Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

Definitions

• the present invention relates to an alkali-soluble resin and a photosensitive resin composition. More particularly, the present invention relates to an alkali-soluble resin, a photosensitive resin composition, and a cured product thereof that can give a cured product with excellent solvent resistance even under low-temperature curing conditions.
• Alkali-soluble resins are compounds used in various fields ranging from civil engineering and construction materials to electronic information materials, and are preferably used as materials such as alkali-developable resist compositions (also referred to as photosensitive resin compositions).
• the photosensitive resin composition is a composition whose physical properties change when the coating film is irradiated with light or electron beams, that is, for example, the exposed part cures and the other part exhibits solubility. It is a composition and is used in various fields such as electronic information materials and optical materials by utilizing this property.
• various optical members and electric and electronic devices such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, organic insulating films, organic protective films, etc.
• Patent Document 1 a compound (a) having an epoxy group, a photobase generator (b), a curing agent (c) having a thiol group, a monomer having an unsaturated bond (d), and photoirradiation
• a photocurable resin composition containing a radical generating agent (e) that generates radicals is disclosed, and a photocurable resin composition having no tackiness when used as a coating film formed before exposure has been found.
• Patent Document 2 a copolymer containing three types of (meth)acrylate repeating units classified according to the types of functional groups present at the terminals and having alkali solubility, photocurability and thermosetting properties,
• the photosensitive resin composition used is disclosed. It has excellent thermosetting properties at relatively low temperatures, can be photo-cured by light irradiation, has an improved degree of curing, and has excellent durability and chemical resistance. is obtained. However, there is room for improvement in solvent resistance.
• Patent Document 3 a resin having a structure in which a monocarboxylic acid is added to a part of the epoxy groups of a polyfunctional epoxy resin and a polybasic acid is added to another part of the epoxy groups, is disclosed. Although this is excellent in crack resistance when cured, it is assumed to be used for filling holes in printed wiring boards, and there is room for improvement in alkali solubility.
• JP 2013-181991 A Japanese Patent Publication No. 2021-521310 JP 2013-40233 A
• the present invention has been made in view of the above-mentioned current situation, and can provide a cured product having excellent solvent resistance even under low temperature curing conditions, and can be suitably used for various applications such as color filters.
• An object of the present invention is to provide an alkali-soluble resin and a photosensitive resin composition containing the resin.
• an alkali-soluble resin having a specific structural unit having an acid group and a polymerizable unsaturated double bond and an epoxy equivalent weight of 5000 g/equivalent or less.
• a photosensitive resin composition containing a specific alkali-soluble resin (A), for example, a cresol novolak type alkali-soluble resin (A) having a main chain, a polymerizable compound (B), and a photopolymerization initiator (C)
• A specific alkali-soluble resin
• A cresol novolak type alkali-soluble resin having a main chain
• B polymerizable compound
• C photopolymerization initiator
• ⁇ 1> An alkali-soluble resin having an acid group and a polymerizable unsaturated double bond and having an epoxy equivalent of 5000 g/equivalent or less, wherein the alkali-soluble resin is a structural unit represented by the following formula (1): , a structural unit represented by the following formula (2), and an alkali-soluble resin having a structural unit represented by the following formula (3).
• A represents a benzene ring or a naphthalene ring
• R 1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
• R 2 represents a substituent bonded to A, a hydroxyl group, or , represents an organic group having 1 to 20 carbon atoms
• a represents the number of R 2 and is an integer of 0 to 5. When there are two or more R 2 , they may be the same or different. is also good.
• A represents a benzene ring or a naphthalene ring
• R 3 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
• R 4 represents a substituent bonded to A, a hydroxyl group, or , represents an organic group having 1 to 20 carbon atoms
• b represents the number of R 4 and is an integer of 0 to 5.
• X represents an organic group.
• A represents a benzene ring or a naphthalene ring
• R 5 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
• R 6 represents a substituent bonded to A, a hydroxyl group, or , represents an organic group having 1 to 20 carbon atoms
• c represents the number of R 6 and is an integer of 0 to 5.
• Y represents an organic group.
• the structural unit represented by the above formula (1) is a structural unit represented by the following formula (1-1), and the structural unit represented by the above formula (2) is a structural unit represented by the following formula (2- 1), and the structural unit represented by the above formula (3) is a structural unit represented by the following formula (3-1), the alkali-soluble resin according to ⁇ 1> above. .
• R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• X represents an organic group.
• R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• Y represents an organic group.
• Z represents a divalent organic group.
• a photosensitive resin composition containing the alkali-soluble resin (A) is a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and the following formula (3)
• A represents a benzene ring or a naphthalene ring
• R 1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
• R 2 represents a substituent bonded to A, a hydroxyl group, or , represents an organic group having 1 to 20 carbon atoms
• a represents the number of R 2 and is an integer of 0 to 5. When there are two or more R 2 , they may be the same or different. is also good.
• A represents a benzene ring or a naphthalene ring
• R 3 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
• R 4 represents a substituent bonded to A, a hydroxyl group, or , represents an organic group having 1 to 20 carbon atoms
• b represents the number of R 4 and is an integer of 0 to 5.
• X represents an organic group.
• A represents a benzene ring or a naphthalene ring
• R 5 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
• R 6 represents a substituent bonded to A, a hydroxyl group, or , represents an organic group having 1 to 20 carbon atoms
• c represents the number of R 6 and is an integer of 0 to 5.
• Y represents an organic group
• Z represents a divalent organic group.
• ⁇ 5> The photosensitive resin composition according to ⁇ 3> or ⁇ 4> above, further comprising an acid compound having an acid dissociation constant pKa of 4.2 or less.
• ⁇ 6> The photosensitive resin composition according to ⁇ 3> or ⁇ 4> above, further comprising a phosphoric acid derivative.
• ⁇ 7> The photosensitive resin composition according to any one of ⁇ 3> to ⁇ 6> above, further comprising a basic compound.
• ⁇ 8> The photosensitive resin composition according to any one of ⁇ 3> to ⁇ 7>, wherein the alkali-soluble resin (A) further has a structural unit represented by the following formula (4).
• L represents a divalent linking group.
• R 9 and R 10 are the same or different and represent a substituent.
• d represents the number of R 9 and is an integer of 0 to 4.
• e represents the number of R 10 and is an integer of 0 to 4.
• R 9 and R 10 are plural, they may be the same or different.
• ⁇ 9> A cured product obtained by curing the alkali-soluble resin described in ⁇ 1> or ⁇ 2> above or the photosensitive resin composition described in any one of ⁇ 3> to ⁇ 8> above.
• ⁇ 10> A display device member comprising the cured product according to ⁇ 9> above.
• ⁇ 11> A display device comprising the cured product according to ⁇ 9> above.
• the alkali-soluble resin and photosensitive resin composition of the present invention can give a cured product with excellent solvent resistance even under relatively low temperature curing conditions of 160° C. or less.
• the cured product of the present invention can be used for various applications such as various optical members used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc., and structural members for electrical and electronic equipment. is preferably used for
• (meth)acrylic acid means “acrylic acid and/or methacrylic acid”
• (meth)acrylate means “acrylate and/or methacrylate”.
• Min to Max means the minimum value Min or more and the maximum value Max or less. Furthermore, when describing preferred numerical values in stages for the upper and lower limits, a numerical range obtained by appropriately combining the upper and lower limits that are separately described is also a preferred numerical range.
• total solid content means the total amount of components forming the cured product, i.e., the total amount of components (solid content, non-volatile content) excluding the solvent that volatilizes during the formation of the cured product.
• an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and other cured product-forming components e.g., coloring materials, dispersing agents, etc.
• the total solid means fractional mass.
• the alkali-soluble resin (A)] of the present invention is a resin exhibiting alkali solubility and has an acid group in its molecule.
• the acid group is preferably a carboxyl group, and other acid groups include functional groups that undergo a neutralization reaction with alkaline water, such as phenolic hydroxyl groups, carboxylic acid anhydride groups, phosphoric acid groups, and sulfonic acid groups. It may have only seeds, or may have two or more kinds.
• the alkali-soluble resin (A) can also act as a binder resin in the photosensitive resin composition described below.
• the alkali-soluble resin (A) of the present invention is an alkali-soluble resin having an acid group and a polymerizable unsaturated double bond and an epoxy equivalent of 5000 g/equivalent or less, and the alkali-soluble resin is represented by the above formula ( 1), a structural unit represented by the above formula (2), and a structural unit represented by the above formula (3).
• the "structural unit" in alkali-soluble resin means the repeating unit which comprises alkali-soluble resin.
• the alkali-soluble resin (A) has an acid group and a polymerizable unsaturated double bond, has an epoxy equivalent in a predetermined range, and is a structural unit represented by the above formula (1), and the above formula (2).
• the effect of the present invention is exhibited by having the structural unit represented by the above formula (3).
• the solvent resistance of the cured product is improved by photo-radical cross-linking by polymerizable unsaturated double bonds (preferably (meth)acryloyl groups). The inventor speculates that it will improve.
• A represents a benzene ring or a naphthalene ring, preferably a benzene ring in terms of the balance between alkali solubility and physical properties of the cured product.
• R 1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
• Examples of the divalent hydrocarbon group include a hydrocarbon group having a chain structure or a hydrocarbon group containing a cyclic structure.
