合成＞
　ｎ－オクタン酸６．４ｇ、ε－カプロラクトン２００ｇ、チタン（ＩＶ）テトラブトキシド５ｇを混合し、１６０℃で８時間加熱した後、室温まで冷却しポリエステル（ｉ－１）を得た。得られたポリエステル（ｉ－１）について、ＧＰＣ法により測定した重量平均分子量、数平均分子量、及びラクトン繰返し単位数を表１に示す。
　反応スキームを以下に示す。
Figure JPOXMLDOC01-appb-C000068
 (Synthesis Example 1)
<Synthesis of polyester (graft chain precursor having a number average molecular weight of 500 to 1,000,000)>
6.4 g of n-octanoic acid, 200 g of ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, and then cooled to room temperature to obtain polyester (i-1). Table 1 shows the weight average molecular weight, number average molecular weight, and number of lactone repeating units of the obtained polyester (i-1) measured by GPC method.
The reaction scheme is shown below.
Figure JPOXMLDOC01-appb-C000068
（合成例２）
＜ポリエステル（数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体）の合成＞
　合成例１において、カルボン酸の種類及び仕込み量を表１に記載のカルボン酸の種類及び仕込み量に代えた以外は、合成例１と同様にして、ポリエステル（ｉ－２）を得た。得られたポリエステル（ｉ－２）について、ＧＰＣ法により測定した重量平均分子量、数平均分子量、及びラクトン繰返し単位数を表１に示す。 (Synthesis Example 2)
<Synthesis of polyester (graft chain precursor having a number average molecular weight of 500 to 1,000,000)>
A polyester (i-2) was obtained in the same manner as in Synthesis Example 1, except that the type and amount of carboxylic acid in Example 1 were changed to the type and amount of carboxylic acid shown in Table 1. Table 1 shows the weight average molecular weight, number average molecular weight, and number of lactone repeating units of the obtained polyester (i-2) measured by GPC method.
Figure JPOXMLDOC01-appb-T000069
Figure JPOXMLDOC01-appb-T000069
（合成例３）
＜窒素原子含有樹脂（Ｊ－１）の合成＞
　ポリエチレンイミン（ＳＰ－０１８、数平均分子量１，８００、日本触媒社製）（一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂に相当）１０ｇ及び前記ポリエステル（ｉ－１）（数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体に相当）１００ｇを混合し、１２０℃で３時間加熱して、中間体（Ｊ－１Ｂ）を得た。その後、６５℃まで放冷し、無水コハク酸（ｐＫａが１４以下である官能基を一部に有する基の前駆体に相当）３．８ｇを含有するプロピレングリコール１－モノメチルエーテル２－アセテート（以下、ＰＧＭＥＡと称することがある。）２００ｇをゆっくり添加し２時間攪拌した。その後、ＰＧＭＥＡを添加し、固形分１０質量％の窒素原子含有樹脂（Ｊ－１）のＰＧＭＥＡ溶液を得た。窒素原子含有樹脂（Ｊ－１）は、ポリエチレンイミンに由来する窒素原子を有する主鎖と、ポリエステル（ｉ－１）由来する数平均分子量が５００～１，０００，０００のグラフト鎖と、無水コハク酸に由来するｐＫａが１４以下である官能基（カルボキシ基）を有する基を有するものである。
　合成スキームを以下に示す。
Figure JPOXMLDOC01-appb-C000070
 (Synthesis Example 3)
<Synthesis of nitrogen atom-containing resin (J-1)>
10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai Co., Ltd.) (corresponding to a resin having at least one of a primary amino group and a secondary amino group) and the polyester (i-1) (number average) (Equivalent to a graft chain precursor having a molecular weight of 500 to 1,000,000) was mixed and heated at 120 ° C. for 3 hours to obtain an intermediate (J-1B). Thereafter, the mixture was allowed to cool to 65 ° C. and propylene glycol 1-monomethyl ether 2-acetate (hereinafter referred to as 3.8 g) containing 3.8 g of succinic anhydride (corresponding to a precursor of a group partially having a functional group having a pKa of 14 or less). , Sometimes referred to as PGMEA) 200 g was slowly added and stirred for 2 hours. Thereafter, PGMEA was added to obtain a PGMEA solution of a nitrogen atom-containing resin (J-1) having a solid content of 10% by mass. The nitrogen atom-containing resin (J-1) comprises a main chain having a nitrogen atom derived from polyethyleneimine, a graft chain having a number average molecular weight of 500 to 1,000,000 derived from polyester (i-1), an anhydrous succinate It has a group having a functional group (carboxy group) whose pKa derived from an acid is 14 or less.
A synthesis scheme is shown below.
Figure JPOXMLDOC01-appb-C000070
　中間体（Ｊ－１Ｂ）の滴定を行ったところ、酸価が０．１１ｍｍｏｌ／ｇであることが確認できた。また、窒素原子含有樹脂（Ｊ－１）の滴定を行ったところ、酸価が０．３１ｍｍｏｌ／ｇ、塩基価が０．８３ｍｍｏｌ／ｇであった。すなわち、窒素原子含有樹脂（Ｊ－１）の酸価と中間体（Ｊ－１Ｂ）の酸価の差よりｋ（前記一般式（Ｉ－１）に相当する繰り返し単位のモル％）が計算でき、窒素原子含有樹脂（Ｊ－１）の塩基価と反応前の樹脂の窒素原子数の差よりｌ１＋ｌ２（前記一般式（Ｉ－２）に相当する繰返し単位のモル％）が計算でき、中間体（Ｊ－１Ｂ）の酸価よりｍ１＋ｍ２（前記一般式（Ｉ－３）に相当する繰返し単位）のモル％が計算でき、ｋ／（ｌ１+ｌ２）／（ｍ１＋ｍ２）／ｎ＝１０／５０／５／３５となる。
　すなわち、得られた窒素原子含有樹脂は、前記一般式（Ｉ－１）で表される繰返し単位において、Ｘが－ＣＯＣＨ２ＣＨ２ＣＯ２Ｈである繰返し単位を１０モル％、前記一般式（Ｉ－２）で表される繰返し単位において、Ｙがポリ（ε－カプロラクトン）であるものを５０モル％含む窒素原子含有樹脂であることがわかる。また、ＧＰＣ法による重量平均分子量は２４，０００であった。中間体の酸価、アミン価、及び窒素原子含有樹脂の酸価、アミン価、重量平均分子量を表２に示す。 When the intermediate (J-1B) was titrated, it was confirmed that the acid value was 0.11 mmol / g. Further, when the nitrogen atom-containing resin (J-1) was titrated, the acid value was 0.31 mmol / g and the base value was 0.83 mmol / g. That is, k (mol% of the repeating unit corresponding to the general formula (I-1)) can be calculated from the difference between the acid value of the nitrogen atom-containing resin (J-1) and the acid value of the intermediate (J-1B). From the difference between the base number of the nitrogen atom-containing resin (J-1) and the number of nitrogen atoms in the resin before the reaction, l 1 + l 2 (mol% of the repeating unit corresponding to the general formula (I-2)) can be calculated. From the acid value of the intermediate (J-1B), the mol% of m 1 + m 2 (repeating unit corresponding to the general formula (I-3)) can be calculated and k / (l 1 + l 2 ) / (m 1 + m 2 ) / n = 10/50/5/35.
