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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/064—Polymers containing more than one epoxy group per molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/144—Polymers containing more than one epoxy group per molecule
• • 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
  • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
  • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
  • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
  • C08G59/1461—Unsaturated monoacids
  • C08G59/1466—Acrylic or methacrylic acids
• • 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

Definitions

• the present invention relates to an alkali-soluble resin, a photosensitive resin composition, a method for producing the same, and uses thereof. More specifically, the present invention relates to an alkali-soluble resin, a photosensitive resin composition, which has excellent photocurability and can give a cured product with a high refractive index, a method for producing the same, a cured product, a display device member using the same, and a display device.
• alkali-soluble resins and photosensitive resin compositions have been investigated for various applications, such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, organic insulating films, organic protective films, and other optical components and electrical and electronic devices used in liquid crystal display devices and solid-state imaging devices, and resins and resin compositions with excellent properties required for each application are being developed.
• Patent Document 1 describes a modified epoxy resin having excellent heat resistance, moisture resistance and flexibility, which is obtained by reacting an epoxy resin having two or more epoxy groups in one molecule (a), a phenol having a substituent containing an aryl group (b), and an unsaturated monobasic acid (c).
• Patent Document 2 describes an alkaline-developable photocurable/thermosetting composition that can provide a solder resist film that is excellent in heat resistance, adhesion, resolution, electroless plating resistance, electrical properties, moisture absorption resistance, etc., and that contains a photosensitive prepolymer obtained by reacting a polybasic acid anhydride with the alcoholic hydroxyl group of the reaction product of an epoxy compound having two or more epoxy groups in one molecule, a specific phenol compound and/or naphthol compound, and an unsaturated group-containing monocarboxylic acid.
• the present invention has been made in consideration of the above-mentioned current situation, and aims to provide an alkali-soluble resin and a photosensitive resin composition that have excellent photocurability and can give a cured product with a high refractive index.
• the inventors conducted extensive research into alkali-soluble resins and discovered that a resin with a specific aromatic ring-containing structure and a polymerizable unsaturated bond-containing structure, and a polymerizable unsaturated bond equivalent within a specific range, can provide a cured product with excellent photocurability and a high refractive index, leading to the completion of the present invention.
• An alkali-soluble resin having an aromatic ring-containing structure represented by the following formula (1) and a polymerizable unsaturated bond-containing structure represented by the following formula (2), wherein the polymerizable unsaturated bond equivalent is 700 to 8000 g/equivalent.
• R 1 represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent.
• R 2 represents an aromatic group which may have a substituent.
• R 3 represents a hydrogen atom or a group represented by formula (3).
• R 4 , R 5 , and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.
• R 9 is a hydrogen atom or a group represented by formula (3). At least one of R 3 and R 9 is a group represented by formula (3).
• R 10 represents a divalent hydrocarbon group which may have a substituent.
• a photosensitive resin composition comprising the alkali-soluble resin according to any one of [1] to [4] above, a polymerizable compound, and a photopolymerization initiator.
• [6] A cured product obtained by curing the alkali-soluble resin according to any one of [1] to [4] above, or the photosensitive resin composition according to [5] above.
• [7] A member for a display device, comprising the cured product according to [6] above.
• [8] A display device comprising the member for a display device according to [7] above.
• a method for producing an alkali-soluble resin comprising: a first step of reacting an epoxy resin (a) having two or more epoxy groups in one molecule with an aromatic group-containing compound (b) and an unsaturated monocarboxylic acid (c); and a second step of reacting the reaction product obtained in the first step with a polybasic acid anhydride (d);
• the method for producing an alkali-soluble resin is characterized in that the amounts of the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) used in the first step are adjusted so that the resulting alkali-soluble resin has a polymerizable unsaturated bond equivalent of 700 to 8,000 g/equivalent.
• a method for producing a photosensitive resin composition comprising the steps of: producing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 to 8000 g/equivalent by the method for producing an alkali-soluble resin according to the above-mentioned [9]; and mixing the obtained alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
• R 23 represents an aromatic group which may have a substituent.
• R 24 represents a hydrogen atom or a group represented by formula (3).
• R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.
• R 9 is a hydrogen atom or a group represented by formula (3). At least one of R 24 and R 9 is a group represented by formula (3).
• R 10 represents a divalent hydrocarbon group which may have a substituent.
• R 1 represents an oxygen atom or a sulfur atom.
• R 2 represents an aromatic group which may have a substituent.
• R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.
• the alkali-soluble resin and photosensitive resin composition of the present invention can provide a cured product with excellent photocurability and a high refractive index, and a display device component and a display device that include the cured product.
• the method for producing an alkali-soluble resin of the present invention can easily produce an alkali-soluble resin with excellent photocurability and a high refractive index.
• the first alkali-soluble resin of the present invention is characterized in that it has an aromatic ring-containing structure represented by the above formula (1) and a polymerizable unsaturated bond-containing structure represented by the above formula (2), and has a polymerizable unsaturated bond equivalent of 700 to 8,000 g/equivalent.
• the reason why the first alkali-soluble resin of the present invention has excellent photocurability and a high refractive index is believed to be due to the following reasons. That is, the first alkali-soluble resin of the present invention has a specific aromatic ring-containing structure, and therefore can give a cured product with a high refractive index. Furthermore, it is presumed that the resin has excellent photocurability because it has a specific range of polymerizable unsaturated bonds in the side chains, and because it has a high crosslink density upon curing, a cured product with an even higher refractive index can be obtained.
• R 1 represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent.
• substituents include an alkyl group, an aralkyl group, an aryl group, a thioester group, a thioether group, a disulfide group, an alkoxy group, an amino group or a salt thereof, a halogen atom, a trifluoromethyl group, a benzamino group, a boronic acid group, a hydroxyl group, a mercapto group, a thiocyanate group, an alkylthiocyanate group, an isothiocyanate group, a thiourea group, a sulfonic acid group, a carboxyl group, an aldehyde group, a heterocyclic group, or a group combining these.
• R 1 is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom, in terms of increasing the refractive index.
• the presence of a sulfur atom can function as an antioxidant, so that weather resistance can be imparted to the resin.
• R2 represents an aromatic group which may have a substituent.
• the aromatic group may have an aromatic ring structure, and may be a monocyclic or polycyclic group.
• the aromatic group may contain a heteroatom.
• the rings constituting the polycyclic aromatic group may be condensed, may be bonded by a single bond, or may be linked in a manner that shares one carbon atom.
• the rings constituting the polycyclic aromatic group may contain at least an aromatic ring, and may be a group consisting of only aromatic rings, or may be a group consisting of aromatic rings and non-aromatic rings.
• the aromatic group may be, for example, a monovalent group obtained by removing one hydrogen atom from a benzene-based aromatic compound, a non-benzene-based aromatic compound, or a heteroaromatic compound.
• benzene-based aromatic compounds include hydrocarbon compounds containing a benzene ring, such as monocyclic hydrocarbon compounds such as benzene; condensed ring hydrocarbon compounds such as naphthalene, anthracene, triphenylene, and pyrene; and polycyclic hydrocarbon compounds such as biphenylene and fluorene.
• the non-benzene aromatic compounds include hydrocarbon compounds containing unsaturated cyclic compounds other than a benzene ring, such as annulene and azulene.
• the heteroaromatic compounds include unsaturated cyclic compounds containing elements other than carbon and hydrogen atoms, such as oxygen atoms, nitrogen atoms, and sulfur atoms.
• monocyclic heteroaromatic compounds such as furan, thiophene, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, triazole, thiazole, thiadizole, and tetrazole
• polycyclic heteroaromatic compounds such as carbazole, benzoxazole, purine, azulene, benzofuran, isobenzofuran, benzothiophene, benzotriazole, isobenzothiophene, indole, isoindole, benzimidazole, and benzothiazole.
• the aromatic group is preferably a monovalent group obtained by removing one hydrogen atom from a benzene-based aromatic compound, more preferably a phenyl group, a naphthyl group, or a biphenyl group, even more preferably a phenyl group or a biphenyl group, and most preferably a phenyl group.
• the number of carbon atoms in the aromatic group is preferably 1 to 30, more preferably 2 to 20, and even more preferably 6 to 12.
• Examples of the substituent that the aromatic group may have include an alkyl group, an aralkyl group, an aryl group, a thioester group, a thioether group, a disulfide group, an alkoxy group, an amino group or a salt thereof, a halogen atom, a trifluoromethyl group, a benzamino group, a boronic acid group, a hydroxyl group, a mercapto group, a thiocyanate group, an alkylthiocyanate group, an isothiocyanate group, a thiourea group, a sulfonic acid group, a carboxyl group, an aldehyde group, a heterocyclic group, or a combination thereof.
• an alkyl group is preferable.
• the substituent preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• the aromatic group may have one or more of the above-mentioned substituents.
• aromatic groups that may have the above-mentioned substituents include, in addition to the specific aromatic groups mentioned above, aromatic hydrocarbon groups such as a tolyl group, a xylyl group, a benzyl group, a phenethyl group, a benzhydryl group, a trityl group, a styryl group, and a cinnamyl group.
• aromatic hydrocarbon groups such as a tolyl group, a xylyl group, a benzyl group, a phenethyl group, a benzhydryl group, a trityl group, a styryl group, and a cinnamyl group.
• aromatic group which may have a substituent include monovalent groups obtained by removing one hydrogen atom from the following aromatic compounds: Thiocyanate compounds such as benzyl thiocyanate; Isothiocyanate compounds such as phenyl isothiocyanate, benzyl isothiocyanate, and 3,4-difluorophenyl isothiocyanate; mercaptan compounds such as trityl mercaptan, 4-aminothiophenol, 4-fluorothiophenol, 2,4-difluorothiophenol, 2-amino-4-(trifluoromethyl)thiophenol hydrochloride, 3,5-dichlorothiophenol, bis(3,5-dichlorophenyl)disulfide, 4-methoxythiophenol, 3-mercapto-4-methyl-1,2,4-triazole, 4-bromothiophenol, 2-mercaptobenzoxazole, 2,6-dimethylthiophenol, 4,4',4'''
• an aromatic hydrocarbon group which may have a substituent is preferable, a phenyl group, a naphthyl group, or a biphenyl group which may have a substituent is more preferable, and a phenyl group or a biphenyl group which may have a substituent is even more preferable.