• Examples of the chain-structured hydrocarbon group include aliphatic hydrocarbon groups.
• Examples of divalent aliphatic hydrocarbon groups include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, t-butylene group, pentylene group, neopentylene group, hexamethylene group, heptylene group, Alkylene groups such as octylene group, 2-ethylhexylene group, nonylene group, decylene group, undecylene group, dodecylene group; vinylene group, propenylene group, isopropenylene group, butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group alkenylene group such as group; alkynylene group such as ethynylene group, propynylene group, 1-butynylene group, 2-butynylene group
• hydrocarbon group containing a cyclic structure examples include a hydrocarbon group having a cyclic structure and a hydrocarbon group having a cyclic structure and a chain structure.
• hydrocarbon group having a cyclic structure examples include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
• divalent alicyclic hydrocarbon groups include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornylene group, an adamantylene group, a tricyclodecanylene group, a tetracyclodecanylene group, and the like.
• cycloalkenylene groups such as cyclopropenylene group, cyclobutenylene group and cyclopentenylene group
• cycloalkylidene groups such as cyclopentylidene group and cyclohexylidene group
• divalent aromatic hydrocarbon group examples include arylene groups such as phenylene group, tolylene group and naphthylene group.
• the hydrocarbon group having a cyclic structure and a chain structure includes a hydrocarbon group composed of a combination of a hydrocarbon group having a cyclic structure and a hydrocarbon group having a chain structure, such as a cinnamylidene group and a biphenylene group. is mentioned.
• the divalent hydrocarbon group is more preferably a divalent aliphatic hydrocarbon group, and even more preferably an alkylene group, in view of easy availability.
• the divalent hydrocarbon group preferably has 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 carbon atom.
• the divalent hydrocarbon group at least one atom constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. Moreover, the divalent hydrocarbon group may have a substituent such as an alkoxy group.
• R 2 represents a substituent bonded to A.
• substituents include a hydroxyl group and an organic group having 1 to 20 carbon atoms.
• Examples of the organic group represented by R 2 include an optionally substituted hydrocarbon group, or the above optionally substituted hydrocarbon group and -O-, -COO-, Groups combined with a bonding group such as —CO—, —NH—, —S—, —SO— or —SO 2 — are included.
• hydrocarbon group examples include a monovalent or divalent hydrocarbon group having a chain structure or a hydrocarbon group containing a cyclic structure.
• hydrocarbon group containing a cyclic structure examples include a hydrocarbon group having a cyclic structure and a hydrocarbon group having a cyclic structure and a chain structure.
• hydrocarbon group having a cyclic structure examples include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
• the divalent hydrocarbon group is as described above.
• Examples of monovalent hydrocarbon groups include those obtained by converting the above-mentioned divalent hydrocarbon groups into monovalent groups.
• the monovalent aliphatic hydrocarbon group includes an alkyl group, an alkenyl group and the like
• the alicyclic hydrocarbon group includes a cycloalkyl group and the like
• the aromatic hydrocarbon group includes an aryl group. etc.
• hydrocarbon group having a cyclic structure and a chain structure examples include a hydrocarbon group composed of a combination of the above-described hydrocarbon group having a cyclic structure and a hydrocarbon group having a chain structure.
• examples include a benzyl group, a phenethyl group, biphenyl group, tolyl group, xylyl group and the like.
• the number of carbon atoms in the hydrocarbon group is preferably 1-20, more preferably 1-10.
• At least one atom constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom.
• the hydrocarbon group may have a substituent, and examples of the substituent include an alkoxy group, an amide group, an amino group, an epoxy group, a glycidyl group, and a hydroxyl group.
• the substituent represented by R 2 is —OH, —O—CH 2 —(C 2 H 3 O), —CR a1 R a2 —(C 6 H 4 ) —O—CH 2 —(C 2 H 3 O), —CR a1 R a2 —(C 6 H 4 )—OH (wherein R a1 and R a2 are the same or different and are hydrogen or methyl ), preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. is more preferred, and a methyl group is particularly preferred.
• a represents the number of substituents R 2 and is an integer of 0-5.
• a is preferably from 0 to 3, more preferably from 0 to 1, and even more preferably 1 from the viewpoint that the developability of the resin is good.
• each R 2 may be the same or different.
• the structural unit (A-1) represented by formula (1) above preferably includes a structural unit represented by formula (1-1) below.
• R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• A represents a benzene ring or a naphthalene ring, preferably a benzene ring.
• R 3 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
• the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 3 includes the same groups as the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 in the above formula (1). mentioned. Among them, R 3 is preferably a divalent aliphatic hydrocarbon group, more preferably an alkylene group.
• R 4 represents a substituent bonded to A.
• substituent include a hydroxyl group and an organic group having 1 to 20 carbon atoms.
• organic group having 1 to 20 carbon atoms represented by R 4 include the same groups as the organic group having 1 to 20 carbon atoms represented by R 2 above.
• R 4 the substituents represented by R 4 are —OH, —O—CH 2 —(C 2 H 3 O), —CR a1 R a2 —(C 6 H 4 )—O—CH 2 —(C 2 H 3 O), —CR a1 R a2 —(C 6 H 4 ) —OH (wherein R a1 and R a2 are the same or different and represent a hydrogen atom or a methyl group), 1 to It is preferably an aliphatic hydrocarbon group of 20, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and is a methyl group. is particularly preferred.
• b represents the number of substituents R 4 and is an integer of 0-5.
• b is preferably 0 to 3, more preferably 0 to 1, and even more preferably 1, from the viewpoint of good developability.
• each R 4 may be the same or different.
• X represents an organic group.
• the organic group represented by X include the above-described organic groups, preferably an organic group having 1 to 20 carbon atoms, more preferably an organic group having 1 to 10 carbon atoms, and an organic group having 1 to 5 carbon atoms.
• Organic groups are more preferred.
• An organic group having a vinyl group or an allyl group is particularly preferred, and an organic group having a (meth)acryloyl group is more preferred.
• —CH 2 —OOC-CR a4 ⁇ CH 2 (R a4 represents a hydrogen atom or a methyl group) is more preferred.
• the structural unit (A-2) represented by the above formula (2) preferably includes a structural unit represented by the following formula (2-1), more preferably the following formula (2-1- 1) may be used as a structural unit.
• R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• X is the same as described above.
• R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• R 7 represents a hydrogen atom or a methyl group.
• A represents a benzene ring or a naphthalene ring, preferably a benzene ring.
• R 5 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
• the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 5 includes the same groups as the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 in the above formula (1). mentioned. Among them, R 5 is preferably a divalent aliphatic hydrocarbon group, more preferably an alkylene group.
• R6 represents a substituent bonded to A.
• substituent include a hydroxyl group and an organic group having 1 to 20 carbon atoms.
• organic group having 1 to 20 carbon atoms represented by R 6 include the same groups as the organic group having 1 to 20 carbon atoms represented by R 2 above.
• R 6 the substituents represented by R 6 are —OH, —O—CH 2 —(C 2 H 3 O), —CR a1 R a2 —(C 6 H 4 )—O—CH 2 —(C 2 H 3 O), —CR a1 R a2 —(C 6 H 4 ) —OH (wherein R a1 and R a2 are the same or different and represent a hydrogen atom or a methyl group), 1 to It is preferably an aliphatic hydrocarbon group of 20, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and is a methyl group. is particularly preferred.
• c represents the number of substituents R 6 and is an integer of 0-5.
• c is preferably from 0 to 3, more preferably from 0 to 1, from the viewpoint of good developability.
• c is 2 or more, that is, when there are 2 or more R 6 , each R 6 may be the same or different.
• Y represents an organic group.
• the organic group represented by Y include the above-described organic groups, preferably an organic group having 1 to 20 carbon atoms, more preferably an organic group having 1 to 10 carbon atoms, and an organic group having 1 to 5 carbon atoms.
• Organic groups are more preferred.
• An organic group having a vinyl group or an allyl group is more preferred, and an organic group having a (meth)acryloyl group is even more preferred.
• Examples of the organic group having a (meth)acryloyl group include the same groups as the organic group having a (meth)acryloyl group represented by X described above.
• Z represents a divalent organic group.
• the divalent organic group represented by Z include an alkylene group having 1 to 20 carbon atoms, an arylene group and the like, which may be partially substituted.
• the substituent is not particularly limited, and examples thereof include halogen atoms such as fluorine, chlorine and iodine atoms.
• substituents include alkyl groups such as methyl and ethyl groups in addition to halogen atoms.
• the alkylene group may have a linear structure, or may have a branched structure or an alicyclic structure. Specifically, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, t-butylene group, pentylene group, neopentylene group, hexamethylene group, heptylene group, octylene group, 2-ethylhethylene xylene group, nonylene group, decylene group, undecylene group, dodecylene group and the like.
• Specific examples of the arylene group include a phenylene group, a tolylene group, a naphthylene group, a diethylnaphthylene group and the like.
• examples of the divalent organic group include the following groups in addition to the above-described alkylene group and arylene group: —O—, —SO 2 —, —CO—, —COO—, —C 6 H 5 O—, —(C n H 2n )O— (n represents an integer of 1 to 10), —NH— .