That is, the obtained nitrogen atom-containing resin contains 10 mol% of repeating units in which X is —COCH 2 CH 2 CO 2 H in the repeating unit represented by the general formula (I-1). It can be seen that the repeating unit represented by I-2) is a nitrogen atom-containing resin containing 50 mol% of Y being poly (ε-caprolactone). Moreover, the weight average molecular weight by GPC method was 24,000. Table 2 shows the acid value of the intermediate, the amine value, and the acid value, amine value, and weight average molecular weight of the nitrogen atom-containing resin.
（合成例４）
＜窒素原子含有樹脂（Ｊ－２）の合成＞
　合成例３において、一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂（表２においては「アミノ基含有樹脂」と称している。）、ポリエステル（数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体に相当）、及びｐＫａが１４以下である官能基を一部に有する基の前駆体（表２においては「Ｘ前駆体」と称している。）の種類、並びに配合量を、表２に記載のものに代えた以外は、合成例３と同様にして、窒素原子含有樹脂（Ｊ－２）を合成した。中間体の酸価、アミン価、及び窒素原子含有樹脂の酸価、アミン価、重量平均分子量を表２に示す。 (Synthesis Example 4)
<Synthesis of nitrogen atom-containing resin (J-2)>
In Synthesis Example 3, a resin having at least one of a primary amino group and a secondary amino group (referred to as “amino group-containing resin” in Table 2), polyester (number average molecular weight of 500 to 1,000,000) 000 graft chain precursors), and types of precursors having functional groups having a pKa of 14 or less (referred to as “X precursors” in Table 2), and blending A nitrogen atom-containing resin (J-2) was synthesized in the same manner as in Synthesis Example 3 except that the amount was changed to that shown in Table 2. Table 2 shows the acid value of the intermediate, the amine value, and the acid value, amine value, and weight average molecular weight of the nitrogen atom-containing resin.
（合成例５）
＜窒素原子含有樹脂（Ｊ－３）の合成＞
　合成例３において、アミノ基含有樹脂（ポリエチレンイミン）を、ポリアリルアミン（ＰＡＡ－０１、日東紡社製）脱水物、に変更した以外は、合成例３と同様にして、窒素原子含有樹脂（Ｊ－３）を合成した。中間体の酸価、アミン価、及び窒素原子含有樹脂の酸価、アミン価、重量平均分子量を表２に示す。 (Synthesis Example 5)
<Synthesis of nitrogen atom-containing resin (J-3)>
In the same manner as in Synthesis Example 3, except that the amino group-containing resin (polyethyleneimine) was changed to polyallylamine (PAA-01, manufactured by Nittobo) dehydrated in Synthesis Example 3, a nitrogen atom-containing resin (J -3) was synthesized. Table 2 shows the acid value of the intermediate, the amine value, and the acid value, amine value, and weight average molecular weight of the nitrogen atom-containing resin.
Figure JPOXMLDOC01-appb-T000071
 　ＳＰ－００６は、日本触媒社製のポリエチレンイミン（数平均分子量６００）である。
　ＰＡＡ－０１Ａは、日本触媒社製のポリアリルアミン（数平均分子量８００）脱水物である。
Figure JPOXMLDOC01-appb-T000071
 SP-006 is a polyethyleneimine (number average molecular weight 600) manufactured by Nippon Shokubai Co., Ltd.
PAA-01A is a polyallylamine (number average molecular weight 800) dehydrated product manufactured by Nippon Shokubai Co., Ltd.
（合成例６）
＜樹脂の合成＞
　コンデンサー、撹拌機を備えた５００ｍＬの３つ口丸底フラスコに、２，２－ビス（ヒドロキシメチル）プロピオン酸（ＤＭＰＡ）１０．８６ｇ（０．０８１モル）とグリセロールモノメタクリレート（ＧＬＭ）１６．８２ｇ（０．１０５モル）をプロピレングリコールモノメチルエーテルモノアセテート７９ｍＬに溶解した。これに、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）３７．５４ｇ（０．１５モル）、２，６-ジ－ｔ－ブチルヒドロキシトルエン０．１ｇ、触媒として、商品名：ネオスタンＵ－６００（日東化成（株）製）０．２ｇを添加し、７５℃にて、５時間加熱撹拌した。その後、メチルアルコール９．６１ｍＬにて希釈し３０分撹拌し、１４５ｇの酸変性ビニル基含有ポリウレタン樹脂Ｕ１溶液を得た。
　上記で得られた酸変性ビニル基含有ポリウレタン樹脂Ｕ１は、固形分酸価が７０ｍｇＫＯＨ／ｇであり、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定した重量平均分子量（ポリスチレン標準）が８，０００であり、ビニル基当量が１．５ｍｍｏｌ／ｇであった。
　前記酸価は、ＪＩＳ　Ｋ００７０に準拠して測定した。ただし、サンプルが溶解しない場合は、溶媒としてジオキサン又はテトラヒドロフランなどを使用した。
　前記重量平均分子量は、高速ＧＰＣ装置（東洋曹達社製ＨＬＣ－８０２Ａ）を使用して測定した。即ち、０．５質量％のＴＨＦ溶液を試料溶液とし、カラムはＴＳＫｇｅｌＧＭＨ６２本を使用し、２００μＬの試料を注入し、前記ＴＨＦ溶液で溶離して、２５℃で屈折率検出器により測定した。次に、標準ポリスチレンで較正した分子量分布曲線より重量平均分子量を求めた。
　前記ビニル基当量は、臭素価をＪＩＳ　Ｋ２６０５に準拠して測定することにより求めた。 (Synthesis Example 6)
<Resin synthesis>
A 500 mL three-necked round bottom flask equipped with a condenser and a stirrer was charged with 10.86 g (0.081 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 16.82 g of glycerol monomethacrylate (GLM). (0.105 mol) was dissolved in 79 mL of propylene glycol monomethyl ether monoacetate. To this, 37.54 g (0.15 mol) of 4,4′-diphenylmethane diisocyanate (MDI), 0.1 g of 2,6-di-t-butylhydroxytoluene, and as a catalyst, trade name: Neostan U-600 (Nitto) 0.2 g of Kasei Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 75 ° C. for 5 hours. Thereafter, the mixture was diluted with 9.61 mL of methyl alcohol and stirred for 30 minutes to obtain 145 g of an acid-modified vinyl group-containing polyurethane resin U1 solution.