• R3 is a hydrogen atom or a group represented by the above formula (3).
• R 10 represents a divalent hydrocarbon group which may have a substituent.
• the divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
• divalent aliphatic hydrocarbon groups include alkylene groups such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a t-butylene group, a pentylene group, a neopentylene group, a hexamethylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group; and alkenylene groups such as a vinylene group, a propenylene group, an isopropenylene group, a butenylene group, a butadienylene group, a pentenylene group,
• divalent alicyclic hydrocarbon groups examples include cycloalkylene groups such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, norbornylene, and adamantylene groups, and cycloalkylidene groups such as cyclopentylidene and cyclohexylidene groups.
• divalent aromatic hydrocarbon groups examples include arylene groups such as phenylene groups, tolylene groups, and naphthylene groups, as well as cinnamylidene groups and biphenylene groups.
• the divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group or a divalent alicyclic hydrocarbon group, more preferably a divalent aliphatic hydrocarbon group, and even more preferably an alkylene group.
• the carbon number of the divalent hydrocarbon group is preferably 2 to 20, more preferably 2 to 8, and even more preferably 2.
• Examples of the substituents that the divalent hydrocarbon group may have include a carboxyl group, a hydroxyl group, an alkoxy group, a halogen atom, and a hydrocarbon group having 1 to 7 carbon atoms.
• R 4 , R 5 and R 6 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• the hydrocarbon group having 1 to 6 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
• R 4 and R 5 are preferably hydrogen atoms
• R 6 is preferably a hydrogen atom or a methyl group.
• R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.
• the divalent organic group represented by R 7 and R 8 include a divalent hydrocarbon group, or a group combining a divalent hydrocarbon group with a bond such as -O-, -CO-, -COO-, -NH-, -SO- or -SO 2 -.
• the divalent hydrocarbon group include the same groups as those described above.
• the divalent hydrocarbon group may include two or more types.
• the divalent organic group is preferably a divalent hydrocarbon group or a group combining a divalent hydrocarbon group with at least one bond selected from the group consisting of -O-, -CO-, and -COO-.
• the group combining the above-mentioned divalent hydrocarbon group with at least one bond selected from the group consisting of -O-, -CO-, and -COO- include -R a -COO-R b - and -R a -O-(CO)-R b - (wherein R a and R b are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms).
• R 7 and R 8 are preferably a direct bond, a divalent hydrocarbon group, or a group consisting of a combination of a divalent hydrocarbon group and at least one bond selected from the group consisting of -O- and -COO-, more preferably a direct bond or a divalent aliphatic hydrocarbon group, and further preferably a direct bond.
• R 9 is a hydrogen atom or a group represented by the above formula (3). At least one of R 3 and R 9 is a group represented by the above formula (3).
• the group represented by the above formula (3) has a carboxyl group, which is an acid group. When a resin has such a group, it becomes alkali-soluble. By adjusting the amount of such acid groups, the alkali-soluble resin becomes a resin with excellent developability.
• the first alkali-soluble resin preferably has a novolac structure as a main chain structure.
• the novolac structure refers to a structure in which a benzene ring or a naphthalene ring is bonded to a divalent hydrocarbon group, which may have a substituent, in the main chain to form a repeating unit.
• alkali-soluble resins having an aromatic ring-containing structure represented by the above formula (1) and a polymerizable unsaturated bond-containing structure represented by the above formula (2) include alkali-soluble resins having a structural unit (A) represented by the following formula (a) and a structural unit (B) represented by the following formula (b).
• A represents a benzene ring or a naphthalene ring.
• R 1 to R 9 are the same as those described above.
• R 11 and R 14 are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
• R 12 and R 15 are the same or different and represent a substituent bonded to A.
• a represents the number of R 12 and is an integer of 0 to 5.
• b represents the number of R 15 and is an integer of 0 to 5.
• R 13 and R 16 are the same or different and represent a direct bond or a divalent organic group.
• structural unit refers to a repeating unit that constitutes an alkali-soluble resin.
• A represents a benzene ring or a naphthalene ring. From the viewpoint of the balance between high refractive index and developability, it is preferable that A is a benzene ring.
• R 11 and R 14 represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
• the divalent hydrocarbon group include the same groups as the divalent hydrocarbon groups described above. Among them, in terms of ease of availability, the divalent hydrocarbon group represented by R 11 and R 14 is preferably a divalent aliphatic hydrocarbon group, and more preferably an alkylene group.
• the carbon number of the divalent hydrocarbon group is preferably 1 to 14, more preferably 1 to 10, and even more preferably 1.
• At least one of the atoms constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom.
• the divalent hydrocarbon group may also have a substituent such as an alkoxy group.
• R 12 and R 15 may be the same or different and represent a substituent bonded to A.
• the substituent bonded to A may be a hydroxyl group or an organic group having 1 to 20 carbon atoms.
• Examples of the organic group having 1 to 20 carbon atoms include those obtained by making the above-mentioned divalent organic group monovalent and having a carbon number of 1 to 20.
• the substituents represented by R 12 and R 15 are preferably -OH, -O-CH 2 -(C 2 H 3 O), -CR c R d -(C 6 H 4 )-O-CH 2 -(C 2 H 3 O), -CR c R d -(C 6 H 4 )-OH (wherein R c and R d are the same or different and represent a hydrogen atom or a methyl group), or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, even more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a methyl group.
• a represents the number of the substituents R 12 and is an integer of 0 to 5. In terms of good developability, a is preferably 0 to 3, more preferably 1 to 3, and even more preferably 1. When a is 2 or more, that is, when there are two or more R 12 , R 12 may be the same as or different from each other.
• b represents the number of the substituents R 15 and is an integer of 0 to 5. In terms of good developability, b is preferably 0 to 3, more preferably 1 to 3, and even more preferably 1. When b is 2 or more, that is, when there are two or more R 15 , the R 15 may be the same as or different from each other.
• R 13 and R 16 are the same or different and represent a direct bond or a divalent organic group.
• the divalent organic group may be the same as the divalent organic group described above.
• R 13 and R 16 are preferably a direct bond.
• the first alkali-soluble resin may have one or more types of the structural unit (A).
• the content of the structural unit (A) in the alkali-soluble resin is preferably 51 to 93 mol%, more preferably 55 to 92 mol%, even more preferably 60 to 91 mol%, still more preferably 60 to 90 mol%, particularly preferably 60 to 80 mol%, and most preferably 60 to 75 mol%, relative to 100 mol% of all structural units.
• the first alkali-soluble resin may have one or more types of the structural unit (B).
• the content of the structural unit (B) in the alkali-soluble resin is preferably 7 to 49 mol%, more preferably 8 to 45 mol%, even more preferably 9 to 40 mol%, and still more preferably 10 to 40 mol%, relative to 100 mol% of all structural units.
• the first alkali-soluble resin may further have a structural unit (C) other than the structural units (A) and (B) described above, and the alkali-soluble resin may have one or more structural units (C).
• A represents a benzene ring or a naphthalene ring.
• R3 is the same as defined above.
• R17 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
• R18 represents a substituent bonded to A.
• c represents the number of R18 and is an integer of 0 to 5. When there are two or more R18s , they may be the same or different.
• R19 represents a direct bond or a divalent organic group.
• R20 represents an organic group.
• Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 17 include the same groups as the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 11 described above, and are preferably divalent aliphatic hydrocarbon groups, and more preferably alkylene groups.
• Examples of the substituent represented by R 18 include the same groups as the substituent represented by R 12 described above, and preferably, -OH, -O-CH 2 -(C 2 H 3 O), -CR c R d -(C 6 H 4 )-O-CH 2 -(C 2 H 3 O), -CR c R d -(C 6 H 4 )-OH (wherein R c and R d are the same or different and represent a hydrogen atom or a methyl group), or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, still more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a methyl group.
• c represents the number of substituents R 18 and is an integer of 0 to 5. In terms of good developability, c is preferably 0 to 3, more preferably 1 to 3, and even more preferably 1. When c is 2 or more, that is, when there are two or more R 18s , R 18s may be the same as or different from each other.
• R 19 represents a direct bond or a divalent organic group.
• Examples of the divalent organic group represented by R 19 include the same groups as the divalent organic group represented by R 13 described above. Among them, R 19 is preferably a direct bond.
• R 20 represents an organic group.
• the organic group represented by R 20 may be the above-mentioned divalent organic group made monovalent, and among them, a group having an acid group is preferable. It is also preferable that the group does not have a double bond. By appropriately selecting the organic group of R 20 , the developability and the reactivity of the double bond can be controlled.
• the acid group may be, for example, a functional group that undergoes a neutralization reaction with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, or a sulfonic acid group.
• a carboxyl group or a carboxylic anhydride group is preferred, and a carboxyl group is more preferred, in terms of good developability.
• Examples of the group having an acid group include a group represented by -R e -R f (wherein R e represents a divalent organic group, and R f represents an acid group).
• the divalent organic group may be the same as the organic group described above. Among them, a group consisting of a combination of a divalent hydrocarbon group and at least one selected from the group consisting of -O- and -COO- is preferred.
• the organic group represented by R20 preferably also has a functional group having a radical scavenging ability or an ultraviolet absorbing ability.
• a functional group having a radical scavenging ability or an ultraviolet absorbing ability By having such a functional group, the weather resistance of the resin can be improved.