• the divalent organic group is preferably an alkylene group having 1 to 10 carbon atoms, —COO—, —C 6 H 5 O—, —SO 2 —, or —NH—, and preferably has 1 carbon atom. ⁇ 5 alkylene groups are more preferred.
• the alkylene group may be linear or branched.
• the structural unit (A-3) represented by the above formula (3) preferably includes a structural unit represented by the following formula (3-1), more preferably the following formula (3-1- 1) may be used as a structural unit.
• R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• Y and Z are the same as described above.
• R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• R 8 represents a hydrogen atom or a methyl group.
• the molar ratio of the structural unit (A-3) is preferably 1/0.05-6.75/0.40-8.10, more preferably 1/0.5-2.0/0.2-2 .0.
• the alkali-soluble resin (A) may contain one or more of the structural units (A-1), (A-2), and (A-3).
• the alkali-soluble resin (A) of the present invention preferably further has a structural unit represented by the following formula (4) in addition to the structural units represented by the above formulas (1) to (3). Any molecular weight can be designed by chain extension by introducing the following structural unit.
• L represents a divalent linking group.
• R 9 and R 10 are the same or different and represent a substituent.
• d represents the number of R 9 and is an integer of 0 to 4.
• e represents the number of R 10 and is an integer of 0 to 4.
• R 9 and R 10 are plural, they may be the same or different.
• L represents a divalent linking group.
• the linking group L includes divalent linking groups such as an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, -SO 2 -, and -NH-.
• the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms. Moreover, it may be linear, branched, or cyclic. Moreover, the alkylene group and the arylene group may have a substituent.
• the substituent is not particularly limited, and examples thereof include halogen atoms such as a fluorine atom, a chlorine atom, and an iodine atom.
• examples of substituents include alkyl groups such as methyl and ethyl groups in addition to halogen atoms.
• the substituent represented by R 9 and R 10 preferably includes a hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. d and e are preferably zero.
• the structural units represented by the above formula (4) include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol It is preferably a structural unit derived from any one compound selected from PH, bisphenol TMC, and bisphenol Z, and particularly preferably a structural unit derived from bisphenol S, bisphenol A, and bisphenol F. It is most preferably a structural unit.
• Particularly preferred structural units are structural units represented by the following formulas (4-1) to (4-3).
• the molar ratio of structural unit (A-3)/structural unit (A-4) represented by formula (4) is 1/0.05 to 6.75/0.40 to 8.10/0.01 to 0.1 is preferred, more preferably 1/0.5 to 2.0/0.2 to 2.0/0.01 to 0.1.
• the molar ratio of other structural units is preferably 0.3 or less, more preferably 0.1 or less, and particularly preferably substantially free.
• a suitable range of the acid value of the alkali-soluble resin (A) is preferably 30 to 200 mgKOH/g, more preferably 40 to 160 mgKOH/g, still more preferably 50 to 140 mgKOH/g, particularly preferably 50 to 120 mgKOH/g. is. Within the above range, good alkali solubility (developability) can be obtained, and high curability and alkali resistance and solvent resistance of the cured product can be maintained.
• the acid value can be measured by the method described in Examples below.
• the weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably, for example, 3000 or more. Thereby, it is possible to give a cured product which is more excellent in heat resistance and mechanical strength. It is more preferably 4,000 or more, and still more preferably 5,000 or more. Such a high molecular weight is very suitable because the dispersibility and heat resistance of the coloring material are improved and the deterioration of the alkali-soluble resin is sufficiently suppressed to improve the reliability.
• the upper limit of Mw is not particularly limited, it is preferably 200,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, and particularly preferably, from the viewpoint of achieving a lower viscosity and further improving developability. 50,000 or less, most preferably 30,000 or less. In the present specification, the weight average molecular weight can be measured by the method described in Examples below.
• the alkali-soluble resin (A) has an epoxy equivalent weight of 5000 g/equivalent or less. By controlling the content within this range, the curability is improved and the solvent resistance is improved.
• the epoxy equivalent is more preferably 3000 g/equivalent or less, still more preferably 2000 g/equivalent or less, and most preferably 1500 g/equivalent or less.
• the epoxy equivalent is preferably 400 g/equivalent or more, more preferably 600 g/equivalent or more, and even more preferably 800 g/equivalent or more, from the viewpoint of storage stability.
• the epoxy equivalent can be obtained by dividing the resin solid content by the number of moles of epoxy groups contained in the resin.
• the epoxy equivalent can also be obtained by a method conforming to JIS K7236:2001.
• the glass transition temperature (Tg) of the alkali-soluble resin (A) is preferably 40°C or higher, more preferably 50°C or higher, even more preferably 60°C or higher, and particularly preferably 70°C or higher. It is believed that such a glass transition temperature improves the strength of the cured product.
• the alkali-soluble resin (A) has a photosensitive polymerizable unsaturated double bond in its side chain.
• the polymerizable unsaturated double bond equivalent of the alkali-soluble resin (A) is preferably 100 to 5000 g/equivalent. By setting it to such a range, it can be expected that both sufficient storage stability of the resin and good plate-making properties such as sensitivity and pattern shape of the photosensitive resin composition of the present invention are achieved at a higher level. .
• the polymerizable unsaturated double bond equivalent is more preferably 330 g/equivalent or more, still more preferably 400 g/equivalent or more, particularly preferably 500 g/equivalent or more, more preferably 3000 g/equivalent or less, still more preferably 2000 g/equivalent.
• the equivalent weight or less particularly preferably 1000 g/equivalent or less.
• polymerizable unsaturated double bond equivalent refers to the mass (g) of the solid content of the resin solution per 1 mol of the polymerizable unsaturated double bond of the alkali-soluble resin. It can be obtained by dividing the mass of the solid content of the resin solution by the amount of polymerizable unsaturated double bonds in the resin. It can also be measured by titration, elemental analysis, various analyzes such as NMR and IR, and differential scanning calorimetry. For example, it may be calculated by measuring the number of ethylenic double bonds contained per 1 g of resin in accordance with the iodine value test method described in JIS K 0070:1992.
• the alkali-soluble resin (A) of the present invention is, for example, a reaction product of a novolak-type epoxy resin and an unsaturated monocarboxylic acid described later, a dibasic acid anhydride such as succinic anhydride, trimellitic anhydride, or pyromellitic anhydride. It can be obtained by reacting it with an acid anhydride such as an aromatic polyvalent carboxylic anhydride such as an acid. In this case, the reaction is carried out by adjusting the charge amount of the compound so that it has an acid group and a polymerizable unsaturated double bond and an epoxy equivalent weight of 5000 g/equivalent or less.
• a reaction product of a novolak-type epoxy resin and an unsaturated monocarboxylic acid described later a dibasic acid anhydride such as succinic anhydride, trimellitic anhydride, or pyromellitic anhydride. It can be obtained by reacting it with an acid anhydride such as an aromatic polyvalent carb
• the number of ethylenically unsaturated bonds (polymerizable unsaturated double bonds) present in one molecule of the alkali-soluble resin (A) is increased to improve photocurability.
• a novolak-type epoxy resin as a raw material.
• Typical novolak-type epoxy resins include phenol novolak-type epoxy resins and cresol novolak-type epoxy resins, and resins obtained by known methods are used. be able to.
• the novolak-type epoxy resin those that are solid at room temperature are preferable, and cresol novolak-type epoxy resins are particularly preferable.
• cresol novolak-type epoxy resin examples include cresol novolak-type epoxy resins represented by the following formula (5).
• R is an alkyl group having 1 to 6 carbon atoms and may be the same or different. Also, n is an integer. Preferably, all R are methyl groups.
• cresol novolac epoxy resin represented by the above formula (5) examples include YDCN-704A, YDCN-700-10, and YDCN-700-7 (all manufactured by Nippon Steel Chemical & Materials Co., Ltd.). be done. These are used alone or in combination of two or more.
• the cresol novolak type epoxy resin preferably has a softening point of 120° C. or lower. It is preferably 68-100°C, most preferably 88-100°C. Within the above range, a cured product having high transparency and high strength can be obtained.
• unsaturated monocarboxylic acids include monobasic acids having one carboxyl group and one or more radically polymerizable unsaturated bonds, and specific examples include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -acryloxypropionic acid, a reaction product of a hydroxyalkyl (meth)acrylate having one hydroxyl group and one (meth)acryloyl group and a dibasic acid anhydride, one hydroxyl group and two or more Reaction products of polyfunctional (meth)acrylates having (meth)acryloyl groups and dibasic acid anhydrides, caprolactone-modified products of these monobasic acids, etc. can be used alone or in combination of two or more. Among them, those having a (meth)acryloyl group such as acrylic acid and methacrylic acid are preferable.
• Representative acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylene tetrahydro phthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, octenylsuccinic anhydride, pentadodecenylsuccinic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, 9,10 -Dibasic acid anhydrides such as reaction products of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with itaconic anhydride or maleic anhydride; trimellitic anhydride, pyromellitic anhydr
• the resin in addition, as a means to set the final physical properties of the resin to an arbitrary amount of polymerizable unsaturated double bonds and acid value, in combination with unsaturated monocarboxylic acid, a long-chain alkyl group, a substituent containing an aromatic ring, an alcoholic hydroxyl 1 or 2 or more of monocarboxylic acids having no polymerizable unsaturated double bond such as a phenol compound or thiophenol compound which may have a group, or acetic acid, propionic acid, dimethylolpropionic acid, etc. You can use it.