The acid-modified vinyl group-containing polyurethane resin U1 obtained above has a solid content acid value of 70 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) is 8,000. The vinyl group equivalent was 1.5 mmol / g.
The acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
The weight average molecular weight was measured using a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.). That is, a 0.5 mass% THF solution was used as a sample solution, 62 columns of TSKgelGMH were used, 200 μL of a sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. Next, the weight average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
The said vinyl group equivalent was calculated | required by measuring a bromine number based on JISK2605.
（合成例７）
＜樹脂の合成＞
　クレゾール・ノボラック型エポキシ樹脂（日本化薬株式会社製、ＥＯＣＮ－１０４Ｓ、軟化点９２℃、エポキシ当量２２０）２，２００質量部（１０当量）、プロピレングリコールモノメチルエーテル１３４質量部（１モル）、アクリル酸６４８．５質量部（９モル）、メチルハイドロキノン４．６質量部、カルビトールアセテート１，１３１質量部、及びソルベントナフサ４８４．９質量部を仕込み、９０℃に加熱し撹拌し、反応混合物を溶解した。次いで、反応液を６０℃まで冷却し、トリフェニルフォスフィン１３．８質量部を仕込み、１００℃に加熱し、約３２時間反応し、酸価が０．５ｍｇＫＯＨ／ｇの反応物（水酸基、１２当量）を得た。次に、これにテトラヒドロ無水フタル酸３６４．７質量部（２．４モル）、カルビトールアセテート１３７．５質量部、及びソルベントナフサ５８．８質量部を仕込み、９５℃に加熱し、約６時間反応し、冷却し、固形分濃度４０質量％のカルボキシル基含有感光性ポリウレタン樹脂Ｕ２を得た。
　得られたカルボキシル基含有感光性ポリウレタン樹脂Ｕ１は、酸価が７０ｍｇＫＯＨ／ｇ、重量平均分子量が１２，０００、ビニル基当量が１．５ｍｍｏｌ／ｇであった。 (Synthesis Example 7)
<Resin synthesis>
Cresol / novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220) 2,200 parts by mass (10 equivalents), propylene glycol monomethyl ether 134 parts by mass (1 mol), acrylic An acid 648.5 parts by mass (9 mol), methylhydroquinone 4.6 parts by mass, carbitol acetate 1,131 parts by mass, and solvent naphtha 484.9 parts by mass were heated to 90 ° C. and stirred, and the reaction mixture was stirred. Dissolved. Next, the reaction solution was cooled to 60 ° C., charged with 13.8 parts by mass of triphenylphosphine, heated to 100 ° C., reacted for about 32 hours, and reacted with an acid value of 0.5 mg KOH / g (hydroxyl group, 12 Equivalent). Next, 364.7 parts by mass (2.4 mol) of tetrahydrophthalic anhydride, 137.5 parts by mass of carbitol acetate, and 58.8 parts by mass of solvent naphtha were added to this and heated to 95 ° C. for about 6 hours. The reaction and cooling were performed to obtain a carboxyl group-containing photosensitive polyurethane resin U2 having a solid content concentration of 40% by mass.
The obtained carboxyl group-containing photosensitive polyurethane resin U1 had an acid value of 70 mgKOH / g, a weight average molecular weight of 12,000, and a vinyl group equivalent of 1.5 mmol / g.
（実施例１）
＜感光性積層体の作製＞
－感光性組成物の調製－
　下記組成の感光性組成物を調製した。
　なお、得られた感光性組成物におけるフィラーの含有量は、感光性組成物の固形分１００質量部に対して３０質量部であった。
［感光性組成物の組成］
　合成例６で得た酸変性ビニル基含有ポリウレタン樹脂Ｕ１溶液　　　　３２．３質量部
　　（固形分４５質量％）
　重合性化合物：ＤＣＰ－Ａ（共栄社化学社製）　　　　　　　　　　　　５．３質量部
　開始剤：ＩＲＧ９０７（チバスペシャリティケミカル社製）　　　　　　０．６質量部
　　　　：ＤＥＴＸ（日本化薬社製）　　　　　　　　　　　　　　　０．００５質量部
　　　　：ＥＡＢ－Ｆ（保土ヶ谷化学社製）　　　　　　　　　　　　０．０１９質量部
　熱架橋剤：エポトートＹＤＦ－１７０（東都化成社製）　　　　　　　　２．９質量部
　顔料分散液：　　　　　　　　　　　　　　　　　　　　　　　　　　４０．７質量部
　その他：メガファックＦ－７８０Ｆ（大日本インキ（株）製：３０質量％メチルエチルケトン溶液）　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．２質量部
　シクロヘキサノン（溶媒）：　　　　　　　　　　　　　　　　　　　　８．０質量部 Example 1
<Production of photosensitive laminate>
-Preparation of photosensitive composition-
A photosensitive composition having the following composition was prepared.
In addition, content of the filler in the obtained photosensitive composition was 30 mass parts with respect to 100 mass parts of solid content of the photosensitive composition.