• the functional group include a hindered phenol group, a hindered amine group, a benzotriazole group, a triazine group, a cyanoacrylate group, a melamine group, and a benzoate group.
• the number of carbon atoms in the organic group represented by R20 is preferably 1 to 20, more preferably 1 to 16, and still more preferably 2 to 12.
• the first alkali-soluble resin may have one or more types of the structural unit (C).
• the content of the structural unit (C) is preferably 0 to 20 mol%, more preferably 0.1 to 20 mol%, even more preferably 0.5 to 15 mol%, and still more preferably 1 to 10 mol%, relative to 100 mol% of all structural units.
• the first alkali-soluble resin may also have a structural unit (D) represented by the following formula (d).
• the resin can be designed to have any molecular weight.
• L represents a direct bond or a linking group.
• R 21 and R 22 are the same or different and represent a substituent.
• d represents the number of R 21 and is an integer of 0 to 4.
• e represents the number of R 22 and is an integer of 0 to 4. When there are multiple R 21 and multiple R 22 , they may be the same as or different from each other.
• linking group examples include an alkylene group, an arylene group, a heteroarylene group, a divalent bond such as --O--, --CO--, --S--, --SO--, --SO 2 -- or --NH--, or a combination thereof.
• the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms. In addition, it may be linear, branched, or cyclic.
• 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 fluorine atoms, chlorine atoms, and iodine atoms, and alkyl groups.
• the structural unit (D) represented by the above formula (d) is preferably a structural unit derived from any one compound selected from 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 PH, bisphenol TMC, and bisphenol Z, more preferably a structural unit derived from bisphenol S, bisphenol A, or bisphenol F, and even more preferably a structural unit derived from bisphenol S.
• the structural unit (D) is preferably a structural unit represented by the following formula (d-1), (d-2), or (d-3).
• the content of the structural unit (D) is preferably 0.1 to 10 mol %, more preferably 0.2 to 5 mol %, and even more preferably 0.5 to 2 mol %, relative to 100 mol % of all structural units.
• the polymerizable unsaturated bond equivalent of the first alkali-soluble resin is 700 to 8000 g/equivalent.
• the polymerizable unsaturated bond equivalent of the alkali-soluble resin is preferably 750 to 6000 g/equivalent, more preferably 800 to 5000 g/equivalent, even more preferably 900 to 4000 g/equivalent, and even more preferably 900 to 2000 g/equivalent.
• the polymerizable unsaturated bond equivalent is the mass of the solid content of the alkali-soluble resin solution per 1 mol of the polymerizable unsaturated bond of the alkali-soluble resin.
• the polymerizable unsaturated bond means a polymerizable double bond.
• the mass of the solid content of the alkali-soluble resin solution is the mass of the monomer components constituting the alkali-soluble resin.
• the polymerizable unsaturated bond equivalent can be determined by dividing the mass (g) of the alkali-soluble resin solid content of the alkali-soluble resin solution by the amount of polymerizable unsaturated bonds (mol) of the alkali-soluble resin. It may also be calculated by measuring the number of ethylenic double bonds contained per 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070:1992.
• the acid value of the first alkali-soluble resin is preferably 30 to 150 mgKOH/g, more preferably 40 to 120 mgKOH/g, and even more preferably 45 to 90 mgKOH/g, in order to further improve developability.
• the acid value is an acid value per 1 g of resin solid content obtained by measurement by neutralization titration using a potassium hydroxide (KOH) solution, and can be determined by the method described in the examples below.
• the epoxy equivalent of the first alkali-soluble resin is preferably more than 10,000 g/equivalent.
• the alkali-soluble resin of the present invention has almost no epoxy groups. Therefore, the storage stability is good.
• the epoxy equivalent of the alkali-soluble resin is more preferably more than 13,000 g/equivalent.
• the epoxy equivalent can be determined by a method in accordance with JIS K7236:2001, and can be determined by dividing the mass (g) of the resin solid content by the number of moles (mol) of epoxy groups contained in the resin.
• the weight average molecular weight of the first alkali-soluble resin is preferably 1000 to 100000. In terms of good curability, the weight average molecular weight of the alkali-soluble resin is more preferably 2000 to 50000, even more preferably 3000 to 20000, even more preferably 3500 to 15000, and particularly preferably 4000 to 10000.
• the weight average molecular weight can be determined by gel permeation chromatography (GPC).
• the glass transition temperature (Tg) of the first alkali-soluble resin is preferably 40° C. or higher, more preferably 60° C. or higher, and even more preferably 80° C. or higher, in terms of improving film strength, and is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 200° C. or lower, in terms of good developability.
• the glass transition temperature (Tg) of the first alkali-soluble resin is preferably 40 to 300° C., more preferably 60 to 250° C., and even more preferably 80 to 200° C.
• the glass transition temperature can be determined by a method in accordance with JIS-K7121.
• the second alkali-soluble resin of the present invention is characterized by having an aromatic ring-containing structure represented by the following formula (4) and a polymerizable unsaturated bond-containing structure represented by the following formula (2).
• R 23 represents an aromatic group which may have a substituent.
• R 24 represents a hydrogen atom or a group represented by formula (3).
• R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.
• R 9 is a hydrogen atom or a group represented by formula (3). At least one of R 24 and R 9 is a group represented by formula (3).
• R 10 represents a divalent hydrocarbon group which may have a substituent.
• the second alkali-soluble resin of the present invention has excellent photocurability and can give a cured product with a high refractive index is believed to be because it has the structure of formula (4) containing a sulfur atom and an aromatic group, which makes it possible to increase the refractive index of the cured product, and because it has the structure of formula (2), which makes it possible to improve the photocurability.
• R 23 represents an aromatic group which may have a substituent.
• Examples of the aromatic group which may have a substituent represented by R 23 include the same groups as the aromatic group which may have a substituent represented by R 2 in the above formula (1).
• R 24 is a hydrogen atom or a group represented by formula (3).
• the group represented by the formula (3) is the same as the group represented by the formula (3) described in the above section ⁇ First alkali-soluble resin>.
• the polymerizable unsaturated bond-containing structure represented by the above formula (2) is the same as the polymerizable unsaturated bond-containing structure represented by the formula (2) described in the above section ⁇ First alkali-soluble resin>.
• the second alkali-soluble resin preferably has a novolac main chain structure, similar to the first alkali-soluble resin.
• the alkali-soluble resin having the aromatic ring-containing structure represented by formula (4) above and the polymerizable unsaturated bond-containing structure represented by formula (2) above is an alkali-soluble resin having a structural unit (E) represented by formula (e) below and a structural unit (B) described in the above section ⁇ First alkali-soluble resin>.
• A represents a benzene ring or a naphthalene ring.
• R 23 and R 24 are the same as those described above.
• R 25 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
• R 26 represents a substituent bonded to A.
• f represents the number of R 26 and is an integer of 0 to 5. When there are two or more R 26 , they may be the same or different.
• R 27 represents a direct bond or a divalent organic group.
• A represents a benzene ring or a naphthalene ring, and preferably represents a benzene ring.
• Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 25 include the same groups as the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 11 in formula (a) described in the above section ⁇ First alkali-soluble resin>.
• Examples of the substituent represented by R 26 include the same groups as the substituent represented by R 12 in the above formula (a).
• f represents the number of R 26 and is an integer of from 0 to 5. In terms of good developability, f is preferably from 0 to 3, more preferably from 1 to 3, and is preferably 1.
• the second alkali-soluble resin may have one or more types of the structural unit (E).
• the content of the structural unit (E) in the second alkali-soluble resin is preferably 1 to 99 mol%, more preferably 20 to 95 mol%, even more preferably 40 to 93 mol%, even more preferably 50 to 90 mol%, particularly preferably 60 to 85 mol%, and most preferably 60 to 80 mol%, relative to 100 mol% of all structural units.
• the content of the structural unit (B) in the second alkali-soluble resin is preferably 1 to 80 mol%, more preferably 2 to 70 mol%, even more preferably 3 to 50 mol%, even more preferably 5 to 40 mol%, particularly preferably 10 to 40 mol%, and most preferably 15 to 40 mol%, relative to 100 mol% of all structural units.
• the second alkali-soluble resin may have other structural units in addition to the structural units (E) and (B) described above.
• Examples of the other structural units include the structural unit (C) or the structural unit (D) described in the section ⁇ First alkali-soluble resin> above.
• the content ratio thereof is preferably the same as the content ratio in the first alkali-soluble resin described above.
• the polymerizable unsaturated bond equivalent of the second alkali-soluble resin is preferably 300 to 8000 g/equivalent, more preferably 500 to 6000 g/equivalent, even more preferably 700 to 5000 g/equivalent, even more preferably 800 to 4000 g/equivalent, and particularly preferably 800 to 2000 g/equivalent.
• the acid value, epoxy group equivalent, weight average molecular weight, and glass transition temperature of the second alkali-soluble resin are preferably the same as the acid value, epoxy group equivalent, weight average molecular weight, and glass transition temperature of the first alkali-soluble resin described above.
• the method for producing the first alkali-soluble resin of the present invention is not particularly limited as long as the above-mentioned first alkali-soluble resin can be obtained. However, a production method including the following steps is preferred in terms of efficiently producing the first alkali-soluble resin of the present invention.
• the amounts of the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) used in the first step are adjusted so that the polymerizable unsaturated bond equivalent of the resulting alkali-soluble resin is 700 to 8,000 g/equivalent, thereby producing the first alkali-soluble resin of the present invention.
• Such a first method for producing an alkali-soluble resin that is, a method for producing an alkali-soluble resin, which comprises a first step of reacting an epoxy resin (a) having two or more epoxy groups in one molecule with an aromatic group-containing compound (b) and an unsaturated monocarboxylic acid (c), and a second step of reacting a polybasic acid anhydride (d) with the reaction product obtained in the first step, wherein the amounts of the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) used in the first step are adjusted so that the resulting alkali-soluble resin has a polymerizable unsaturated bond equivalent of 700 to 8,000 g/equivalent, also constitutes one aspect of the present invention.