• the types and amounts used are appropriately selected according to the required properties such as the physical properties of the cured product.
• the alkali-soluble resin (A) of the present invention is not particularly limited, and can be obtained through the above-described reaction steps and similar reaction steps such as changing the order of preparation, and is synthesized by the following reactions. is preferred.
• a predetermined amount of unsaturated monocarboxylic acid is reacted with a novolac type epoxy resin.
• an epoxy group and a carboxyl group are reacted at a ratio of 1:1 to open the epoxy ring and ester-bond an unsaturated monocarboxylic acid residue to the resin skeleton.
• an OH group is generated by ring-opening of the epoxy ring.
• the acid equivalent/epoxy equivalent ratio is preferably in the range of 0.1 to 0.9. Within this range, both storage stability and low-temperature curability are further improved.
• the first step it is preferable to react while stirring at 70°C to 150°C.
• a known phosphorus compound or a known amine compound as a catalyst, more preferably a phosphorus compound from the viewpoint of suppressing ring-opening polymerization of epoxy groups, and most preferably triphenylphosphine.
• the amine compound triethylamine, dimethylbenzylamine, and the like are preferable from the viewpoint of activity. It is also preferable to use an antioxidant such as p-methoxyphenol to prevent oxidation of unsaturated bonds. It is preferable that a resin having the structural unit (A-1) and the structural unit (A-2) is obtained by the reaction in the first step.
• the product of the first step is reacted with a predetermined amount of acid anhydride.
• the OH group generated by ring-opening of the epoxy ring reacts with the acid anhydride at a ratio of 1:1 to form an ester bond.
• the acid anhydride is a dicarboxylic acid anhydride
• a carboxyl group is generated at the other end of the acid anhydride residue at the same time. Therefore, a carboxyl group is bound to the resin skeleton via an ester bond.
• an alkali-soluble resin having the structural unit (A-3) is obtained by the reaction in the second step.
• the resin by adding and reacting a bisphenol compound during the reaction of the first step.
• a bisphenol compound By increasing the molecular weight, the hardness of the cured product can be increased.
• the most preferable alkali-soluble resin (A) in the present invention is synthesized from an epoxy resin, a phenol compound, an unsaturated monocarboxylic acid, and an acid anhydride, and uses a cresol novolak type epoxy resin as at least a part of the epoxy resin, is obtained by using one having a bisphenol skeleton as at least a part of.
• an alkali-soluble resin having the above structural unit (A-4) in addition to the above structural units (A-1) to (A-3) is obtained.
• Any molecular weight can be designed by introducing the structural unit (A-4) to extend the chain.
• epoxy resin other known epoxy resins other than the cresol novolac type epoxy resin described above may be used in combination.
• epoxy resins include hydrogenated (hydrogenated) alicyclic epoxy resins such as bisphenol A type ; diglycidyl ester type epoxy resin; polyhydric alcohol diglycidyl ether type epoxy resin, particularly polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or bisphenol which is a precursor of the above bisphenol type epoxy resin Dihydric alcohols obtained by adding alkylene oxide to a compound, and diglycidyl ether type epoxy resins obtained by reacting epichlorohydrin; bifunctional epoxy compounds such as diglycidylamine type epoxy resins, tetraglycidylaminodiphenylmethane, etc.
• polyfunctional glycidyl amine resins polyfunctional glycidyl ether resins such as tetraphenylglycidyl ether ethane; phenolic novolac type epoxy resins; Reaction product of epichlorohydrin with polyphenol compound obtained by condensation reaction with aromatic aldehyde; Reaction of epichlorohydrin with polyphenol compound obtained by addition reaction of phenol compound and diolefin compound such as divinylbenzene or dicyclopentadiene product; epoxidized ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracid; trifunctional or higher epoxy compounds such as epoxy resins having a heterocyclic ring such as triglycidyl isocyanurate.
• the amount used is preferably 50 mol % or less when the total solid content of the epoxy resin is 100 mol %.
• a more preferred amount of other epoxy resins used is 30 mol % or less, and a further preferred amount is 10 mol % or less.
• the most preferable usage amount is 5 mol % or less, and it is preferable not to use it substantially. Within the above range, more rigidity is exhibited, and the effect of improving the dimensional stability of the cured product is sufficiently obtained.
• the alkali-soluble resin (A) of the present invention is chain-extended in order to increase the molecular weight
• a phenol compound having a bisphenol skeleton as at least a part thereof.
• those having a bisphenol S skeleton are preferable, and since the sulfone group is electron-withdrawing, the acidity of the phenolic hydroxyl group increases, and the reactivity with the epoxy group increases.
• Examples of such a phenol compound having a bisphenol S skeleton include bisphenol S, tetrabromobisphenol S, tetramethylbisphenol S, and the like, and they can be used singly or in combination of two or more.
• bisphenol S is most preferable from the viewpoint of availability.
• phenol compound a known bifunctional phenol compound having no bisphenol S skeleton may be used in combination.
• examples of such phenol compounds include bisphenol A, bisphenol F, and 9,9-bis(4-hydroxyphenyl).
• Known bisphenols other than bisphenol S such as fluorene and bis(4-hydroxyphenyl)sulfide, and biphenols can be mentioned.
• a trifunctional or higher functional phenol compound may be partially used in combination, examples of which include novolak resins and 1,1,1-tris(4-hydroxyphenyl)ethane.
• the amount used is preferably 50 mol % or less when the total solid content of the phenol compound is 100 mol %.
• a more preferable usage amount is 30 mol % or less, and a further preferable usage amount is 10 mol % or less.
• the most preferable usage amount is 5 mol % or less, and it is preferable not to use it substantially. Within the above range, the reactivity is improved and the chain elongation reaction proceeds more efficiently.
• the synthesis reaction of the precursor of the alkali-soluble resin (A) in the present invention (before the reaction with the acid anhydride), that is, the reaction of the first stage described above, ⁇ Method of preparing phenol compound, epoxy resin and unsaturated monocarboxylic acid at the same time and synthesizing them all at once, - A method in which a phenol compound and an epoxy resin are first subjected to a chain extension reaction, and then an unsaturated monocarboxylic acid is reacted.
• the reaction solvent is not limited as long as it is an inert organic solvent in which the above compounds are dissolved, but hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; Esters such as cellosolve acetate, carbitol acetate, (di)propylene glycol monomethyl ether acetate, (dimethyl)glutarate, (dimethyl)succinate, and (dimethyl)adipate; ketones such as methyl isobutyl ketone and methyl ethyl ketone ; ethers such as (di)ethylene glycol dimethyl ether and the like.
• the total amount of the phenolic hydroxyl group in the phenolic compound and the carboxyl group in the unsaturated monocarboxylic acid is 0.01 to 0.8 mol with respect to 1 mol of the epoxy group in the epoxy resin. It is preferable to let
• Synthesis reaction conditions of the alkali-soluble resin (precursor) are not particularly limited, but in the presence or absence of diluents such as polymerizable compounds and solvents described later, hydroquinone and oxygen and a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, a tertiary phosphine such as triphenylphosphine, benzyltriphenyl
• a reaction catalyst such as a quaternary phosphonium salt such as phosphonium bromide, an organic acid or inorganic salt of a metal, or a chelate compound
• the reaction is usually carried out at 80 to 150°C.
• the alkali-soluble resin (precursor) obtained above contains an alcoholic hydroxyl group formed by ring-opening of the epoxy group through reaction between the epoxy group of the epoxy resin and a phenolic hydroxyl group or unsaturated monocarboxylic acid. base exists.
• the alkali-soluble resin ( A) is obtained.
• the solvent for the addition reaction in the second step is not particularly limited, and any solvent that can be used in the synthesis in the first step can be used. Industrially, it is convenient to add an acid anhydride to the reaction solution to carry out the second-stage addition reaction following the first-stage synthesis.
• a catalyst may be used for the above addition reaction, if necessary.
• Specific catalysts include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine and tetraphenylphosphonium bromide. , carboxylic acid metal salts such as lithium acetate, and inorganic metal salts such as lithium carbonate.
• the above acid anhydride is such that the acid anhydride group in the acid anhydride is 0.1 to 1 mol per 1 mol of the hydroxyl group in the vinyl ester (precursor of the alkali-soluble resin obtained in the first step reaction). It is preferable to react so that the amount becomes 1 mol, more preferably 0.15 to 0.9 mol, and still more preferably 0.2 to 0.8 mol.
• the reaction temperature is preferably 45 to 150°C, more preferably 50 to 70°C, still more preferably 55 to 65°C.
• the alkali-soluble resin (A) of the present invention preferably contains an acid compound having an acid dissociation constant pKa of 4.2 or less. That is, it is preferably an alkali-soluble resin solution containing the alkali-soluble resin (A) and an acid compound having an acid dissociation constant pKa of 4.2 or less. By containing the acid compound, the storage stability of the alkali-soluble resin (A) can be improved.
• the acid dissociation constant pKa means the negative common logarithm (reciprocal logarithm) of the equilibrium constant Ka in the dissociation reaction in which hydrogen ions are released from an acid, and particularly means the value in water at 25°C.