[Composition of photosensitive composition]
32.3 parts by mass (solid content: 45% by mass) of the acid-modified vinyl group-containing polyurethane resin U1 solution obtained in Synthesis Example 6
Polymerizable compound: DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.) 5.3 parts by mass Initiator: IRG907 (manufactured by Ciba Specialty Chemicals) 0.6 part by mass: DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.005 parts by mass: EAB -F (Hodogaya Chemical Co., Ltd.) 0.019 parts by mass Thermal crosslinking agent: Epototo YDF-170 (manufactured by Toto Kasei Co., Ltd.) 2.9 parts by mass Pigment dispersion: 40.7 parts by mass Others: Megafac F-780F (large) Nippon Ink Co., Ltd. product: 30 mass% methyl ethyl ketone solution) 0.2 mass part Cyclohexanone (solvent): 8.0 mass parts
　前記顔料分散液は、下記の通り調製して得たものである。即ち、下記成分を予め混合した後、モーターミルＭ－２５０（アイガー社製）で、直径１．０ｍｍのジルコニアビーズを用い、周速９ｍ／ｓにて３時間分散して調製したものである。 The pigment dispersion is prepared as follows. That is, the following components were mixed in advance, and then dispersed with a motor mill M-250 (manufactured by Eiger) using zirconia beads having a diameter of 1.0 mm at a peripheral speed of 9 m / s for 3 hours.
　シリカ：（アドマテック社製、ＳＯ－Ｃ２、平均粒子径０．５μｍ）　　９．８質量部
　合成例３で得た窒素原子含有樹脂（Ｊ－１）（固形分１０質量％）　　０．２２質量部
　フタロシアニンブルー　　　　　　　　　　　　　　　　　　　　　０．０２１質量部
　アントラキノン系黄色顔料（ＰＹ２４）　　　　　　　　　　　　　０．００６質量部
　シクロヘキサノン　　　　　　　　　　　　　　　　　　　　　　　　３０．７質量部 Silica: (manufactured by Admatech, SO-C2, average particle size 0.5 μm) 9.8 parts by mass Nitrogen atom-containing resin (J-1) obtained in Synthesis Example 3 (solid content 10% by mass) 0.22 parts by mass Phthalocyanine blue 0.021 parts by mass Anthraquinone yellow pigment (PY24) 0.006 parts by mass Cyclohexanone 30.7 parts by mass
－感光性フィルムの製造－
　支持体としての厚み１６μｍのポリエチレンテレフタレートフィルム（東レ株式会社製、１６ＦＢ５０）上に、前記感光性組成物を塗布し、乾燥させて、前記支持体上に厚さ３０μｍの感光層を形成した。前記感光層上に、保護層としての厚み２０μｍのポリプロピレンフィルム（王子特殊紙株式会社製、アルファンＥ－２００）を積層し、感光性フィルムを製造した。 -Production of photosensitive film-
The photosensitive composition was applied onto a polyethylene terephthalate film having a thickness of 16 μm as a support (manufactured by Toray Industries, Inc., 16FB50) and dried to form a photosensitive layer having a thickness of 30 μm on the support. On the photosensitive layer, a 20 μm-thick polypropylene film (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) as a protective layer was laminated to produce a photosensitive film.
－基体への積層－
　銅張積層板（スルーホールなし、銅厚み１２μｍ）の表面に化学研磨処理を施して基体を調製した。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（ニチゴーモートン株式会社製、ＶＰ１３０）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ィルム（支持体）とがこの順に積層された感光性積層体を調製した。
　なお、圧着条件は、真空引きの時間を４０秒間、圧着温度を７０℃、圧着圧力を０．２ＭＰａ、加圧時間を１０秒間とした。 -Lamination on substrate-
A substrate was prepared by subjecting the surface of a copper-clad laminate (no through holes, copper thickness 12 μm) to chemical polishing treatment. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Thus, a photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were such that the vacuuming time was 40 seconds, the pressure bonding temperature was 70 ° C., the pressure bonding pressure was 0.2 MPa, and the pressure application time was 10 seconds.
＜評価方法＞
＜＜埋め込み性の評価＞＞
　厚み２５μｍのポリイミドフイルム（アピカルＮＰＩ、鐘淵化学工業社製）をベースフイルムとし、該ベースフイルムに接着剤を塗布して、圧延銅箔（三井金属社製、厚み１２μｍ）を貼り付けた。次いで、上記圧延銅箔上に、ドライフイルムレジストを用いて、ライン／スペース＝１００μｍ／１００μｍで長さ８ｃｍの直線状ラインを５０本と、この直線状ラインに対して並行に、ライン／スペース＝５０μｍ／５０μｍで長さ８ｃｍの他の直線状ラインが５０本とを形成して、厚み１８μｍのパターン回路を形成して、回路付き銅張積層板を得た。
　続いて、前記感光性フィルムのロールから保護フィルム（保護層）を剥離し、感光層面を、上記回路付き銅張り積層板にラミネートして、貼り合わせサンプルを得た。該ラミネートは、温度６０℃、７５，０００Ｐａ・ｍの条件下で行った。
　Ｌ／Ｓ（ライン／スペース）＝５０μｍ／５０μｍの配線パターン間への感光層の埋め込み状態を、光学顕微鏡を用いて５０倍～２００倍の倍率で観察し、下記基準に基づいて評価した。結果を下記表３に示す。
〔評価基準〕
　　○：前記感光性フィルムが、前記パターン回路とベースフイルムとの段差を埋め込み、前記感光性フィルムと前記回路付き銅張り積層板との間に隙間ができていない場合
　　○△：前記感光性フィルムと上記回路付き銅張り積層板との間に隙間が生じている場合や、パターン回路と感光性積層体との間に空気の泡等が生じている場合
　　△：溶融粘度が高すぎてラミネートできない場合
　　×：溶融粘度が低すぎて、基板への積層時気泡は入らないが、基板と支持体の間から感光層が大量に浸みだす場合 <Evaluation method>
<< Evaluation of embeddability >>
A polyimide film (Apical NPI, Kaneka Chemical Co., Ltd.) having a thickness of 25 μm was used as a base film, an adhesive was applied to the base film, and a rolled copper foil (Mitsui Metals Co., Ltd., thickness 12 μm) was attached. Next, on the rolled copper foil, using a dry film resist, 50 linear lines having a line / space = 100 μm / 100 μm and a length of 8 cm, and in parallel to the linear line, the line / space = 50 linear lines of 50 μm / 50 μm in length and another 8 cm in length formed 50 to form a pattern circuit having a thickness of 18 μm to obtain a copper-clad laminate with circuit.
Subsequently, the protective film (protective layer) was peeled from the roll of the photosensitive film, and the surface of the photosensitive layer was laminated on the copper-clad laminate with a circuit to obtain a bonded sample. The lamination was performed under conditions of a temperature of 60 ° C. and 75,000 Pa · m.
The embedded state of the photosensitive layer between the wiring patterns of L / S (line / space) = 50 μm / 50 μm was observed at a magnification of 50 to 200 times using an optical microscope and evaluated based on the following criteria. The results are shown in Table 3 below.