• Each step will be described below.
• the starting material epoxy resin (a) having two or more epoxy groups in one molecule is not particularly limited, and any known epoxy resin having two or more epoxy groups in one molecule can be used, including bisphenol-type epoxy resins; biphenyl-type epoxy resins; alicyclic epoxy resins; polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenylglycidyl ether ethane; phenol novolac-type epoxy resins and cresol novolac-type epoxy resins.
• Resins reaction products of epichlorohydrin and polyphenol compounds obtained by condensation reaction of phenolic compounds such as phenol, o-cresol, m-cresol, naphthol, and aromatic aldehydes having a phenolic hydroxyl group; reaction products of epichlorohydrin and polyphenol compounds obtained by addition reaction of phenolic compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene; ring-opening polymers of 4-vinylcyclohexene-1-oxide epoxidized with peracid; epoxy resins having heterocycles such as triglycidyl isocyanurate; and the like.
• those obtained by reacting two or more molecules of these epoxy resins with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol to bond and extend the chain can also be used.
• they may be homopolymers or copolymers of monomers having an epoxy group such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate.
• the epoxy resin (a) having two or more epoxy groups per molecule as the starting material preferably has an epoxy equivalent of 500 g/equivalent or less, in order to provide an alkali-soluble resin having superior developability and photocurability. More preferably, the epoxy equivalent is 400 g/equivalent or less, and even more preferably, the epoxy equivalent is 300 g/equivalent or less.
• the aromatic group-containing compound (b) is not particularly limited as long as it is a compound having an aromatic group and a group capable of reacting with an epoxy group, and examples of the aromatic compounds include the above-mentioned aromatic compounds.
• the aromatic group includes the groups having the aromatic ring structure described above. Examples of the group capable of reacting with the epoxy group include an acidic group, an amino group, and a hydroxyl group. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a mercapto group, and preferably a phenolic hydroxyl group and a mercapto group.
• the aromatic group-containing compound is preferably an aromatic group-containing acid compound having the aromatic group and an acidic group.
• the aromatic group-containing compound is not particularly limited as long as it is a compound that can impart the above-mentioned aromatic ring-containing structure to the resulting resin, but preferred examples include phenol derivatives such as phenylphenol, thiophenol derivatives such as toluenethiol and benzenethiol, and alcohol derivatives such as hydroxyphenethyl alcohol. Among these, thiophenol derivatives are preferred, and benzenethiol is most preferred, in that the thioether bond produced can achieve both a high refractive index and high-speed developability. These may be used alone or in combination of two or more types.
• a chain-extended acid group can be introduced into the alkali-soluble resin by reacting with a polybasic acid anhydride in step (2) described below. Since such an acid group is positioned away from the main chain, it improves developability and reactivity during curing.
• the unsaturated monocarboxylic acid (c) is not particularly limited as long as it has an unsaturated bond and a carboxyl group, but preferably has 3 to 20 carbon atoms. More preferably, it has 3 to 10 carbon atoms, and even more preferably, it has 3 to 4 carbon atoms.
• the unsaturated monocarboxylic acid (c) may be 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 with a dibasic acid anhydride, or a reaction product of a polyfunctional (meth)acrylate having one hydroxyl group and two or more (meth)acryloyl groups with a dibasic acid anhydride.
• those having a (meth)acryloyl group such as acrylic acid or methacrylic acid are preferred.
• Methacrylic acid is particularly preferred from the viewpoint that the resulting alkali-soluble resin gives a cured product with particularly excellent solvent resistance. These may be used alone or in combination of two or more.
• the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) may be added all at once, or in portions or successively. However, in order to prevent side reactions, addition in portions or successively is preferred.
• the epoxy resin (a) in the first step of reacting an aromatic group-containing compound (b) and an unsaturated monocarboxylic acid (c) with an epoxy resin (a) having two or more epoxy groups in one molecule, the epoxy resin (a) may be reacted with the unsaturated monocarboxylic acid (c) and then with the aromatic group-containing compound (b), or the unsaturated monocarboxylic acid (c) and the aromatic group-containing compound (b) may be reacted with the epoxy resin (a) all at once, or the epoxy resin (a) may be reacted with the aromatic group-containing compound (b) and then with the unsaturated monocarboxylic acid (c).
• the amount of the aromatic group-containing compound (b) added is preferably 0.51 to 0.93 moles of acid groups in the aromatic group-containing compound (b) per chemical equivalent (molar equivalent) of the epoxy group in the epoxy resin (a), more preferably 0.55 to 0.92 moles, even more preferably 0.6 to 0.91 moles, even more preferably 0.6 to 0.9 moles, particularly preferably 0.6 to 0.8 moles, and most preferably 0.6 to 0.75 moles.
• the reaction rate of the epoxy resin (a) and the aromatic group-containing compound (b) can be increased by replacing the atmosphere in the reaction tank with an inert gas such as nitrogen to reduce the oxygen concentration.
• the oxygen concentration in the reaction tank is preferably 1% by volume or less, more preferably 0.5% by volume or less, and even more preferably 0.3% by volume or less.
• the total amount of aromatic group-containing compound (b) and unsaturated monocarboxylic acid (c) used is 0.8 to 1.2 moles per mole of epoxy group in epoxy resin (a). By using them in such a ratio, it becomes easier to improve the curability of the finally obtained alkali-soluble resin and the physical properties of the cured product. It is preferably 0.85 to 1.15 moles, more preferably 0.9 to 1.1 moles.
• an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 to 8,000 g/equivalent can be obtained.
• the reaction of the epoxy resin (a) with the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) may be carried out in either order or simultaneously, as described above.
• reaction catalyst such as a tertiary amine, a tertiary phosphine such as trimethylphosphine, tributylphosphine or triphenylphosphine, lithium chloride, a quaternary ammonium salt or a quaternary phosphonium salt, usually at 60 to 140° C.
• a diluent such as a polymerizable compound or a solvent described later
• a reaction catalyst such as a tertiary amine, a tertiary phosphine such as trimethylphosphine, tributylphosphine or triphenylphosphine, lithium chloride, a quaternary ammonium salt or a quaternary phosphonium salt, usually at 60 to 140° C.
• tertiary phosphines are preferred from the viewpoints of reaction efficiency, stability during the reaction, and storage stability of the alkali-soluble resin, and triphenylphosphin
• the amount of the reaction catalyst is not particularly limited, but is preferably 0.05 to 5 parts by mass per 100 parts by mass of the epoxy resin (a) having two or more epoxy groups in one molecule. More preferably, it is 0.1 to 3 parts by mass, and even more preferably, it is 0.2 to 2 parts by mass.
• a polymerization inhibitor may be used.
• the polymerization inhibitor is not particularly limited, and known ones can be used.
• benzoquinone hydroquinones (e.g., hydroquinone, hydroquinone monomethyl ether, p-tert-butylhydroquinone, p-benzoquinone, etc.), phenols (e.g., 2,6-di-t-butyl-4-methylphenol, 6-t-butyl-2,4-dimethylphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol)), catechols (e.g., p-tert-butylcatechol, etc.), amines (e.g., N,N-diethylhydroxylamine, etc.), 1,1-diphenyl-2-picrylhydrazyl, tri-p-nitrophenylmethyl, phenothiazine, piperidine 1-oxyls (e.g., 2,2,6,6-
• the amount of the polymerization inhibitor used is preferably 0.001 to 1 mass% relative to 100 mass% of the epoxy resin (a) having two or more epoxy groups in one molecule. More preferably, it is 0.01 to 0.5 mass%.
• reaction solvent examples include 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, (di)methyl glutarate, (di)methyl succinate, and (di)methyl adipate; ketones such as methyl isobutyl ketone and methyl ethyl ketone; and ethers such as (di)ethylene glycol dimethyl ether.
• 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)
• the reaction temperature in the first step is not particularly limited as long as the reaction proceeds, but is preferably 40 to 140°C. By carrying out the reaction at such a temperature, the reaction can proceed efficiently.
• the reaction temperature is more preferably 50 to 135°C, and even more preferably 60 to 130°C.
• the epoxy resin (a) may be reacted with a carboxylic acid having no double bond together with the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c).
• the double bond equivalent, epoxy equivalent, glass transition temperature, etc. of the alkali-soluble resin can be adjusted.
• the carboxylic acid having no double bond include propionic acid, acetic acid, butyric acid, decanoic acid, and 2-ethylhexyl carboxylic acid.
• the epoxy resin (a) may also be reacted with an acid compound having a functional group with radical scavenging ability or ultraviolet absorbing ability, together with the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c).
• an acid compound having a functional group with radical scavenging ability or ultraviolet absorbing ability together with the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c).
• Examples of the functional group having a radical scavenging ability or an ultraviolet absorbing ability include the above-mentioned functional groups having a radical scavenging ability or an ultraviolet absorbing ability.
• Examples of the acid group contained in the acid compound include the acid groups described above, and among them, a carboxyl group is preferable.
• acid compounds having functional groups with the above-mentioned radical scavenging ability or ultraviolet absorbing ability include, for example, 3,5-di-tert-butyl 4-hydroxybenzoic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3-methylsalicylic acid, trimethylhydroquinone, 3-phenylsalicylic acid, 4-hydroxy-3,5-dimethylbenzoic acid, 3,5-di-tert-butylsalicylic acid, mycophenolic acid, xanthohumol, monoethyl 3,5-di-tert-butyl 4-hydroxybenzylphosphonate, etc., and among these, 3,5-di-tert-butyl 4-hydroxybenzoic acid and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid are preferred.
• the reaction product (intermediate) obtained in the first step is reacted with a polybasic acid anhydride (d), which reacts with the hydroxyl groups present in the reaction product to obtain the alkali-soluble resin of the present invention having a carboxyl group introduced therein.