• pKa values for example, reference can be made to literature such as Kagaku Binran, Basic Edition II (revised 5th edition, Maruzen Co., Ltd.), and values not listed in the literature are calculated by the method described in the literature. can do.
• acid compounds having an acid dissociation constant pKa of 4.2 or less include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, and phosphine.
• Aromatic sulfonic acids such as sulfinic acid, naphthalenesulfinic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, diisobutylna
• the phosphoric acid derivative is preferably phosphate, phosphite, phosphorous acid, hypophosphorous acid, phosphonic acid or phosphinic acid, and more preferably phosphate, phosphonic acid or phosphinic acid.
• Examples of the ester group of the phosphate or phosphite include an alkyl ester group, an aryl ester group, an aralkyl ester group, and an ester group having a polymerizable unsaturated double bond.
• the alkyl of the alkyl ester group includes methyl, ethyl, octyl, 2-ethylhexyl and the like.
• Aryl of the above aryl ester group includes phenyl, tolyl, naphthyl and the like. Benzyl etc. are mentioned as aralkyl of the said aralkyl ester group.
• Examples of the ester group having a polymerizable unsaturated double bond include a 2-acryloyloxyethyl ester group and a 2-methacryloyloxyethyl ester group.
• phosphoric acid esters include monoalkyl phosphates such as methyl phosphate; dialkyl phosphates such as dibutyl phosphate; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl trialkyl phosphates such as pentaerythrityl diphosphate, tris(2-chloroethyl) phosphate, tris(2,3-dichloropropyl) phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; monoaryl phosphate; diaryl phosphate; , tricresyl phosphate, tris(nonylphenyl) phosphate, triaryl phosphates such as 2-ethylphenyl diphenyl phosphate; 2-methacryloyloxye
• the phosphonic acid examples include alkylphosphonic acids such as methylphosphonic acid and arylphosphonic acids such as phenylphosphonic acid.
• the phosphinic acid examples include alkylphosphinic acids such as methylphosphinic acid and arylphosphinic acids such as phenylphosphinic acid.
• a phosphate ester containing an ester group having a polymerizable unsaturated double bond is preferable.
• the photosensitive resin composition containing the alkali-soluble resin solution (composition) is cured, together with the alkali-soluble resin and the polymerizable compound It forms a crosslinked structure, suppresses volatilization and elution of contained components, and can significantly suppress problems such as contamination of the reaction system and deterioration of electrical insulation.
• the phosphate ester preferably contains 2 or 3 or more polymerizable unsaturated double bonds.
• commercially available products can be used as the phosphate ester containing an ester group having a polymerizable unsaturated double bond.
• Kagaku Kagaku
• Phosmer M manufactured by Unichemical
• light ester P-2M is preferred.
• the molecular weight of the phosphoric acid derivative is preferably 400 or less, more preferably 350 or less.
• the resin solid content when added can be reduced, and the storage stability is further improved.
• the effects of improving the anionicity of the acid group and reducing the nucleophilic force are further enhanced.
• the molecular weight of the phosphoric acid derivative is preferably 150 or more, more preferably 250 or more. When the molecular weight of the phosphoric acid derivative is 150 or more, the compatibility with the resin composition can be further improved.
• the content of the phosphoric acid derivative is not particularly limited, and may be appropriately set according to the application and the blending of other components. , preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and even more preferably 0.02 to 2% by mass.
• total solid content means the total amount of components forming the cured product (excluding the solvent and the like that volatilize during the formation of the cured product).
• the content of the phosphoric acid derivative is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the alkali-soluble resin in the alkali-soluble resin solution. It is preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 3 parts by mass.
• the content of the phosphoric acid derivative is preferably 50 to 400 mol% with respect to 100 mol% of the basic compound used, It is more preferably 70 to 300 mol %, even more preferably 80 to 200 mol %.
• the alkali-soluble resin solution and the photosensitive resin composition containing the alkali-soluble resin are stored stably. The properties are further improved, and the coloring of the cured product can be further suppressed.
• the alkali-soluble resin solution preferably contains a protic polar solvent.
• Storage stability can be improved by containing a protic polar solvent.
• the said alkali-soluble resin has an acid group and an epoxy group as above-mentioned. Since these groups are highly reactive, curing of the alkali-soluble resin at low temperatures is facilitated, but storage stability may decrease. can be suppressed.
• protic polar solvent examples include water, alcohol solvents, amine solvents, and phenol solvents.
• the protic polar solvent is preferably an alcohol solvent.
• saturated alcohols are preferably mentioned, and monofunctional alcohols (monoalcohols), polyhydric alcohols, glycol monoethers and the like are mentioned.
• alcohol solvent examples include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n.
• - propyl ether ethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene Primary alcohols such as glycol monomethyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol, tripropylene glycol mono-n-butyl ether; Isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, cyclohexanol, 2-heptanol, 3-heptanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n -propyl ether, propylene glycol mono-n-
• the alcohol-based solvent is a secondary alcohol or a tertiary alcohol in terms of suppressing reactivity with epoxy groups and reducing the viscosity of the alkali-soluble resin solution (curable resin composition). is preferred.
• the number of carbon atoms in the alcohol-based solvent is preferably 1 to 10, more preferably 2 to 8, and 3 to 6 in that the boiling point is relatively low and removal by heating is easy. is more preferred.
• Propylene glycol monomethyl ether is particularly preferred as the alcohol solvent.
• Examples of the amine-based solvent include diethyleneamine, dimethylamine, and oleylamine.
• phenolic solvent examples include phenol, cresol, o-cresol, m-cresol, p-cresol and xylenol.
• protic polar solvent Only one type of the protic polar solvent may be used, or two or more types may be used in combination.
• the boiling point of the protic polar solvent is preferably 70 to 170° C., and 100 to 160° C. because it is easy to remove by heating, has a certain boiling point, and is easy to form a flat film. more preferably 120 to 150°C.
• the content of the protic polar solvent is preferably 10% by mass or more, more preferably 30% by mass, and 40% by mass or more with respect to 100% by mass of the total solid content of the alkali-soluble resin solution. It is even more preferable to have
• the content of the protic polar solvent is preferably 1000% by mass or less with respect to 100% by mass of the total solid content of the alkali-soluble resin solution in terms of facilitating concentration adjustment in the alkali-soluble resin solution. , is more preferably 300% by mass or less, and even more preferably 200% by mass or less.
• the alkali-soluble resin solution may contain a basic compound.
• the crosslinking reaction proceeds well even under low-temperature curing conditions of 160° C. or less when curing the photosensitive resin composition containing the alkali-soluble resin solution, and the solvent resistance is further improved. Excellent cured products can be obtained.
• Examples of the basic compound include ammonia; primary amines such as methylamine; secondary amines such as dimethylamine; tertiary amines such as triethylamine and diethylmethylamine; Amines; Cycloaliphatic amines such as cyclohexylamine; Heterocyclic amines such as piperidine, morpholine, N-ethylpiperidine, N-ethylmorpholine and pyridine; Aromatics such as benzylamine, N-methylaniline and N,N-dimethylaniline amines; tetraalkylammonium halides such as tetramethylammonium chloride and tetraethylammonium chloride; tetraalkylammonium organic acid salts such as tetramethylammonium acetate; tetraalkylammonium inorganic acid salts such as tetramethylammonium hydrogensulfate and tetraeth
• the content of the above-mentioned basic compound is not particularly limited, and may be appropriately set according to the application and the blending of other components. It is preferably 10 mass %, more preferably 0.01 to 6 mass %, even more preferably 0.02 to 4 mass %.
• the content of the basic compound is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the alkali-soluble resin. .1 to 6 parts by mass is more preferable.
• the amount of the basic compound can be added to adjust the content in the alkali-soluble resin solution.
• the photosensitive resin composition of the present invention comprises an alkali-soluble resin (A) having a specific structural unit having an acid group and a polymerizable unsaturated double bond and an epoxy equivalent of 5000 g/equivalent or less, a polymerizable compound ( B) and a photoinitiator (C) are included at least. If necessary, one or more other components may be included, and one or more of each component may be used. Moreover, the said photosensitive resin composition may contain the alkali-soluble resin solution mentioned above as said alkali-soluble resin (A).
• the alkali-soluble resin (A) contained in the photosensitive resin composition of the present invention is the alkali-soluble resin (A) described above.
• the content of the alkali-soluble resin (A) in the photosensitive resin composition is not particularly limited, and may be appropriately set according to the application and the blending of other components. It is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and 80% by mass or less with respect to the total amount of 100% by mass. It is preferably 75% by mass or less, more preferably 70% by mass or less.
• the polymerizable compound is a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation of free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), active energy rays such as electron beams, etc. Examples thereof include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.
• Examples of the monofunctional compounds include N-substituted maleimide-based monomers; (meth)acrylic acid esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; Unsaturated monocarboxylic acids with chain extension between groups; Unsaturated acid anhydrides; Aromatic vinyls; Conjugated dienes; Vinyl esters; Vinyl ethers; is mentioned.
• a monomer having an active methylene group or an active methine group can also be used.