〔Evaluation criteria〕
○: When the photosensitive film embeds a step between the pattern circuit and the base film, and there is no gap between the photosensitive film and the copper-clad laminate with circuit ○ △: With the photosensitive film When there is a gap between the above-mentioned copper-clad laminate with circuit or when air bubbles are generated between the pattern circuit and the photosensitive laminate △: When the melt viscosity is too high to laminate X: When melt viscosity is too low and bubbles do not enter during lamination on the substrate, but a large amount of photosensitive layer oozes between the substrate and the support
＜＜解像性＞＞
　前記感光性積層体を室温（２３℃）で５５％ＲＨにて１０分間静置した。得られた感光性積層体のポリエチレンテレフタレートフィルム（支持体）上から、公知のパターン形成装置を用いて、丸穴パターンを用い、丸穴の直径の幅５０μｍ～２００μｍの丸穴が形成できるよう露光を行った。
　この際の露光量は、前記感度の評価における前記感光性フィルムの感光層を硬化させるために必要な光エネルギー量である。室温にて１０分間静置した後、前記感光性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）を剥がし取った。
　銅張積層板上の感光層の全面に、現像液として３０℃の１質量％炭酸ナトリウム水溶液をスプレー圧０．１５ＭＰａにて最短現像時間の２倍の時間スプレーし、未硬化領域を溶解除去した。
　このようにして得られた硬化樹脂パターン付き銅張積層板の表面を光学顕微鏡で観察し、パターンの丸穴底部に残渣が無いこと、パターン部の捲くれ・剥がれなどの異常が無く、かつスペース形成可能な最小の丸穴パターン幅を測定し、これを解像度とし、下記基準で評価した。該解像度は数値が小さいほど良好である。結果を下記表３に示す。
〔評価基準〕
　　○：直径９０μｍ以下の丸穴が解像可能で、解像性に優れている。
　　○△：直径９０μｍを超え１２０μｍ以下の丸穴が解像可能で、解像性良好である。
　　△：直径１２０μｍを超え２００μｍ以下の丸穴が解像可能で、解像性がやや劣る。
　　×：丸穴が解像不可で、解像性が劣る。 << Resolution >>
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). Using the well-known pattern forming apparatus, a round hole pattern is exposed on the polyethylene terephthalate film (support) of the resulting photosensitive laminate so that a round hole with a diameter of 50 μm to 200 μm can be formed. Went.
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the photosensitive film in the sensitivity evaluation. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
The entire surface of the photosensitive layer on the copper clad laminate was sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as a developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve and remove uncured areas. .
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, there is no residue at the bottom of the round hole of the pattern, there are no abnormalities such as blistering / peeling of the pattern, and space The minimum round hole pattern width that can be formed was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution. The results are shown in Table 3 below.
〔Evaluation criteria〕
A: A round hole having a diameter of 90 μm or less can be resolved, and the resolution is excellent.
(Circle) (triangle | delta): The round hole more than 90 micrometers in diameter and 120 micrometers or less can be resolved, and resolution is favorable.
Δ: A round hole having a diameter exceeding 120 μm and not more than 200 μm can be resolved, and the resolution is slightly inferior.
X: A round hole cannot be resolved and the resolution is inferior.
＜＜現像残渣＞＞
　現像残渣は、解像性評価において、３００μｍ丸穴パターンの残渣の状態により評価した。結果を下記表３に示す。
〔評価基準〕
　　○：丸穴パターン内に残渣は見られず、現像残渣除去性に優れる。
　　○△：丸穴パターンの周辺にやや残渣が見られるが、現像残渣除去性は良好。
　　△：丸穴パターン内周辺に明らかな残渣が見られ、現像残渣除去性にやや劣る。
　　×：丸穴パターン内に残渣が見られ、現像残渣除去性に劣る。 << Development residue >>
The development residue was evaluated by the state of the residue of the 300 μm round hole pattern in the resolution evaluation. The results are shown in Table 3 below.
〔Evaluation criteria〕
○: No residue is observed in the round hole pattern, and the development residue removability is excellent.
○ △: Some residue is observed around the round hole pattern, but the development residue removability is good.
(Triangle | delta): A clear residue is seen in the circumference | surroundings in a round hole pattern, and a development residue removal property is a little inferior.
X: Residues are observed in the round hole pattern, and the development residue removability is poor.
＜＜耐熱性＞＞
　基板上に各感光性組成物からなるソルダーレジスト層を形成しロジン系フラックスを塗布した評価基板を、予め２６０℃に設定したはんだ槽に３０秒間浸漬し、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ、剥れ、及び変色について、下記基準により評価した。結果を下記表３に示す。
〔評価基準〕
　　○：全く変化が認められず、耐熱性に優れる。
　　○△：膨れ、剥がれが僅かに見られるものの、耐熱性は良好である。
　　△：一部膨れ、剥がれが見られ、耐熱性に劣る。
　　×：塗膜に膨れ、剥れがある。 << Heat resistance >>
An evaluation substrate on which a solder resist layer made of each photosensitive composition is formed on a substrate and a rosin-based flux is applied is immersed in a solder bath previously set at 260 ° C. for 30 seconds, and the flux is washed with denatured alcohol. The swelling, peeling, and discoloration of the resist layer due to were evaluated according to the following criteria. The results are shown in Table 3 below.
〔Evaluation criteria〕
○: No change is observed and heat resistance is excellent.
○: Swelling and peeling are slightly seen, but the heat resistance is good.
(Triangle | delta): Partial swelling and peeling are seen and it is inferior to heat resistance.
X: The coating film swells and peels off.
