Resin, curable resin composition, photosensitive resin composition, and cured product

Abstract

To provide a resin that yields a cured product having a high refractive index, and a cured product of the resin, and a curable resin composition.SOLUTION: The present invention provides a resin having an aromatic ring-containing structure represented by a general formula (1) (where R1 is an optionally substituted aromatic group and R2 is a hydrogen atom or a carboxyl group-containing group).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a resin, a curable resin composition, a photosensitive resin composition, and a cured product thereof. More specifically, the present disclosure relates to a resin, a curable resin composition, a photosensitive resin composition, and a cured product thereof that can provide a cured product having a high refractive index. [Background technology]

[0002] Conventionally, various resins and resin compositions having properties according to various applications have been developed for various optical components and electric / electronic devices, such as color filters, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, organic insulating films, and organic protective films used in liquid crystal displays and solid-state imaging devices. In recent years, optical components and electric / electronic devices have become smaller, thinner, and more energy-efficient, and as a result, higher quality performance is required for the various components used. In order to meet such demands, further research is being conducted on resins and resin compositions that are materials for various components.

[0003] To date, various resins have been developed to meet a variety of needs. For example, Patent Documents 1 and 2 describe alkali-developable photocurable and thermosetting compositions for obtaining cured films that maintain or improve the properties required for solder resists for printed wiring boards, interlayer insulating layers for multilayer wiring boards, and the like, which contain photosensitive prepolymers obtained by reacting polybasic acid anhydrides with alcoholic hydroxyl groups of the reaction product of an epoxy compound having two or more epoxy groups per molecule, and a specific phenol compound and / or naphthol compound, or a phenol compound further having a hydroxyl group-containing substituent, and an unsaturated group-containing monocarboxylic acid. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-315107 [Patent Document 2] JP 2004-171026 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, conventional resins have a low refractive index. For use in optical applications and other applications requiring a high refractive index, a high refractive index of 1.60 or more is required, but such a demand has not yet been fully met.

[0006] In view of the above-mentioned current situation, an object of the present disclosure is to provide a resin capable of giving a cured product with a high refractive index, as well as a cured product of the resin, a curable resin composition, and a photosensitive resin composition. [Means for solving the problem]

[0007] The present inventors have conducted extensive research into resins used in curable resin compositions and have found that the inclusion of a specific aromatic ring-containing structure makes it possible to give a cured product with a high refractive index, which has led to the present disclosure.

[0008] That is, the present disclosure provides the following aspects. [1] A resin having an aromatic ring-containing structure represented by the following general formula (1):

[0009] [ka] (In the formula, R 1 R represents an aromatic group which may have a substituent. 2 represents a hydrogen atom or a carboxyl group-containing group. [2] The resin according to the above [1], further comprising at least one structure selected from the group consisting of a structure represented by the following general formula (2) and a structure represented by the following general formula (3):

[0010] [ka] (In the formula, R2 R represents a hydrogen atom or a carboxyl group-containing group. 3 represents an organic group.

[0011] [ka] [3] The resin according to the above [1] or [2], which is represented by the following general formula (4):

[0012] [ka]

[0013] (In the formula, R 1 R represents an aromatic group which may have a substituent. 2 and R 4 are the same or different and each represents a hydrogen atom or a carboxyl group-containing group. 1 R represents a divalent organic group. 5 represents an organic group. n represents 0 or 1. [4] A above 1 The resin according to any one of the above [1] to [3], wherein the divalent organic group represented by the following formula (5) is a divalent group represented by the following general formula (5):

[0014] [ka]

[0015] (In the formula, R 7 and R 11 R may be the same or different and represents a divalent organic group containing an aromatic group. 8 and R 10 R may be the same or different and represents a hydrogen atom or a carboxyl group-containing group. 9 represents a divalent organic group containing an aromatic group; and m represents an integer of 1 or more. [5] A curable resin composition comprising the resin according to any one of the above [1] to [4] and at least one selected from the group consisting of metal oxide particles, a photoradical polymerization initiator, a thermal radical polymerization initiator, a thermal acid generator, a photoacid generator, and a photobase generator. [6] A photosensitive resin composition comprising the resin according to any one of the above [1] to [4], an alkali-soluble resin, a photoradical polymerization initiator, and a polymerizable compound. [7] A cured product obtained by curing the resin according to any one of [1] to [4] above, the curable resin composition according to [5] above, or the photosensitive resin composition according to [6] above, wherein the cured product has a refractive index of 1.60 or more. Effect of the Invention