• polyfunctional compound examples include the following compounds. Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol Bifunctional (meth)acrylate compounds such as di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate; trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dip
• a trifunctional or higher polyfunctional (meth)acrylate compound such as a modified product of dipentaerythritol hexaacrylate represented by; Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditri Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl
• Polyfunctional urethane (meth)acrylates obtained by reaction of polyfunctional isocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; polyfunctional aromatic vinyls such as divinylbenzene; These polymerizable compounds may be used singly or in combination of two or more.
• the polymer having a vinyl ether group in the side chain improves the curability of the resin composition, it may reduce the storage stability. It is preferable not to contain a polymer having a vinyl ether group in a side chain.
• the functionality of the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more. Further, the functional number is preferably 10 or less, more preferably 8 or less. Although the molecular weight of the polymerizable compound is not particularly limited, it is preferably 2000 or less from the viewpoint of handling.
• polyfunctional polymerizable compounds from the viewpoint of reactivity, economy, availability, etc., preferably polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, (meth)acryloyl groups
• examples include compounds having a (meth)acryloyl group, such as containing isocyanurate compounds, and more preferably polyfunctional (meth)acrylate compounds.
• the photosensitive resin composition becomes more excellent in photosensitivity and curability, and a cured product with higher hardness and higher transparency can be obtained.
• the polyfunctional polymerizable compound it is more preferable to use a trifunctional or higher polyfunctional (meth)acrylate compound.
• the above polymerizable compounds may be used alone or in combination of two or more.
• the content of the polymerizable compound is not particularly limited as long as the effect of the present invention is exhibited and may be set appropriately. From the standpoint of viscosity, it is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.
• the photopolymerization initiator (C) is preferably a radically polymerizable photopolymerization initiator.
• a radically polymerizable photopolymerization initiator is one that generates polymerization initiation radicals upon irradiation with active energy rays such as electromagnetic waves and electron beams.
• the photopolymerization initiator include, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (“IRGACURE369”, manufactured by BASF), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpho Aminoketone compounds such as phosphorus-4-yl-phenyl)-butan-1-one (“IRGACURE379”, manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one (“IRGACURE651”, BASF), benzyl ketal compounds such as phenylglyoxylic acid methyl ester (“DAROCUR MBF”, manufactured by BASF); 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, manufactured by BASF), 2- Hydr
• the content of the photopolymerization initiator (C) is not particularly limited as long as the effect of the present invention is exhibited, and may be set as appropriate. It is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 8% by mass with respect to the total amount of 100% by mass.
• the photosensitive resin composition preferably further contains an acid compound having an acid dissociation constant pKa of 4.2 or less.
• the acid compound include those similar to those described above.
• the content of the oxide includes the same amount as the content of the oxide for the alkali-soluble resin described above.
• the photosensitive resin composition preferably further contains a basic compound.
• the basic compound include those similar to those described above.
• the content of the basic compound includes the same amount as the content of the basic compound for the alkali-soluble resin described above.
• the photosensitive resin composition may further contain a coloring material.
• the coloring materials may be used singly or in combination according to the color of the target pixel.
• Pigments organic pigments, inorganic pigments), dyes, and the like are preferably used as the coloring material.
• the above pigments are not particularly limited, but examples include azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone-based, perylene-based, perinone-based, isoindolinone-based, isoindoline-based, dioxazine-based, thioindigo-based, and anthraquinone-based pigments).
• organic pigments such as dye lake-based pigments; white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) , Chromatic pigments (yellow, cadmium, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine blue, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.) ), black pigments (carbon black, bone black, graphite, iron black, titanium black, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) Inorganic pigments such as; Among them
• pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. I.
• red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60; C.I. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. I. Green pigments such as Pigment Green 7, 36, 58, 59; C.I. I. Pigment Brown 23, 25 and other brown pigments; C.I. I. Pigment Black 1, 7, carbon black, titanium black, black pigments such as iron oxide, and the like.
• Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60
• C.I. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38
• C.I. I. Green pigments such as Pigment Green 7, 36, 58
• the dye is not particularly limited, but for example, the organic dyes described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599. can be used. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, xanthene dyes and the like are preferable.
• dyes include acid alizarin violet N; acid black 1, 2, 24, 48; , 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; , 63, 74, 95; 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54 , 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof.
• the present invention it is preferable to use at least a dye as a coloring material in order to meet the recent demands for higher color purity and higher brightness, and even if a dye is used, excellent physical properties of the cured product can be exhibited. Therefore, it is very useful.
• the content of the dye is preferably 10% by mass or more with respect to 100% by mass of the total amount of the coloring materials. More preferably 20% by mass or more, still more preferably 40% by mass or more, particularly preferably 60% by mass or more, and most preferably 80% by mass or more.
• the upper limit is 100% by mass, that is, a mode in which only a dye is used as a coloring material is also suitable, and a mode in which less than 100% by mass, that is, a mode in which a dye and another coloring material (for example, a pigment) are used together is also suitable.
• the mass ratio is preferably 10 to 99/90 to 1, more preferably 20 to 99/80 to 1, still more preferably 40 to 99/60 to 1, Especially preferably 60-99/40-1, most preferably 80-99/20-1.
• the total amount of the colorant is preferably 1% by mass or more with respect to 100% by mass of the total solid content of the photosensitive resin composition.
• the content is more preferably 5% by mass or more, and still more preferably 10% by mass or more, thereby making it possible to sufficiently meet recent demands for higher color purity and higher brightness.
• the upper limit is not particularly limited, but from the viewpoint of sufficiently exhibiting image forming properties such as photosensitivity, solubility and curability due to other components (for example, alkali-soluble resins and polymerizable compounds), it is 80% by mass. The following are preferable. More preferably 70 mass % or less, still more preferably 60 mass % or less.
• the photosensitive resin composition of the present invention preferably further contains a photoacid generator.
• a photoacid generator is a compound that generates an acid when exposed to an active energy ray such as radiation.
• Onium salts such as iodonium salts or selenium salts; iron-allene complexes; silanol-metal chelate complexes; sulfonic acid derivatives; organic halogen compounds; and the like.
• the content of the photoacid generator (E) is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition. is more preferable, and 1 to 8% by mass is even more preferable.
• the photosensitive resin composition of the present invention preferably further contains a polyfunctional thiol compound.
• the resin of the present invention preferably contains a (meth)acryloyl group in the side chain, and it is presumed that this is because an enethiol reaction occurs concurrently during exposure or heating to improve the crosslink density.
• the polyfunctional thiol compound has two or more mercapto groups in one molecule, preferably has a molecular weight of 200 to 1000, and particularly preferably a tri- to penta-functional secondary thiol. Curability and storage stability can be further improved by adding these polyfunctional thiol compounds.
• polyfunctional thiol compounds examples include butanediol bisthiopropionate, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate ) (Karenzu PE-1), 1,4-bis(3-mercaptobutyryloxy)butane (Karenzu BD-1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3, Mercaptopropionic acid derivatives such as 5-triazine-2,4,6(1H,3H,5H)-trione (Karenz NR-1) can be used.
• the polyfunctional thiol compound preferably does not have hydroxyl groups and/or aromatic rings in its molecule.
• polyfunctional thiol compounds include, for example, “Thiocalcol 20” manufactured by Kao Corporation, “Karenzu MT PE1” manufactured by Showa Denko K.K., “Karenzu MT BD1", “Karenzu MT NR1", “TPMB”, “TEMB ”, SC Organic Chemical Co., Ltd. “TMMP”, “TEMPIC”, “PEMP”, “EGMP-4”, “DPMP”, “TMMP II-20P”, “PEMP II-20P”.
• the content of the polyfunctional thiol compound (F) is preferably 0.3 to 15% by mass, preferably 0.5 to 10% by mass, with respect to 100% by mass of the total solid content of the photosensitive resin composition. is more preferable, and 1 to 8% by mass is even more preferable.
• the photosensitive resin composition of the present invention preferably contains a solvent.
• the solvent is not particularly limited, and examples thereof include inert organic solvents used in the synthesis reaction of the above-described alkali-soluble resin. Among them, it is preferable to use glycol monoether esters, monoalcohols and/or glycol monoethers. More preferably, at least glycol monoether esters are used, and it is also preferable to use glycol monoether esters and glycol monoethers in combination.
• the content of the solvent (G) is not particularly limited, and is preferably set appropriately according to the mode of use (for example, coating) of the photosensitive resin composition.
• the total solid content in 100% by mass of the photosensitive resin composition is more preferably 5 to 70% by mass, particularly preferably 10 to 50% by mass.
• the photosensitive resin composition of the present invention preferably also contains a dispersant.
• the dispersant is not particularly limited, for example, it has an interaction site for the coloring material and an interaction site for the dispersion medium (alkali-soluble resin, solvent, etc.), and stabilizes the dispersion of the coloring material in the dispersion medium. It is preferable to have the function of In general, dispersants that are classified into resin-type dispersants (polymeric dispersants), surfactants (low-molecular-weight dispersants), and pigment derivatives and that are commonly used may be used.
• the content of the dispersant (H) is not particularly limited, and may be appropriately set according to the purpose and application. Considering such a balance, the solid content of the dispersant is preferably 0.01 to 60 parts by mass with respect to 100 parts by mass of the total solid content of the coloring material. More preferably 0.1 to 50 parts by mass, still more preferably 0.5 to 40 parts by mass.
• the photosensitive resin composition of the present invention may optionally contain other components in addition to the components described above.