＜＜強靭性＞＞
　前記感光性積層体に、厚み１２μｍの銅箔をガラスエポキシ基材に積層したプリント基板上にソルダーレジスト層を定法にて形成し、２ｍｍ角フォトマスクを介し、オーク製作所社製ＨＭＷ－２０１ＧＸ型露光機を使用して、２ｍｍ角パターンが形成できる最適露光量（３００ｍＪ／ｃｍ２～１Ｊ／ｃｍ２）で露光を行った。次いで、常温で１時間静置した後、３０℃の１質量％炭酸ナトリウム水溶液にて６０秒間スプレー現像を行い、更に８０℃で１０分間加熱（乾燥）した。続いて、オーク製作所社製紫外線照射装置を使用して１Ｊ／ｃｍ２のエネルギー量で感光層に対する紫外線照射を行った。更に感光層を１５０℃で６０分間加熱処理を行うことにより、２ｍｍ角の矩形開口部を有するソルダーレジストを形成した評価用基板を得た。
　得られた基板を－６５℃の大気中に１５分間晒した後、次いで１５０℃の大気中に１５分間晒した後、再度－６５℃の大気中に晒す熱サイクルを１，０００回繰り返した。熱サイクルを通した評価用基板のソルダーレジスト上のひび及び剥離程度を光学顕微鏡により観察した。結果を下記表３に示す。
〔評価基準〕
　　○：ソルダーレジストにひび、剥れが無く、強靭性に優れる。
　　○△：ソルダーレジストに僅かにひびがあるものの、強靭性は良好である。
　　△：ソルダーレジストに僅かにひび、剥れがあり、強靭性にやや劣る。
　　×：ソルダーレジストに明らかなひび、剥れがあり、強靭性が劣る。 << Toughness >>
A solder resist layer is formed on a printed circuit board obtained by laminating a copper foil having a thickness of 12 μm on a glass epoxy base material on the photosensitive laminate, and a HMW-201GX type exposure made by Oak Seisakusho through a 2 mm square photomask. The exposure was performed with an optimum exposure dose (300 mJ / cm 2 to 1 J / cm 2 ) that can form a 2 mm square pattern. Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm 2 using an ultraviolet irradiation device manufactured by Oak Seisakusho. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist having a 2 mm square opening was formed.
The obtained substrate was exposed to an atmosphere of −65 ° C. for 15 minutes, then exposed to an atmosphere of 150 ° C. for 15 minutes, and then exposed to the air of −65 ° C. again for 1,000 times. The crack and peeling degree on the solder resist of the evaluation substrate through the thermal cycle were observed with an optical microscope. The results are shown in Table 3 below.
〔Evaluation criteria〕
○: The solder resist is not cracked or peeled off and has excellent toughness.
○ Δ: Although the solder resist is slightly cracked, the toughness is good.
Δ: The solder resist is slightly cracked and peeled, and is slightly inferior in toughness.
X: The solder resist has obvious cracks and peeling, and the toughness is inferior.
＜＜絶縁性＞＞
　厚み１２μｍの銅箔をガラスエポキシ基材に積層したプリント基板の銅箔にエッチングを施して、ライン幅／スペース幅が５０μｍ／５０μｍであり、互いのラインが接触しておらず、互いに対向した同一面上の櫛形電極を得た。この基板の櫛形電極上に、前記感光性積層体を形成し、ソルダーレジスト層を定法にて形成し、最適露光量（３００ｍＪ／ｃｍ２～１Ｊ／ｃｍ２）で露光を行った。次いで、常温で１時間静置した後、３０℃の１質量％炭酸ナトリウム水溶液にて６０秒間スプレー現像を行い、更に８０℃で１０分間加熱（乾燥）した。続いて、オーク製作所社製紫外線照射装置を使用して１Ｊ／ｃｍ２のエネルギー量で感光層に対する紫外線照射を行った。更に感光層を１５０℃で６０分間加熱処理を行うことにより、ソルダーレジストを形成した評価用基板を得た。
　加熱後の評価用基板の櫛形電極間に電圧が印加されるように、ポリテトラフルオロエチレン製のシールド線をＳｎ／Ｐｂはんだにより、それらの櫛形電極に接続した後、評価用積層体に５Ｖの電圧を印可した状態で、該評価用積層体を１３０℃、８５％ＲＨの超加速高温高湿寿命試験（ＨＡＳＴ）槽内に２００時間静置した。その後の評価用積層体のソルダーレジストのマイグレーションの発生程度を１００倍の金属顕微鏡により観察した。結果を下記表３に示す。
〔評価基準〕
　　○：マイグレーションの発生が確認できず、絶縁性に優れる。
　　○△：マイグレーションの発生が銅上僅かに確認されるが、絶縁性は良好である。
　　△：マイグレーションの発生が確認され、絶縁性にやや劣る。
　　×：電極間が短絡し、絶縁性に劣る。 << Insulation >>
The copper foil of the printed circuit board obtained by laminating a copper foil having a thickness of 12 μm on a glass epoxy substrate is etched, the line width / space width is 50 μm / 50 μm, the lines are not in contact with each other, and the same facing each other A comb electrode on the surface was obtained. The photosensitive laminate was formed on the comb-shaped electrode of this substrate, a solder resist layer was formed by a conventional method, and exposure was performed with an optimum exposure amount (300 mJ / cm 2 to 1 J / cm 2 ). Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm 2 using an ultraviolet irradiation device manufactured by Oak Seisakusho. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist was formed.
After connecting the polytetrafluoroethylene shield wires to the comb electrodes with Sn / Pb solder so that a voltage is applied between the comb electrodes of the evaluation substrate after heating, 5V is applied to the evaluation laminate. With the voltage applied, the evaluation laminate was allowed to stand in a super accelerated high temperature and high humidity life test (HAST) bath at 130 ° C. and 85% RH for 200 hours. Thereafter, the degree of migration of the solder resist in the laminate for evaluation was observed with a 100-fold metal microscope. The results are shown in Table 3 below.
〔Evaluation criteria〕
○: The occurrence of migration cannot be confirmed, and the insulation is excellent.
○ Δ: Migration is slightly observed on copper, but insulation is good.
(Triangle | delta): Generation | occurrence | production of migration is confirmed and it is somewhat inferior to insulation.
X: The electrodes are short-circuited and insulative.
（実施例２）
　実施例１において、シリカの配合量を、感光性組成物の固形分１００質量部に対して３０質量部から４０質量部に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 (Example 2)
In Example 1, the photosensitive laminate was prepared in the same manner as in Example 1 except that the amount of silica was changed from 30 parts by mass to 40 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Prepared and evaluated. The results are shown in Table 3.
（実施例３）
　実施例１において、シリカの配合量を、感光性組成物の固形分１００質量部に対して３０質量部から１５質量部に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 (Example 3)
In Example 1, the photosensitive laminate was prepared in the same manner as in Example 1 except that the amount of silica was changed from 30 parts by mass to 15 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition. Prepared and evaluated. The results are shown in Table 3.
（実施例４）
　実施例１において、窒素原子含有樹脂（Ｊ－１）を窒素原子含有樹脂（Ｊ－２）に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 Example 4
A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that the nitrogen atom-containing resin (J-1) was replaced with the nitrogen atom-containing resin (J-2) in Example 1. The results are shown in Table 3.