• a polybasic acid anhydride (d) which reacts with the hydroxyl groups present in the reaction product to obtain the alkali-soluble resin of the present invention having a carboxyl group introduced therein.
• the resulting alkali-soluble resin can be developed in an alkali, and can therefore be used as an alkali-developable curable resin for image formation, etc.
• the polybasic acid anhydride (d) used in the second step is not particularly limited, but preferably has 3 to 30 carbon atoms. More preferably, it has 4 to 20 carbon atoms, and even more preferably, it has 4 to 10 carbon atoms.
• the polybasic acid anhydride (d) may be, for example, dibasic acid anhydrides such as phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, 3,6-endo methylene tetrahydrophthalic anhydride, methyl end methylene tetrahydrophthalic anhydride, tetrabromo phthalic anhydride, and trimellitic acid; aliphatic or aromatic tetrabasic acid dianhydrides such as biphenyl tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane t
• polybasic acid anhydrides may be used. Among these, it is preferable to use a dibasic acid anhydride. Furthermore, from the viewpoint of producing a cured product of the resulting alkali-soluble resin that has particularly excellent solvent resistance, polybasic acid anhydrides such as phthalic anhydride that give an alkali-soluble resin having a cyclic structure in its structure are particularly preferred.
• the second step it is preferable to react the polybasic acid anhydride (d) in a ratio of 0.1 moles to 1.1 moles per chemical equivalent of hydroxyl groups in the reaction product obtained in the first step.
• the addition reaction of the polybasic acid anhydride (d) can be efficiently carried out, and carboxyl groups can be suitably introduced into the resulting alkali-soluble resin.
• reaction of the reaction product obtained in the reaction of the first step with the polybasic acid anhydride (d) in the above-mentioned second step can be carried out in the presence or absence of a diluent such as a polymerizable compound or a solvent described later, and, if necessary, in the coexistence of the above-mentioned polymerization inhibitor or reaction catalyst, in the same manner as the reaction of the first step.
• a reaction catalyst may be used, and a tertiary phosphine is preferable, and triphenylphosphine is more preferable.
• the reaction temperature in the second step is not particularly limited as long as the reaction proceeds, but is preferably 45 to 130°C. By carrying out the reaction at such a temperature, the reaction can proceed efficiently.
• the reaction temperature is more preferably 50 to 120°C, and even more preferably 55 to 110°C.
• the epoxy resin (a) is chain-extended by reacting the epoxy resin (a) with a compound capable of introducing the structural unit (D), and the chain-extended epoxy resin (a) is subjected to the first step, thereby producing an alkali-soluble resin having the structural unit (D).
• Examples of compounds into which the structural unit (D) can be introduced include the bisphenol compounds from which the structural unit (D) is derived.
• reaction catalyst may be used.
• reaction catalyst used in the reaction include the same catalysts as those used in the first and second steps described above.
• the method for producing the first alkali-soluble resin may include other steps as long as it includes the first and second steps.
• the second method for producing an alkali-soluble resin may include a method including the same first and second steps as the first method for producing an alkali-soluble resin, except that the aromatic group-containing compound used is one that contains a sulfur atom and that the polymerizable unsaturated bond equivalent of the alkali-soluble resin is not limited to 700 to 8000 g/equivalent.
• the aromatic group-containing compound (b') used in the second method for producing an alkali-soluble resin preferably contains a sulfur atom.
• the aromatic group-containing compound (b') is preferably one of the aromatic group-containing compounds (b) used in the first method for producing an alkali-soluble resin described above, in which the group capable of reacting with an epoxy group contains a sulfur atom.
• the aromatic group-containing compound (b') is preferably a compound containing the aromatic group and a mercapto group described above.
• the amount of the aromatic group-containing compound (b') added is preferably 0.01 to 0.99 moles of acid groups in the aromatic group-containing compound (b') per chemical equivalent (molar equivalent) of epoxy groups in the epoxy resin (a), more preferably 0.2 to 0.95 moles, even more preferably 0.4 to 0.93 moles, even more preferably 0.6 to 0.9 moles, particularly preferably 0.6 to 0.85 moles, and most preferably 0.6 to 0.80 moles.
• the polymerizable unsaturated bond equivalent is not limited, but by adjusting the amounts of aromatic group-containing compound (b') and unsaturated monocarboxylic acid (c) used in the first step, an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 300 to 8000 g/equivalent can be obtained.
• the method for producing an alkali-soluble resin of the present invention described above includes the first and second steps described above, and the reaction product (intermediate) obtained in the first step is preferably a resin having an aromatic ring-containing structure represented by the following formula (1') and a polymerizable unsaturated bond-containing structure represented by the following formula (2') and having a polymerizable unsaturated double bond equivalent of 600 to 7000 g/equivalent.
• R 1 represents an oxygen atom or a sulfur atom.
• R 2 represents an aromatic group which may have a substituent.
• R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.
• R 1 and R 2 in the above formula (1') are the same as those in the above formula (1), and R 4 to R 8 in the above formula (2') are the same as those in the above formula (2).
• the polymerizable unsaturated bond equivalent of the resin is not particularly limited, but is preferably 650 to 6000 g/equivalent, more preferably 700 to 5000 g/equivalent, and even more preferably 750 to 4000 g/equivalent.
• Preferred examples of the resin having an aromatic ring-containing structure represented by formula (1') include resins having a structural unit (A') in which "--CH--O--R 3 " in formula (a) is "--CH--OH".
• the content of the structural unit (A') in the above resin is preferably in the same range as the content of the structural unit (A) described above.
• Preferred examples of the resin having a polymerizable unsaturated bond-containing structure represented by formula (2') include resins having a structural unit (B') in which "--CH--O--R 9 " in formula (b) is "--CH--OH.”
• the content of the structural unit (B') in the above resin is preferably in the same range as the content of the structural unit (B) described above.
• the above resin may further have the above-mentioned structural unit (C) and structural unit (D).
• photosensitive resin composition The photosensitive resin composition containing the first and/or second alkali-soluble resin of the present invention, a polymerizable compound, and a photopolymerization initiator is also one of the present inventions. Since the photosensitive resin composition of the present invention contains the above-mentioned alkali-soluble resin, it can provide a cured product with excellent photocurability and a high refractive index.
• the first alkali-soluble resin of the present invention and the above-mentioned second alkali-soluble resin are collectively referred to as the alkali-soluble resin of the present invention.
• the content of the first and/or second alkali-soluble resin is not particularly limited and may be appropriately set depending on the application, the blending of other components, and the like.
• the content is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, even more preferably 15 to 75 mass%, and particularly preferably 15 to 70 mass%, relative to 100 mass% of the total solid content of the photosensitive resin composition.
• total solid content refers to the total amount of components that form the cured product (components excluding the solvent and curing catalyst that volatilize during the formation of the cured product).
• the polymerizable compound is a low molecular weight compound having a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), and electron beams.
• active energy rays such as free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), and electron beams.
• Examples of the polymerizable compound 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 monomers; (meth)acrylic acid esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; and the like.
• Monomers having an active methylene group or an active methine group can also be used.
• polyfunctional compound examples include the following compounds.
• bifunctional (meth)acrylate compounds such as 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 di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F alkylene oxide di(meth)acrylate;
• a polyfunctional (meth)acrylate compound having three or more functional groups such as a modified product of dipentaerythritol hexaacrylate represented by the formula:
• Multifunctional vinyl ethers such as 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, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added penta
• (Meth)acrylic acid esters containing vinyl ether groups such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate;
• Multifunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol
• Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (me
• the number of functionalities of the above polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more.
• the number of functionalities is preferably 10 or less, more preferably 8 or less.
• the number of functional groups is preferably 3 to 10, more preferably 4 to 8.
• the molecular weight of the polymerizable compound is not particularly limited, but is preferably, for example, 2000 or less from the viewpoint of handling.
• a compound having a (meth)acryloyl group such as a polyfunctional (meth)acrylate compound, a polyfunctional urethane (meth)acrylate compound, or a (meth)acryloyl group-containing isocyanurate compound, is mentioned, and more preferably, a polyfunctional (meth)acrylate compound.
• a compound having a (meth)acryloyl group the photosensitive resin composition has better photosensitivity and curing properties, and a cured product having even higher hardness and transparency can be obtained. It is even more preferable to use a polyfunctional (meth)acrylate compound having three or more functionalities as the polyfunctional polymerizable compound.
• the content of the polymerizable compound is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 40% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.
• Photopolymerization initiator Specific examples of the photopolymerization initiator include aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE (registered trademark) 907", manufactured by BASF Corporation), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE 369", manufactured by BASF Corporation), and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one ("IRGACURE 379", manufactured by BASF Corporation); 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE 651", manufactured by BASF Corporation), phenylglyoxylic acid methyl ester ("DAROCUR benzyl ketal compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BAC
• the content of the photopolymerization initiator 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, relative to 100% by mass of the total solid content of the photosensitive resin composition.
• the photosensitive resin composition of the present invention contains at least the above-mentioned alkali-soluble resin, polymerizable compound, and photopolymerization initiator, and may further contain one or more other components as necessary. In addition, one or more of each of the components may be used. The other components are described below.
• the photosensitive resin composition may further contain a polyfunctional thiol compound.
• a polyfunctional thiol compound When the photosensitive resin composition contains the alkali-soluble resin having a polymerizable unsaturated bond in the side chain and a polyfunctional thiol compound, an enethiol reaction occurs simultaneously during exposure or heating, and the crosslink density can be improved. In particular, when an acrylate-type polymerizable unsaturated bond is present in the resin, the enethiol reaction proceeds well.
• the polyfunctional thiol compound is preferably a compound having two or more mercapto groups in one molecule and a molecular weight of 200 to 1000, and a tri- to penta-functional secondary thiol is particularly preferred.