• other components include binder resins other than the alkali-soluble resin (A); other solvents; other coloring materials; other dispersing agents; fine particles; silane-based, aluminum-based, titanium-based coupling agents; fillers, other epoxy resins, other phenolic resins, thermosetting resins such as polyvinylphenol; plasticizers; polymerization inhibitors; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinonediazide compounds; These may be used individually by 1 type, and may be used in combination of 2 or more type. These other components may be appropriately selected from known ones and used, and the amount thereof to be used can be set as appropriate.
• the photosensitive resin composition preferably contains a colorant.
• the content of the other component (I) may be appropriately set according to the purpose and application. preferable. More preferably 0.01 to 30% by mass, still more preferably 0.1 to 20% by mass, and particularly preferably 0.3 to 10% by mass.
• the method for preparing the photosensitive resin composition of the present invention is not particularly limited, and a known method may be used.
• each component described above is mixed and dispersed using various mixers and dispersers. method.
• the mixing/dispersing step is not particularly limited, and may be performed by a known method. In addition, other steps that are normally performed may be further included.
• the photosensitive resin composition contains a colorant, it is preferably prepared through known steps such as a colorant dispersion treatment step.
• a cured product obtained by curing the alkali-soluble resin or photosensitive resin composition of the present invention has excellent solvent resistance.
• a cured product of such an alkali-soluble resin or a photosensitive resin composition is also one aspect of the present invention.
• the film thickness is preferably 0.1 ⁇ m or more. When the film thickness is 0.1 ⁇ m or more, even better solvent resistance can be exhibited.
• the film thickness is more preferably 0.5 ⁇ m or more, and even more preferably 1 ⁇ m or more.
• the upper limit of the film thickness is not particularly limited, and may be appropriately set according to the purpose and application of the cured film. It is even more preferable to have
• the method for obtaining the cured product is not particularly limited, and a known method may be used.
• the above-described alkali-soluble resin (solution) or photosensitive resin composition is applied on a substrate, or molded.
• a cured product can be obtained by drying, heating, or irradiating energy rays such as ultraviolet rays, or a combination thereof, to obtain a cured product.
• a cured product having excellent solvent resistance can be obtained even under low-temperature curing conditions.
• the method for producing such a cured product include, for example, a step of applying the photosensitive resin composition on a substrate to form a coating film, a step of irradiating the formed coating film with light, and light irradiation
• a preferred method includes a step of heating the coated film at 160° C. or lower.
• the base material is not particularly limited, and may be appropriately selected according to the purpose and application. Examples thereof include base materials made of various materials such as a glass plate and a plastic plate.
• the method of applying the photosensitive resin composition to form a coating film is not particularly limited, and known methods such as spin coating, slit coating, roll coating and cast coating can be used.
• a coating film by coating the photosensitive resin composition on a substrate and then drying the coating.
• the drying can be performed by a known method, and specifically, it can be performed by a method similar to the drying method described in the "arrangement step" of " ⁇ color filter manufacturing method>” described later.
• the manufacturing method includes a step of irradiating the coating film with light after forming the coating film.
• the method of irradiating the coating film formed above with light is not particularly limited, and can be carried out by a known method. can be carried out in a manner similar to that described in .
• the light irradiation may be performed through a photomask.
• a photomask a mask in which a light-shielding portion is formed according to an intended pattern is preferably used.
• a desired pattern can be formed on the coating film by performing the development step.
• the development method is not particularly limited, and can be carried out by a known method. Specifically, it is carried out by the same method as described in "Development step" in " ⁇ Color filter manufacturing method>" described later. be able to.
• the manufacturing method also includes a step of heating the irradiated coating film at 160° C. or less. Since the above-described production method uses the photosensitive resin composition described above, the heating step (post-curing step) after light irradiation can be performed under relatively low temperature conditions such as 160° C. or lower.
• the heating temperature is preferably 155° C. or lower, more preferably 150° C. or lower.
• the lower limit of the heating temperature is preferably 70° C. or higher, more preferably 90° C. or higher, from the viewpoint of maintaining curability.
• the heating method other than the temperature is not particularly limited, and can be performed by a known method. It can be carried out.
• the alkali-soluble resin of the present invention and the photosensitive resin composition containing the same are excellent in alkali developability. Further, even under low-temperature curing conditions of 160° C. or lower, for example, about 90° C., the curing reaction proceeds sufficiently, and a cured product having excellent solvent resistance can be obtained. Therefore, it can be suitably used in applications that require sufficient curing under low-temperature conditions and applications that require solvent resistance.
• the alkali-soluble resin and the photosensitive resin composition of the present invention are, for example, color filters used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. , black matrix, photospacer, black column spacer, ink, printing plate, printed wiring board, semiconductor element, photoresist, insulating film, film, organic protective film, etc. It can be suitably used for the purpose of Among them, it is preferably used for color filter applications.
• the photosensitive resin composition of the present invention is suitably used as an optical material, and is also suitably used as a negative type.
• a color filter having a cured product of the above photosensitive resin composition on a substrate is also one of preferred embodiments of the present invention.
• the cured product formed from the above-mentioned photosensitive resin composition is particularly suitable as, for example, a black matrix or a segment that needs to be colored, such as each pixel of red, green, blue, yellow, etc.
• a black matrix or a segment that needs to be colored such as each pixel of red, green, blue, yellow, etc.
• segments that do not necessarily require coloring such as photospacers, protective layers, and alignment control ribs.
• the substrate used in the color filter examples include glass substrates such as white plate glass, soda plate glass, alkali-strengthened glass, silica-coated soda plate glass; Sheets, films or substrates made of thermoplastic resins such as additives; Sheets, films or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates such as aluminum plates, copper plates, nickel plates and stainless steel plates a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member composed of various materials such as a glass substrate having a coloring material layer on its surface (for example, a color filter for LCD); Among them, a glass substrate and a sheet, film or substrate made of a heat-resistant resin are preferable from the viewpoint of heat resistance. Also, the substrate is preferably a transparent substrate. If necessary, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a silane coupling agent, or the like.
• a step of disposing the above-described photosensitive resin composition on a substrate also referred to as an arrangement step
• a step of irradiating the arranged photosensitive resin composition with light also referred to as a light irradiation step
• a step of developing with a developer also referred to as a developing step
• a step of heat treatment also referred to as a heating step.
• a manufacturing method that employs a technique that includes a single color and then repeats the same technique for each color. Note that the order in which the pixels of each color are formed is not particularly limited.
• Placement step (preferably coating step)
• the placement step is preferably performed by coating.
• the method for applying the photosensitive resin composition on the substrate include spin coating, slit coating, roll coating, casting coating, and the like, and any of these methods can be preferably used.
• the coating film after coating the photosensitive resin composition on the substrate. Drying of the coating film can be performed using, for example, a hot plate, an IR oven, a convection oven, or the like.
• the drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the dryer, etc., but usually the drying can be performed at a temperature of 50 to 160° C. for 10 to 300 seconds. preferred.
• the light source of actinic rays used includes, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, Lamp light sources such as carbon arcs and fluorescent lamps, laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers are used.
• the system of the exposure machine there are a proximity system, a mirror projection system, and a stepper system, and the proximity system is preferably used.
• the active energy beam may be irradiated through a predetermined mask pattern.
• the exposed portion is cured, and the cured portion becomes insoluble or slightly soluble in the developer.
• Development process is a process in which, after the light irradiation process described above, development is performed with a developer to remove the unexposed portions to form a pattern. Thereby, a patterned cured film can be obtained. Development can be carried out at a development temperature of generally 10 to 50° C. by methods such as immersion development, spray development, brush development and ultrasonic development.
• the developer used in the development step is not particularly limited as long as it dissolves the photosensitive resin composition, but usually an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may be used.
• alkaline aqueous solution it is preferable to wash with water after development.
• the organic solvent and alkaline aqueous solution include those described in JP-A-2015-157909.
• the heating step is a step of further hardening the exposed portion (cured portion) by baking after the above-described developing step (also referred to as a "post-curing step").
• Examples include a step of post-exposure with a light amount of 0.5 to 5 J/cm 2 using a light source such as a high-pressure mercury lamp, and a step of post-heating at a temperature of 60 to 200° C. for 10 seconds to 120 minutes. be done.
• a post-curing step it is possible to further increase the hardness and adhesion of the patterned cured film.
• the heating step is generally carried out at a temperature of about 200 to 260° C., but if the photosensitive resin composition is used, the heating process can be performed under relatively low temperature conditions of 200° C. or less, preferably 160° C. or less. Sufficient curing can be performed. Therefore, it is possible to obtain excellent solvent resistance without impairing the properties held by the substrate or the cured product.
• the heating temperature is preferably 160° C. or lower, more preferably 155° C. or lower, and even more preferably 150° C. or lower. Moreover, the heating temperature is preferably 70° C. or higher, more preferably 90° C. or higher, and even more preferably 95° C. or higher.
• the heating time in the heating step is not particularly limited, but is preferably 5 to 60 minutes, for example.
• the heating method is not particularly limited, either, but for example, it can be performed using a heating device such as a hot plate, a convection oven, or a high-frequency heater.
• the thickness of the cured film obtained by the heating step is preferably 0.1 to 20 ⁇ m.
• the film thickness is more preferably 0.5 to 15 ⁇ m, still more preferably 1 to 10 ⁇ m.