（実施例５）
　実施例１において、窒素原子含有樹脂（Ｊ－１）を窒素原子含有樹脂（Ｊ－３）に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 (Example 5)
A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that the nitrogen atom-containing resin (J-1) was replaced with the nitrogen atom-containing resin (J-3) in Example 1. The results are shown in Table 3.
（実施例６）
　実施例１において、酸変性ビニル基含有ポリウレタン樹脂Ｕ１をカルボキシル基含有感光性ポリウレタン樹脂Ｕ２に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 (Example 6)
A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that the acid-modified vinyl group-containing polyurethane resin U1 was replaced with the carboxyl group-containing photosensitive polyurethane resin U2 in Example 1. The results are shown in Table 3.
（実施例７）
　実施例１において、シリカをシリカ（アドマテック社製、ＳＯ－Ｃ３、平均粒子径０．９μｍ）に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 (Example 7)
A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that silica was replaced with silica (manufactured by Admatech, SO-C3, average particle size: 0.9 μm) in Example 1. The results are shown in Table 3.
（実施例８）
　実施例１において、シリカをシリカ（アドマテック社製、ＳＯ－Ｃ１、平均粒子径０．２５μｍ）に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 (Example 8)
A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that silica was changed to silica (manufactured by Admatech, SO-C1, average particle diameter of 0.25 μm) in Example 1. The results are shown in Table 3.
（実施例９）
　実施例１において、シリカをアルミナ（信越石英社製、ＡＯ－８０２、平均粒子径０．７μｍ）に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 Example 9
A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that silica was replaced with alumina (manufactured by Shin-Etsu Quartz, AO-802, average particle size 0.7 μm) in Example 1. The results are shown in Table 3.
（比較例１）
　実施例１において、窒素原子含有樹脂（Ｊ－１）を酸変性ビニル基含有ポリウレタン樹脂Ｕ１に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 (Comparative Example 1)
A photosensitive laminate was prepared and evaluated in the same manner as in Example 1 except that the nitrogen atom-containing resin (J-1) was replaced with the acid-modified vinyl group-containing polyurethane resin U1 in Example 1. The results are shown in Table 3.
（比較例２）
　実施例１において、窒素原子含有樹脂（Ｊ－１）をソルスパース２４０００（ルーブリゾール社製、塩基性分散剤（本発明の感光性組成物における前記窒素原子含有樹脂とは異なる。））に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。 (Comparative Example 2)
In Example 1, the nitrogen atom-containing resin (J-1) was replaced with Solsperse 24000 (manufactured by Lubrizol, a basic dispersant (different from the nitrogen atom-containing resin in the photosensitive composition of the present invention)). Except for the above, a photosensitive laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.
（比較例３）
　実施例１において、窒素原子含有樹脂（Ｊ－１）をソルスパース２６０００（ルーブリゾール社製、酸性基含有樹脂）に代えた以外は、実施例１と同様にして、感光性積層体を作製し、評価した。結果を表３に示す。
　なお、ソルスパース２６０００は、本発明の感光性組成物における窒素原子含有樹脂とは異なるものであり、かつカラーフィルタ用の感光性組成物の分散剤として汎用されているものである。 (Comparative Example 3)
In Example 1, a photosensitive laminate was prepared in the same manner as in Example 1 except that the nitrogen atom-containing resin (J-1) was replaced with Solsperse 26000 (Lubrisol, acid group-containing resin). evaluated. The results are shown in Table 3.
Solsperse 26000 is different from the nitrogen atom-containing resin in the photosensitive composition of the present invention, and is widely used as a dispersant for the photosensitive composition for color filters.
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000072
　本発明の感光性組成物は、フィラーの含有量が多い場合においても粘度が高くならず、かつ解像性が高く、現像残渣がなく、さらに、耐熱性、強靭性、絶縁性に優れることから、ソルダーレジストとして好適に使用することができる。 The photosensitive composition of the present invention has high viscosity even when the filler content is high, has high resolution, no development residue, and is excellent in heat resistance, toughness, and insulation. It can be suitably used as a solder resist.

Claims (15)

  1. 　窒素原子含有樹脂、該窒素原子含有樹脂以外の樹脂、熱架橋剤、及びフィラーを含有し、
    　前記窒素原子含有樹脂が、窒素原子を有する主鎖と、前記主鎖に存在する窒素原子と結合し、かつｐＫａが１４以下である官能基を一部に有する基と、前記主鎖と結合し、かつ数平均分子量が５００～１，０００，０００のグラフト鎖とを有することを特徴とする感光性組成物。     Containing a nitrogen atom-containing resin, a resin other than the nitrogen atom-containing resin, a thermal crosslinking agent, and a filler,
    The nitrogen atom-containing resin is bonded to the main chain having a nitrogen atom, a group having a functional group having a pKa of 14 or less, bonded to the main chain having a nitrogen atom, and the main chain. And a photosensitive composition having a graft chain having a number average molecular weight of 500 to 1,000,000.
  2. 　フィラーが、シリカである請求項１に記載の感光性組成物。 The photosensitive composition according to claim 1, wherein the filler is silica.
  3. 　フィラーの含有量が、感光性組成物の固形分１００質量部に対して、１０質量部～９７質量部である請求項１から２のいずれかに記載の感光性組成物。 The photosensitive composition according to claim 1, wherein the filler content is 10 to 97 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive composition.
  4. 　窒素原子を有する主鎖が、アミノ基を有する重合体から構成される主鎖である請求項１から３のいずれかに記載の感光性組成物。 The photosensitive composition according to claim 1, wherein the main chain having a nitrogen atom is a main chain composed of a polymer having an amino group.
  5. 　アミノ基を有する重合体から構成される主鎖が、ポリ（アルキレンイミン）、ポリアリルアミン、ポリジアリルアミン、メタキシレンジアミン－エピクロルヒドリン重縮合物、及びポリビニルアミンから選択される１種以上で構成される主鎖である請求項４に記載の感光性組成物。 A main chain composed of a polymer having an amino group is composed mainly of at least one selected from poly (alkyleneimine), polyallylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, and polyvinylamine. The photosensitive composition according to claim 4 which is a chain.