• polyfunctional thiol compound examples include mercaptopropionic acid derivatives such as butanediol bisthiopropionate, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakis thiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz (registered trademark) PE-1), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz BD-1), and 1,3,5-tris (3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-trione (Karenz NR-1).
• the polyfunctional thiol compound is preferably a compound that does not have a hydroxyl group and/or an aromatic ring in the molecule.
• the content of the polyfunctional thiol compound is preferably 0.3 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 8% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.
• the photosensitive resin composition also preferably contains metal oxide particles.
• metal oxide particles By containing metal oxide particles in the photosensitive resin composition, a cured product with a high refractive index can be obtained. In addition, the photosensitivity and dielectric properties are good. Although the reason for this is unclear, it can be assumed that when the difference in refractive index between the resin and the metal oxide particles is small, the loss of light due to Rayleigh scattering or the like during exposure can be reduced. Since the resolution is not impaired even when the photosensitive resin composition is highly filled with metal oxide particles, the dielectric properties can be improved.
• the above-mentioned metal oxide particles include, for example, oxide particles of metals having high refractive index and optical transparency, including atoms such as Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te.
• oxide particles of metals having high refractive index and optical transparency including atoms such as Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te.
• the above-mentioned metal oxide particles preferably include at least one metal element selected from the group consisting of Ti, Al, Zr, Zn, Sn, Ce, and Si, in that they can provide a cured product with a higher refractive index, and more preferably include Zr from the viewpoint of providing a cured film with a high dielectric constant, and more preferably include Si from the viewpoint of providing a cured film with high hardness.
• the metal oxide may be an oxide of a single metal, a solid solution of two or more kinds of oxides, or a composite oxide.
• single metal oxides include aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), indium oxide (In 2 O 3 ), zinc oxide (ZnO), tin oxide (SnO 2 ), lanthanum oxide (La 2 O 3 ), yttrium oxide (Y 2 O 3 ), cerium oxide (CeO 2 ), magnesium oxide (MgO), and silicon oxide (SiO 2 ).
• solid solutions of two or more kinds of oxides include ITO and ATO.
• composite oxides include barium titanate (BaTiO 3 ), perovskite (CaTiO 3 ), and spinel (MgAl 2 O 4 ).
• zirconium dioxide particles ( ZrO2 particles) and/or silicon dioxide particles ( SiO2 particles) are preferred because they can provide a cured product with a high refractive index, a high dielectric constant, or high hardness.
• the metal oxide particles are preferably surface-modified metal oxide particles, since this can enhance dispersibility in the photosensitive resin composition.
• the surface modification of the metal oxide particles can be achieved by a known method, such as a method of mixing the metal oxide particles with a surface modifier in a solvent, or a method of performing a hydrothermal reaction in the presence of water.
• the surface modifier is not particularly limited, and examples thereof include known coupling agents, surfactants, carboxylic acid compounds, etc. Only one type of surface modifier may be used, or two or more types may be used.
• the surface modifier is preferably a carboxylic acid compound.
• the carboxylic acid compound include carboxylic acids which may have a substituent and (meth)acrylic acid.
• substituent include an ester group, an ether group, an amide group, a thioester group, a thioether group, a carbonate group, a urethane group, and a urea group.
• carboxylic acid compound examples include aliphatic carboxylic acids and cyclic carboxylic acids such as acetic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, salicylic acid, naphthenic acid, decanoic acid, and lauric acid.
• aliphatic carboxylic acids and cyclic carboxylic acids such as acetic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, salicylic acid, naphthenic acid, decanoic acid, and lauric acid.
• the metal oxide particles are preferably those described in JP 2013-216858 A.
• the crystallite diameter of the metal oxide particles is preferably 1 to 20 nm, more preferably 1 to 15 nm, and even more preferably 1 to 10 nm.
• the crystallite diameter can be determined by X-ray diffraction analysis.
• the number average primary particle diameter of the metal oxide particles is preferably less than 30 nm, more preferably 1 to 25 nm, even more preferably 3 to 20 nm, even more preferably 5 to 20 nm, and particularly preferably 5 to 15 nm.
• the number average primary particle diameter can be determined by magnifying and observing the metal oxide particles with a transmission electron microscope (TEM), field emission transmission electron microscope (FE-TEM), field emission scanning electron microscope (FE-SEM), etc., randomly selecting 100 particles, measuring their length in the major axis direction, and calculating the arithmetic average.
• TEM transmission electron microscope
• FE-TEM field emission transmission electron microscope
• FE-SEM field emission scanning electron microscope
• the refractive index of the metal oxide particles is preferably 1.70 to 2.70, and more preferably 1.90 to 2.70.
• the specific surface area of the metal oxide particles is preferably from 10 to 400 m 2 /g, more preferably from 20 to 200 m 2 /g, and further preferably from 30 to 150 m 2 /g.
• the content of the metal oxide particles is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, relative to 100% by mass of the total solid content of the alkali-soluble resin composition.
• the photosensitive resin composition may also contain other components other than the above-mentioned components as necessary.
• the other components include solvents, coloring materials (pigments, dyes), dispersants, heat resistance improvers, leveling agents, development aids, coupling agents such as silanes, aluminum, and titanium, fillers, thermosetting resins such as phenolic resins, polyvinylphenols, epoxy compounds, and epoxy resins, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoamers, antistatic agents, slip agents, surface modifiers, thixotropic agents, thixotropic aids, quinone diazide compounds, polyhydric phenol compounds, cationic polymerizable compounds, and thermal acid generators. These may be used alone or in combination of two or more. These other components can be appropriately selected from known ones and used, and the amount used can be appropriately set.
• the present invention also includes a photosensitive resin composition (also referred to as photosensitive resin composition (x)) that contains the resin (intermediate) reactant of the first step described above, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
• a photosensitive resin composition also referred to as photosensitive resin composition (x)
• the resin (intermediate) reactant of the first step described above an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
• the alkali-soluble resin contained in the photosensitive resin composition (x) is not particularly limited, and any known alkali-soluble resin can be used, and the alkali-soluble resin of the present invention described above may also be used.
• the polymerizable compound and photopolymerization initiator contained in the photosensitive resin composition (x) may be the same as those described above.
• the content of each of these components may be the same as described above.
• the photosensitive resin composition (x) may also contain other components, and examples of the other components include those similar to those in the photosensitive resin composition described above. The content of each of these components can be set appropriately.
• the method for producing the photosensitive resin composition of the present invention is not particularly limited and may be a known method, for example, a method in which the above-mentioned components are mixed and dispersed using various mixers and dispersers.
• the mixing and dispersion process is not particularly limited and may be performed by a known method.
• the method may further include other steps that are usually performed.
• the method for producing the photosensitive resin composition is preferably a method including a step of producing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 to 8000 g/equivalent by the above-mentioned method for producing an alkali-soluble resin, or a step of mixing the obtained alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
• a method for producing a photosensitive resin composition is also one aspect of the present invention.
• the alkali-soluble resin or photosensitive resin composition of the present invention can be used to obtain a cured product having a high refractive index and excellent curability.
• the cured product obtained by curing the alkali-soluble resin or photosensitive resin composition of the present invention also constitutes one aspect of the present invention.
• the above-mentioned photosensitive resin composition (x) also has a high refractive index and can give a cured product with excellent curing properties.
• the cured product of such a photosensitive resin composition (x) also constitutes one aspect of the present invention.
• the cured product is a cured film
• its film thickness is preferably 0.1 to 50 ⁇ m, more preferably 0.5 to 40 ⁇ m, and even more preferably 1 to 30 ⁇ m.
• the method for obtaining the cured product is not particularly limited, and any known method may be used.
• the above-mentioned alkali-soluble resin or photosensitive resin composition is applied or molded onto a substrate, and then heated or irradiated with active energy rays such as ultraviolet rays, or a combination of these, to obtain a cured product.
• the method for producing a cured product is preferably a method including a step of applying the above-mentioned photosensitive resin composition onto a substrate to form a coating film, a step of irradiating the formed coating film with light, and a step of heating the irradiated coating film.
• the substrate is not particularly limited and may be appropriately selected depending on the purpose and application. Examples include substrates made of various materials such as glass plates and plastic plates.
• the method for applying the photosensitive resin composition to a substrate to form a coating film is not particularly limited, and can be performed by a known method such as spin coating, slit coating, roll coating, or casting coating.
• the drying can be performed by a known method, for example, using a hot plate, an IR oven, a convection oven, etc.
• the drying conditions are appropriately selected depending on the boiling point of the solvent components contained, the type of curing component, the film thickness, the performance of the dryer, etc., but it is usually preferable to perform the drying at a temperature of 50 to 160°C for 10 to 300 seconds.
• the method of irradiating the formed coating film with light is not particularly limited, and can be performed by a known method.
• light sources of actinic rays used for light irradiation include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers.
• the irradiation may be performed through a photomask.
• a photomask a mask having light-shielding portions formed according to a desired pattern is preferably used.
• the method may include a step of performing light irradiation through a photomask, followed by development treatment with a developer to remove the unirradiated parts.
• the irradiated parts are cured by light irradiation, and the cured product is made insoluble or poorly soluble in the developer.
• the unirradiated parts dissolve in the developer, and are removed by the development treatment to obtain a patterned cured film.
• the development treatment can be usually performed at a development temperature of 10 to 50° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.
• the developer is not particularly limited as long as it dissolves the photosensitive resin composition.
• an organic solvent or an alkaline aqueous solution is used, and a mixture of these may also be used.
• an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development.
• organic solvents and alkaline aqueous solutions include those similar to those described in JP 2015-157909 A.
• the coating film After the light irradiation, it is preferable to heat the coating film to 160°C or less. It is more preferable that the heating temperature of the coating film is 150°C or less.
• the lower limit of the heating temperature is preferably 70°C or more, and more preferably 80°C or more, in terms of maintaining the curability.