• a display device including the color filter described above is also one of preferred embodiments of the present invention.
• a member for a display device and a display device having a cured product of the photosensitive resin composition are also included in preferred embodiments of the present invention.
• the cured product (cured film) formed from the photosensitive resin composition is stable, has excellent adhesion and solvent resistance, and has high hardness, exhibits high smoothness, and has high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or an insulating film in various display devices.
• the display device for example, a liquid crystal display device, a solid-state imaging device, a touch panel display device, or the like is suitable.
• the member When the cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multilayer member composed of the cured film, or the single-layer or multilayer It may be a member in which another layer is further combined with the member of (1), or a member including the cured film in its configuration.
• the alkali-soluble resin and photosensitive resin composition of the present invention are excellent in alkali developability and can give a cured product excellent in solvent resistance even under low-temperature curing conditions.
• the alkali-soluble resin and photosensitive resin composition of the present invention can be used as various optical members and structural members used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. It can be suitably used for various applications such as electric and electronic equipment.
• Solvent-resistant photosensitive resin composition is spin-coated on a 5 cm square glass substrate, dried at 90 ° C. for 2 minutes, exposed at 100 mJ using a high pressure mercury lamp, and heat treated at 90 ° C. for 30 minutes (after curing) to obtain a cured film having a thickness of 2 ⁇ m. Then, the cured film was immersed in 20 g of propylene glycol monomethyl ether at 30° C. for 5 minutes and then taken out, and the absorbance of the immersion solvent after the cured film was taken out was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation).
• the photosensitive resin composition is applied to a 10 cm square glass substrate by spin coating, and after heat treatment (90 ° C., 3 minutes), a 30 ⁇ m line-and-space opening is placed at a distance of 50 ⁇ m from the coating film.
• a UV aligner manufactured by Dai Nippon Kaken Co., Ltd., trade name “MA-1100” equipped with a 2.0 kW ultra-high pressure mercury lamp was used to irradiate 60 mJ/cm 2 (365 nm illuminance conversion).
• Exposure is performed with an exposure amount, a 0.05% potassium hydroxide aqueous solution is sprayed with a spin developing machine to dissolve and remove unexposed areas, and the remaining exposed areas are washed with pure water for 10 seconds for development. Then, the developability was evaluated. Specifically, the coating film developed through the photomask as described above was observed with a surface roughness meter (manufactured by Ryoka System Co., Ltd., trade name “VertScan 2.0”), and line thickness from 30 ⁇ m was observed. evaluated. The smaller the numerical value, the smaller the thickness of the pattern line and the better the miniaturization.
• Example 1 Preparation of alkali-soluble resin solution A-1 (SAH adduct solution of AA adduct of YDCN-704A) Propylene glycol monomethyl ether was added to a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube and a dropping vessel inlet port.
• Acetate 132.2 g, YDCN-704A 100.0 g manufactured by Nippon Steel Chemical & Material, epoxy equivalent 207.8 g / equivalent), triphenylphosphine 0.18 g, Antage W-400 0.18 g (Kawaguchi Chemical Industry Co., Ltd. company) and heated to 115°C.
• Example 2 Preparation of alkali-soluble resin solution A-2 (SAH adduct solution of MAA adduct of YDCN-704A) Propylene glycol monomethyl ether was added to a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube and a dropping vessel inlet port. 128.5 g of acetate, 100.0 g of YDCN-704A, 0.18 g of triphenylphosphine and 0.18 g of Antage W-400 were charged and heated to 115°C.
• SAH adduct solution of MAA adduct of YDCN-704A Propylene glycol monomethyl ether was added to a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube and a dropping vessel inlet port. 128.5 g of acetate, 100.0 g of YDCN-704A, 0.18 g of triphenylphosphine and 0.
• Example 4 Preparation of alkali-soluble resin solution A-4 (SAH adduct solution of AA adduct of BS-PN adduct of YDCN-704A) Reaction tank equipped with thermometer, stirrer, gas inlet pipe, cooling pipe and dropping tank inlet 117.0 g of propylene glycol monomethyl ether acetate, 100.0 g of YDCN-704A, 0.37 g of triphenylphosphine, and 1.2 g of BS-PN (manufactured by Konishi Kagaku Kogyo Co., Ltd.) were charged and heated while replacing with nitrogen. The temperature was raised to 115°C.
• SAH adduct solution of AA adduct of BS-PN adduct of YDCN-704A Reaction tank equipped with thermometer, stirrer, gas inlet pipe, cooling pipe and dropping tank inlet 117.0 g of propylene glycol monomethyl ether acetate, 100.0 g of YDCN-7
• Example 7 Preparation of alkali-soluble resin solution A-7 (SAH adduct solution of AA/PA adduct of YDCN-704A) Propylene glycol 140.1 g of monomethyl ether acetate, 100.0 g of YDCN-704A, 0.18 g of triphenylphosphine and 0.19 g of Antage W-400 were charged and heated to 115°C.
• SAH adduct solution of AA/PA adduct of YDCN-704A Propylene glycol 140.1 g of monomethyl ether acetate, 100.0 g of YDCN-704A, 0.18 g of triphenylphosphine and 0.19 g of Antage W-400 were charged and heated to 115°C.
• a dropping tank prepare a beaker in which 20.8 g of acrylic acid and 3.6 g of propionic acid are well mixed, and after the temperature of the reaction tank reaches 115° C., oxygen/nitrogen While bubbling MIX gas at 20 ml/min, dropping was started from the dropping tank over 2 hours to carry out an addition reaction. After completion of dropping, 0.18 g of triphenylphosphine was additionally added, and the reaction was allowed to proceed for 4 hours to complete the reaction.
• Example 8 Preparation of alkali-soluble resin solution A-8 (SAH adduct solution of AA/PA adduct of YDCN-704A) Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a condenser tube and a dropping vessel inlet, propylene glycol was added. 115.6 g of monomethyl ether acetate, 100.0 g of YDCN-704A, 0.35 g of triphenylphosphine and 0.17 g of Antage W-400 were charged and heated to 115°C. On the other hand, a mixture of 6.9 g of acrylic acid and 8.9 g of propionic acid was prepared in a beaker.
• SAH adduct solution of AA/PA adduct of YDCN-704A Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a condenser tube and a dropping vessel inlet, propy
• n-dodecyl mercaptan 2.0 g of n-dodecyl mercaptan and 8 g of propylene glycol monomethyl ether acetate were stirred and mixed in a dropping tank (B). After the temperature of the reactor reached 90° C., while maintaining the same temperature, dropping was started from the dropping tank over 3 hours to carry out polymerization. After the dropping was completed, the temperature was maintained at 90° C. for 30 minutes, then the temperature was raised to 115° C., and aging was performed for 90 minutes.
• Pigment Dispersion 1 (Preparation of pigment dispersion 1) 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a dispersant, and C.I. I. Pigment Green 58 at 2.25 parts and C.I. I. Pigment Yellow 138 was mixed with 1.5 parts and dispersed for 3 hours using a paint shaker to obtain Pigment Dispersion 1 (solid content: 22% by mass).
• Example 9 Solid content, 35.0 parts of alkali-soluble resin solution A-1, 30.0 parts of dipentaerythritol hexaacrylate as a polymerizable compound, 5. Irgacure OXE-02 (manufactured by BASF Japan) as a photopolymerization initiator. 0 part, 30.0 parts of Pigment Dispersion 1, and further a dilution solvent (propylene glycol monomethyl ether acetate) were added so that the solid content concentration was 20% by mass, and the mixture was stirred to obtain a photosensitive resin composition 1. .
• a dilution solvent propylene glycol monomethyl ether acetate
• the obtained photosensitive resin compositions 1 to 11 were evaluated for solvent resistance and line thickness. Table 3 shows the results.
• the photosensitive resin composition containing an alkali-soluble resin having a specific structural unit and an epoxy equivalent of 5000 g/equivalent or less exhibits excellent solvent resistance even under low-temperature curing conditions of 90°C. was found to give
• the photosensitive resin composition of Example 13 using an alkali-soluble resin A-5 synthesized without chain extension with BS-PN (bisphenol S) and using triethylamine as a catalyst, and THPA In the photosensitive resin composition of Example 14 using the alkali-soluble resin A-6 synthesized using tetrahydrophthalic anhydride), the solvent resistance of the cured product was good.
• Example 9 when Example 9 and Example 15 are compared, solvent resistance was further improved by blending a polyfunctional thiol. It is believed that polyfunctional thiols could accelerate curing.
• Examples 16 and 17 containing alkali-soluble resin solutions A-7 and A-8 to which propionic acid is added which is not involved in photocuring or thermosetting have little line thickness of the pattern and are excellent in fineness characteristics.
• Met. Although not shown in the table, each photosensitive resin composition of Examples also had good alkali developability.
• Examples 1, 2, 3, 6, 7, and 8 with the addition of an acid compound have less viscosity increase during storage than the resins of Examples 4 and 5 without addition, and have good storage stability. Met.
• the photosensitive resin composition of the present invention has excellent curability and alkali developability, is suitable for resists for forming members in the field of electronic information, such as plating resists and color filter resists, and has excellent solvent resistance. Therefore, it is particularly suitable for forming pixels (colored layers) of color filters.

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