  6. 　ｐＫａが１４以下である官能基を一部に有する基が、下記一般式（Ｖ－１）から（Ｖ－３）で表される基のいずれかである請求項１から５のいずれかに記載の感光性組成物。
    Figure JPOXMLDOC01-appb-C000001
     　ただし、前記一般式（Ｖ－１）、及び前記一般式（Ｖ－２）中、Ｕは単結合及び二価の連結基のいずれかを表す。ｄ及びｅは、それぞれ独立に、０及び１のいずれかを表す。
    　前記一般式（Ｖ－３）中、Ｗは、アシル基及びアルコキシカルボニル基のいずれかを表す。     6. The group having in part a functional group having a pKa of 14 or less is any of the groups represented by the following general formulas (V-1) to (V-3): Photosensitive composition.
    Figure JPOXMLDOC01-appb-C000001
     However, in the general formula (V-1) and the general formula (V-2), U represents either a single bond or a divalent linking group. d and e each independently represents either 0 or 1;
    In the general formula (V-3), W represents either an acyl group or an alkoxycarbonyl group.
  7. 　窒素原子含有樹脂が、下記一般式（Ｉ－１）で表される繰返し単位、及び下記一般式（Ｉ－２）で表される繰返し単位を有する請求項１から６のいずれかに記載の感光性組成物。
    Figure JPOXMLDOC01-appb-C000002
     　ただし、前記一般式（Ｉ－１）及び（Ｉ－２）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子、ハロゲン原子、及びアルキル基のいずれかを表す。ａは、それぞれ独立に、１～５の整数のいずれかを表す。「＊」は、繰返し単位間の連結部を表す。Ｘは、ｐＫａが１４以下である官能基を一部に有する基を表す。Ｙは、数平均分子量が５００～１，０００，０００のグラフト鎖を表す。     The photosensitive resin according to any one of claims 1 to 6, wherein the nitrogen atom-containing resin has a repeating unit represented by the following general formula (I-1) and a repeating unit represented by the following general formula (I-2). Sex composition.
    Figure JPOXMLDOC01-appb-C000002
     However, in the general formulas (I-1) and (I-2), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group. a represents each independently an integer of 1 to 5. “*” Represents a connecting portion between repeating units. X represents a group partially having a functional group having a pKa of 14 or less. Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
  8. 　窒素原子含有樹脂が、下記一般式（ＩＩ－１）で表される繰返し単位、及び下記一般式（ＩＩ－２）で表される繰返し単位を有する請求項１から６のいずれかに記載の感光性組成物。
    Figure JPOXMLDOC01-appb-C000003
     　ただし、前記一般式（ＩＩ－１）及び（ＩＩ－２）中、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子、及びアルキル基のいずれかを表す。「＊」は、繰返し単位間の連結部を表す。Ｘは、ｐＫａが１４以下である官能基を一部に有する基を表す。Ｙは、数平均分子量が５００～１，０００，０００のグラフト鎖を表す。     The photosensitive resin according to any one of claims 1 to 6, wherein the nitrogen atom-containing resin has a repeating unit represented by the following general formula (II-1) and a repeating unit represented by the following general formula (II-2). Sex composition.
    Figure JPOXMLDOC01-appb-C000003
     However, in the general formulas (II-1) and (II-2), R 3 , R 4 , R 5 and R 6 each independently represent any of a hydrogen atom, a halogen atom and an alkyl group. “*” Represents a connecting portion between repeating units. X represents a group partially having a functional group having a pKa of 14 or less. Y represents a graft chain having a number average molecular weight of 500 to 1,000,000.
  9. 　数平均分子量が５００～１，０００，０００のグラフト鎖が、下記一般式（ＩＩＩ－１）で表されるグラフト鎖である請求項１から８のいずれかに記載の感光性組成物。
    Figure JPOXMLDOC01-appb-C000004
     　ただし、前記一般式（ＩＩＩ－１）中、Ｚは、ポリエステル鎖を部分構造として少なくとも有する重合体残基であって、下記一般式（ＩＶ）で表される遊離のカルボン酸を有するポリエステルからカルボキシル基を除いた重合体残基を表す。
    Figure JPOXMLDOC01-appb-C000005
     　ただし、前記一般式（ＩＶ）中、Ｚは、前記一般式（ＩＩＩ－１）中のＺと同じである。     9. The photosensitive composition according to claim 1, wherein the graft chain having a number average molecular weight of 500 to 1,000,000 is a graft chain represented by the following general formula (III-1).
    Figure JPOXMLDOC01-appb-C000004
     However, in the general formula (III-1), Z is a polymer residue having at least a polyester chain as a partial structure, and from a polyester having a free carboxylic acid represented by the following general formula (IV) to a carboxyl It represents a polymer residue excluding a group.
    Figure JPOXMLDOC01-appb-C000005
     However, in the general formula (IV), Z is the same as Z in the general formula (III-1).
  10. 　窒素原子含有樹脂が、一級アミノ基及び二級アミノ基の少なくともいずれかを有する樹脂と、ｐＫａが１４以下である官能基を一部に有する基の前駆体と、数平均分子量が５００～１，０００，０００のグラフト鎖の前駆体とを反応させて得られる樹脂である請求項１から９のいずれかに記載の感光性組成物。 The nitrogen atom-containing resin is a resin having at least one of a primary amino group and a secondary amino group, a precursor of a group partially having a functional group having a pKa of 14 or less, and a number average molecular weight of 500 to 1, The photosensitive composition according to claim 1, which is a resin obtained by reacting with a precursor of a graft chain of 000,000.
  11. 　さらに、重合性化合物と、光重合開始剤とを含有する請求項１から１０のいずれかに記載の感光性組成物。 Furthermore, the photosensitive composition in any one of the Claims 1-10 containing a polymeric compound and a photoinitiator.
  12. 　請求項１から１１のいずれかに記載の感光性組成物からなる感光層を支持体上に有することを特徴とする感光性フィルム。 A photosensitive film comprising a photosensitive layer comprising a photosensitive composition according to any one of claims 1 to 11 on a support.
  13. 　基体上に、請求項１から１１のいずれかに記載の感光性組成物を含む感光層を有することを特徴とする感光性積層体。 A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to claim 1 on a substrate.
  14. 　請求項１から１１のいずれかに記載の感光性組成物により形成された感光層に対して露光を行うことを少なくとも含むことを特徴とする永久パターン形成方法。 A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of claims 1 to 11.
  15. 　請求項１４に記載の永久パターン形成方法によって形成された永久パターンを備えることを特徴とするプリント基板。 A printed circuit board comprising a permanent pattern formed by the permanent pattern forming method according to claim 14.
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