• the heating temperature is preferably 70 to 160°C, more preferably 80 to 150°C.
• the heating time is not particularly limited, and is preferably 5 to 60 minutes, for example.
• the heating method is also not particularly limited, and can be performed using known heating equipment such as a hot plate, a convection oven, or a high-frequency heater.
• the alkali-soluble resin and photosensitive resin composition of the present invention have excellent curability and can give a cured product having a high refractive index. Therefore, the alkali-soluble resin and photosensitive resin composition can be suitably used in applications requiring curability and a high refractive index.
• the alkali-soluble resin and photosensitive resin composition of the present invention also have a high development speed and can be suitably used in applications requiring developability. Therefore, they are suitable for use in optical materials, and particularly suitable for use as resists.
• the photosensitive resin composition of the present invention can be suitably used for both negative and positive types.
• the alkali-soluble resin and photosensitive resin composition of the present invention which have a high refractive index, can be used in, for example, magnetic recording materials, catalyst materials, ultraviolet absorbing materials, dental materials, contact lenses, intraocular lenses, high refractive index lenses for glasses, optical computing, optical storage media, anti-reflection films, conformal coatings, microlens arrays, automotive topcoats, paints, coating agents, hair cosmetics, gradient refractive index optical components and dynamic gradient refractive index components, nanoimprint materials, photocurable plastics, polymerizable compounds for hologram recording, surface coating materials for glass, transparent coating materials for solar cells, plastic lenses, printing plates, semiconductor light-emitting elements (light-emitting diodes, organic light-emitting diodes, laser diodes, etc.), It can be widely applied to various applications such as glass, film and sheet surfaces used in sensor elements such as CCD/CMOS and display elements such as displays, photocurable resins (OCR) used to bond image display members such as liquid crystals to
• optical material refers to a material used for components of devices in the optical field or the electrical and electronic fields, and is used as a material for, for example, color filters, light extraction layers, black matrices, photospacers, black column spacers, photoresists, overcoats, flattening layers for TFTs, insulating films for TFTs, surface coatings for optical lenses, etc., used in liquid crystal, organic EL, quantum dot, mini/micro LED display devices, solid-state imaging devices, touch panel display devices, etc.
• the alkali-soluble resin of the present invention can be suitably used for applications in which photolithography is applied because of its alkali solubility, and can become a cured film having high refractive index, high hardness, and high transparency, so that the photosensitive resin composition of the present invention is most preferably a curable resin composition for color filters, light extraction layers, and color conversion layers for organic EL display devices.
• the alkali-soluble resin of the present invention can be suitably used as a highly refractive member that is capable of photolithography and has high transparency.
• the above-mentioned alkali-soluble resin and photosensitive resin composition are preferably used for display devices, and a member for a display device and a display device containing a cured product of the above-mentioned photosensitive resin composition are also part of the present invention.
• alkali-soluble resin and photosensitive resin composition can also be suitably used for various optical components such as inks, printed wiring boards, insulating films, films, and organic protective films, as well as components of electrical and electronic devices.
• the weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using polystyrene as a standard substance under the following measurement conditions: Apparatus: Gel permeation chromatography apparatus HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSKgel Super HZM-M (Tosoh Corporation) Detector: RI detector for liquid chromatography Measurement temperature: 40°C Solvent: THF (tetrahydrofuran) Sample concentration: 0.05 g/10 cc Sample flow rate: 0.6 ml/min
• ⁇ Acid value> 3 g of the resin solution was precisely weighed out and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1 N KOH aqueous solution as a titrant. The titration was performed using an automatic titrator (product name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of solid content (mg KOH/g) was calculated from the acid value of the resin solution and the solid content of the resin solution.
• the solid content of the resin solution was determined by the following method.
• ⁇ Refractive index (resin)> The resin solution in Table 1 was uniformly applied onto a 5 cm square glass substrate (soda lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.) using a spin coater (manufactured by Mikasa Co., Ltd., 1H-D7). The coated plate was dried at 90 ° C. for 3 minutes to obtain a laminate. After removing the resin composition adhering to the end of the glass substrate, the obtained laminate was heat-treated at 95 ° C. for 60 minutes using a Perfect Oven Thermostat (manufactured by Espec Co., Ltd.), cooled to room temperature, and a laminate with a coating film thickness of 0.5 ⁇ m was obtained.
• a Perfect Oven Thermostat manufactured by Espec Co., Ltd.
• the obtained laminate was used as a measurement sample, and the reflectance of the coating film was simulated based on the Fresnel formula from the reflectance due to the measured coating film interference using the following device, to calculate the refractive index of the coating film at a light wavelength of 589 nm.
• Apparatus Filmetrics Film Thickness Measurement System F-20. Standard fiber stage SS-1 (spot diameter 1.5 mm).
• ⁇ Refractive Index (Photosensitive Resin Composition)> The photosensitive resin compositions according to the formulations in Tables 2 and 4 were uniformly applied onto a 5 cm square glass substrate (soda lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.) using a spin coater (1H-D7, manufactured by Mikasa Co., Ltd.). The coated plate was dried at 90°C for 3 minutes, and then exposed to light at 100 mJ using a high-pressure mercury lamp to obtain a laminate in which a coating film was formed on the glass substrate.
• the obtained laminate was subjected to a heat treatment at 95°C for 60 minutes using a Perfect Oven Thermostat (manufactured by Espec Corporation), and cooled to room temperature to obtain a laminate with a coating film thickness of 0.5 ⁇ m.
• the obtained laminate was used as a measurement sample, and the refractive index was determined in the same manner as the refractive index of the resin described above.
• the photosensitive resin composition according to the formulation in Table 3 was spin-coated on a 5 cm square glass substrate, dried at 100°C for 3 minutes, exposed to light at 200 mJ using a high-pressure mercury lamp, and then heat-treated (post-cured) at 150°C for 40 minutes to obtain a cured film having a thickness of 2 ⁇ m.
• the cured film was then immersed in 20 g of propylene glycol monomethyl ether (PGME) at 40°C for 10 minutes, and then removed.
• the absorbance of the immersion liquid (PGME) after removing the cured film was measured using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The higher the absorbance value, the more the colorant was dissolved in the immersion liquid, and the photosensitive resin composition was evaluated to have low solvent resistance.
• ⁇ Development speed> The photosensitive resin composition was applied to a 10 cm square glass substrate by spin coating, and then heat-treated (90°C, 3 minutes). After that, the substrate was exposed to light at an exposure dose of 60 mJ/cm2 (converted to 365 nm illuminance) using a UV aligner (manufactured by Dai Nippon Kaken Co., Ltd., product name "MA-1100") equipped with a 2.0 kW ultra-high pressure mercury lamp through a photomask having 30 ⁇ m line-and-space openings at a distance of 50 ⁇ m from the coating film.
• a UV aligner manufactured by Dai Nippon Kaken Co., Ltd., product name "MA-1100
• a 0.05% aqueous potassium hydroxide solution was sprayed using a spin developer to dissolve and remove the unexposed areas, and the remaining exposed areas were developed by washing with pure water for 10 seconds, thereby evaluating developability.
• the coating film developed through the photomask as described above was observed with a surface roughness meter (manufactured by Ryoka Systems Co., Ltd., product name "VertScan 2.0"), and the spraying time of 0.05% potassium hydroxide aqueous solution required for the unexposed areas to flow was defined as the development time.
• ⁇ Development time less than 20 seconds
• ⁇ Development time 20 seconds or more but less than 30 seconds
• the photosensitive resin composition solution in Table 4 was uniformly applied onto a 5 cm square glass substrate (soda lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.) using a spin coater (manufactured by Mikasa Co., Ltd., 1H-D7).
• the coated plate was dried at 100°C for 3 minutes to obtain a laminate.
• the obtained laminate was exposed to light at 100 mJ using a high-pressure mercury lamp.
• the laminate was subjected to a heat treatment at 230°C for 30 minutes and cooled to room temperature to obtain a laminate with a coating film thickness of 2 ⁇ m.
• the obtained laminate was used as a measurement sample, and a weather resistance test was carried out using the following equipment, conditions, and evaluation method.
• Evaluation method The film thickness reduction rate (%) before and after the test was measured using a film thickness measurement system F-20 manufactured by Filmetrics Inc. The smaller the value, the better the weather resistance was evaluated to be.
• the zirconia particles were heated from room temperature to 800° C. at a rate of 10° C./min in an air atmosphere using a TG-DTA (thermogravimetric-differential thermal analysis) device, and the mass reduction rate of the particles was measured. From the mass reduction rate, the proportion of the compound surface-modifying the zirconia particles and the proportion of the zirconia particles were determined.
• TG-DTA thermogravimetric-differential thermal analysis
• Example Synthesis Example 1 Production of Alkali-Soluble Resin (A-1) 132.1 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of cresol novolac epoxy resin (trade name "YDCN-704A", manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 206 g/equivalent) were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, and the temperature was raised to 120° C. by heating.
• A-1 132.1 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of cresol novolac epoxy resin (trade name "YDCN-704A", manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 206 g/equivalent) were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a
• the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 102.1 g (0.6 moles) of o-phenylphenol and 1 g of triphenylphosphine were added to carry out an addition reaction, and the reaction was completed by reacting for 8 hours.
• the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 110.6 g (0.65 moles) of o-phenylphenol, 6.9 g (0.05 moles) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added to carry out an addition reaction, and the reaction was completed by reacting for 8 hours.
• the system was replaced with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 volume % or less, and 126.0 g (0.74 moles) of o-phenylphenol, 1.4 g (0.01 moles) of p-hydroxyphenyl-2-ethanol, and 1.1 g of triphenylphosphine were added to carry out an addition reaction, and the reaction was completed by reacting for 8 hours.
• reaction vessel After the temperature of the reaction vessel reached 120° C., the system was replaced with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 93.6 g (0.55 moles) of o-phenylphenol, 13.8 g (0.1 moles) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added to carry out an addition reaction, and the reaction was completed by reacting for 8 hours.
• the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 66.1 g (0.6 moles) of thiophenol and 0.9 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to react for 8 hours to complete the reaction.
• the system was substituted with nitrogen while maintaining the same temperature, and 108.9 g (0.64 moles) of p-phenylphenol, 1.4 g (0.01 moles) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours until the reaction was completed.
• reaction vessel After the temperature of the reaction vessel reached 120° C., the system was substituted with nitrogen while maintaining the same temperature, and 102.1 g (0.6 moles) of o-phenylphenol, 6.9 g (0.05 moles) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours until the reaction was completed.
• methyl methacrylate (MMA) 70.0 g of methyl methacrylate (MMA), 142.2 g of glycidyl methacrylate (GMA) (1 mol of epoxy group), and 4.2 g of t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corp., "Perbutyl (registered trademark) O") were prepared in a beaker by stirring, and in the dropping vessel (B), 2.1 g of n-dodecyl mercaptan (nDM) and 7.8 g of propylene glycol monomethyl ether acetate were prepared by stirring.
• nDM n-dodecyl mercaptan
• reaction vessel After the temperature of the reaction vessel reached 90 ° C., while maintaining the same temperature, dropping was started from the dropping vessel over 3 hours, and polymerization was carried out. After the dropwise addition, the inside of the reaction vessel was kept at 90°C for 1 hour, and then the temperature was raised to 115°C and aged for 90 minutes. Then, the reaction vessel was cooled to room temperature, and under nitrogen gas bubbling, 74.9g (0.68 mol) of thiophenol and 0.9g of triphenylphosphine were added to carry out an addition reaction, and the reaction was allowed to proceed for 8 hours to complete the reaction.
• the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 66.1 g (0.6 moles) of thiophenol and 0.9 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to react for 8 hours to complete the reaction.
• the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 66.1 g (0.6 moles) of thiophenol and 0.9 g of triphenylphosphine were added to carry out an addition reaction, and the reaction was completed by reacting for 8 hours.
• Comparative Synthesis Example 1 Production of Comparative Alkali-Soluble Resin (B-1) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, 117.5 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1 were charged, and the temperature was increased to 120° C. by heating.
• the system was substituted with nitrogen while maintaining the same temperature, and 68.1 g (0.4 moles) of o-phenylphenol and 1 g of triphenylphosphine were charged to carry out an addition reaction, which was then allowed to proceed for 8 hours until the reaction was completed. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 43.2 g (0.6 mol) of acrylic acid, 0.6 g of triphenylphosphine, 0.3 g of Antage W-400, and 18.5 g of propylene glycol monomethyl ether acetate were added to carry out an addition reaction, and the reaction was completed by reacting for 16 hours.
• Comparative Synthesis Example 2 Production of Comparative Alkali-Soluble Resin (B-2) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, 157.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1 were charged, and the temperature was increased to 120° C.
• the system was substituted with nitrogen while maintaining the same temperature, and 161.7 g (0.95 mole) of o-phenylphenol and 1.1 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours until the reaction was completed. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 3.6 g (0.05 mol) of acrylic acid, 0.7 g of triphenylphosphine, 0.4 g of Antage W-400, and 1.5 g of propylene glycol monomethyl ether acetate were added to carry out an addition reaction, and the reaction was completed by reacting for 16 hours.
• Photosensitive resin compositions 1 to 31 were obtained by mixing the resin solutions obtained in the Example Synthesis Examples and Comparative Synthesis Examples in the formulations (solid content amounts) shown in Tables 3 and 4, dipentaerythritol hexaacrylate, a photopolymerization initiator (Irgacure (registered trademark) OXE-02, manufactured by BASF), Pigment Dispersion 1 or zirconia particle dispersion, and propylene glycol monomethyl ether acetate.
• the Pigment Dispersion 1 and the Zirconia Particle Dispersion were prepared by the following methods.
• Pigment Dispersion 1 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a dispersant, 2.25 parts of C.I. Pigment Green 58 as a colorant, and 1.5 parts of C.I. Pigment Yellow 138 were mixed and dispersed for 3 hours using a paint shaker to obtain pigment dispersion 1.
• the mixture was then heated to 180° C. and held at that temperature for 16 hours (pressure inside the autoclave was 0.94 MPa) to react and produce zirconium oxide particles.
• the mixture after the reaction was then taken out, and the precipitate that had accumulated at the bottom was filtered out and washed with acetone, and then dried.
• the dried precipitate 100 g was dispersed in toluene (800 mL), resulting in a cloudy solution.
• the mixture was filtered again with a quantitative filter paper (manufactured by Advantec Toyo Co., Ltd., No. 5C) to remove coarse particles and the like from the precipitate.
• the filtrate was concentrated under reduced pressure to remove toluene, and white zirconium oxide nanoparticles 1 (coated ZrO2 particles 1) were collected.
• white zirconium oxide nanoparticles 1 (coated ZrO2 particles 1) were collected.
• the crystal structure of the obtained coated ZrO2 particle 1 was confirmed by the XRD diffraction pattern, diffraction lines belonging to tetragonal and monoclinic crystals were detected. From the intensity of the diffraction lines, the ratio of tetragonal and monoclinic crystals was 54/46, and the particle diameter (crystallite diameter) was 5 nm.
• the average particle size (number average primary particle size) of the coated ZrO2 particles 1 obtained by measurement with an electron microscope (FE-TEM JEM-2100F TEM manufactured by JEOL Ltd., magnification 600,000 times) was 12 nm. Furthermore, when the obtained coated ZrO2 particles 1 were analyzed by infrared absorption spectroscopy, absorption derived from C-H and absorption derived from COOH were confirmed. The absorption is considered to be due to 2 -ethylhexanoic acid and/or carboxylate derived from 2-ethylhexanoic acid coating the surface of the coated ZrO2 particles 1.
• the mass reduction rate of the coated ZrO2 particles 1 measured according to the above ⁇ Measurement of Mass Reduction Rate> was 12% by mass. Therefore, it was found that the 2 -ethylhexanoic acid and/or carboxylate derived from 2-ethylhexanoic acid coating the surface of the coated ZrO2 particles 1 accounted for 12% by mass of the entire coated ZrO2 particles 1.
• Production Example 2 Production of zirconium oxide nanoparticles coated with 2-ethylhexanoic acid and/or carboxylate derived from 2-ethylhexanoic acid and 2-acryloyloxyethyl succinate (coated ZrO2 particles 2))
• the coated ZrO2 particles 1 (10 g) obtained in the above Production Example 1 and 2-acryloyloxyethyl succinate (1.5 g) were stirred and mixed in propylene glycol monomethyl ether acetate (12 g, hereinafter referred to as "PGMEA") until uniformly dispersed.
• PMEA propylene glycol monomethyl ether acetate
• n-hexane (36 g) was added to aggregate the dispersed particles to make the solution cloudy, and the aggregated particles were separated from the cloudy liquid using filter paper. Thereafter, the separated aggregated particles were added to n-hexane (36 g), stirred for 10 minutes, and then the aggregated particles were separated using filter paper. The obtained particles were vacuum-dried at room temperature to prepare zirconium oxide nanoparticles (coated ZrO2 particles 2 ) surface-treated with 2-ethylhexanoic acid and/or a carboxylate derived from 2-ethylhexanoic acid and 2-acryloyloxyethyl succinate.
• the obtained coated ZrO2 particles 2 were dispersed in deuterated chloroform to prepare a measurement sample, which was then analyzed by 1H -NMR. As a result, it was found that the molar ratio of 2-ethylhexanoic acid and/or carboxylate derived from 2-ethylhexanoic acid to 2-acryloyloxyethyl succinate was 24:76.
• the amount of 2-ethylhexanoic acid and/or carboxylate derived from 2-ethylhexanoic acid, and 2-acryloyloxyethyl succinate coating the coated zirconium oxide particles was 18% by mass of the entire coated zirconium oxide particles.
• the coated ZrO2 particles 2 (7 g), methyl ethyl ketone (3 g), and DISPER BYK-111 (manufactured by BYK-Chemie Japan, 0.14 g) obtained above were mixed and stirred uniformly to obtain a zirconia particle dispersion.
• the number average primary particle diameter of the coated ZrO2 particles 2 measured by an electron microscope was 12 nm.
• the developing rate and solvent resistance were evaluated by the above-mentioned methods using the obtained photosensitive resin compositions 1 to 15. The results are shown in Table 3. The developing speed, refractive index and weather resistance of the obtained photosensitive resin compositions 16 to 31 were evaluated by the above-mentioned methods. The results are shown in Table 4.
• the alkali-soluble resins of the examples which have a predetermined aromatic ring-containing structure and a polymerizable unsaturated bond-containing structure and have a polymerizable unsaturated bond equivalent of 700 to 8000 g/equivalent, and the cured products of the photosensitive resin compositions containing the same all had a high level of refractive index of about 1.6.
• the resins having a structure containing sulfur atoms and benzene rings had a high refractive index.
• the development speed was slightly worsened by blending metal oxide particles, the refractive index was further improved.
• the alkali-soluble resins of the examples also had good solvent resistance and developability.
• the photosensitive resin composition using the resin having a structure containing sulfur atoms and benzene rings had good weather resistance, and when a resin having a functional group with radical scavenging ability was used, the results were very good.
• the resin intermediate (A-11) of Example Synthesis Example 11 is a synthetic intermediate of the resin (A-5) of Example Synthesis Example 5, and since it does not have alkali solubility, when this resin is used alone, it does not have the developability when a photosensitive resin composition is prepared, but it can impart a high refractive index and high solvent resistance to the photosensitive resin composition. When used in combination with another alkali-soluble resin, a photosensitive resin composition with excellent developability can be prepared.

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