[0016] The resins, curable resin compositions, and photosensitive resin compositions of the present disclosure can provide cured products with high refractive indexes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] A preferred embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited to the following description, and can be appropriately modified and applied within the scope of the present disclosure. Note that a combination of two or more of the individual preferred embodiments of the present disclosure described below also falls under the preferred embodiment of the present disclosure. In this specification, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid", and "(meth)acrylate" means "acrylate and / or methacrylate". In addition, in this specification, a numerical range "(minimum value) to (maximum value)" means not less than (minimum value) and not more than (maximum value), for example, "5 to 10" means "not less than 5 and not more than 10." Furthermore, when the upper and lower limit values ​​are described as suitable numerical values ​​in stages, a numerical range obtained by appropriately combining the upper and lower limit values ​​described separately is also a suitable numerical range.

[0018] 1. Resin The present disclosure relates to a resin (hereinafter also referred to as "resin (X)") characterized by having an aromatic ring-containing structure represented by the above general formula (1). The reason why the resin of the present disclosure can provide a cured product with a high refractive index is believed to be that the refractive index of the cured product of the resin is high due to the inclusion of an aromatic group via a sulfur atom, which has a high atomic refractive index.

[0019] In the above general formula (1), R 1 represents an aromatic group which may have a substituent. The aromatic group may have an aromatic ring structure, may be monocyclic or polycyclic, and may contain a heteroatom.

[0020] 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. In addition, 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.

[0021] Examples of the aromatic group include monovalent groups obtained by removing one hydrogen atom from a benzene-based aromatic compound, a non-benzene-based aromatic compound, or a heteroaromatic compound.

[0022] Examples of the benzene-based aromatic compound 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.

[0023] Examples of the non-benzene aromatic compound include hydrocarbon compounds containing unsaturated cyclic compounds other than a benzene ring, such as annulene and azulene.

[0024] Examples of the heteroaromatic compound include unsaturated cyclic compounds containing an element other than carbon and hydrogen atoms, such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heteroaromatic compound include monocyclic heteroaromatic compounds such as furan, thiophene, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, triazole, thiazole, thiadizole, and tetrazole; and polycyclic heteroaromatic compounds such as carbazole, benzoxazole, purine, azulene, benzofuran, isobenzofuran, benzothiophene, benzotriazole, isobenzothiophene, indole, isoindole, benzimidazole, and benzothiazole.

[0025] Among these, 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.

[0026] The aromatic group preferably has 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms.

[0027] 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. Among these, an alkyl group is preferable. The above-mentioned substituent preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 6 carbon atoms. The aromatic group may have one or more of the above-mentioned substituents.

[0028] Specific examples of the aromatic group which may have the above-mentioned substituent 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.

[0029] Specific examples of the 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''-(1,3,5,2,4,6-trioxatriborinane-2,4,6-triyl)tribenzenethiol, 1,3,5-tris[3-(2mercaptoethylsulfanyl)propyl]isocyanate, 6-amino-8-mercaptopurine, 4-mercaptobenzamide, 4-mercaptophenylboronic acid, 2-naphthalenethiol, and diphenyl disulfide; Thiocarboxylic acid compounds such as thioacetic acid-S-phenyl ester; Sulfonyl halogen compounds such as 2-mesitylenesulfonyl chloride; Sulfonic acid compounds such as benzenesulfonic acid; Thiourea compounds such as diphenylthiourea; Thiadiazole compounds such as 2,5-dimercapto-1,3,4-thiadiazole, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole, and 2,5-dithioacetic acid-1,3,4-thiadiazole; Azide compounds such as 4-dodecylbenzenesulfonyl azide, 4-acetylaminobenzenesulfonyl azide, and diphenylphosphoryl azide; 1H-Tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-5-mercapto-1H-tetrazole, 2-methoxy-5-(5-trifluoromethyl-1H-tetrazol-1-yl) -Benzaldehyde, 5,5'-bi-1H-tetrazole diammonium salt, 4,5-di(5-tetrazolyl)-[1,2,3]triazole, 5,5'-azobis-1H-tetrazole, 1-methyl-5-benzoyl-1H-tetrazole, (1-methyl-1H-tetrazol-5-yl)phenylmethanone oxime (E+Z), 5-ethylthio-1H-tetrazole, 1-benzyl-5-phenyl-1H-tetrazole and other tetrazole compounds; thiazolidine compounds such as 2,4-thiazolidinedione, 2-thio-4-thiazolidone, and 2-imino-4-thiazolidinone; 4-Thiazolecarboxylic acid; Ketone compounds such as 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, and 4-hydroxypropiophenone; Dicarboxyaldehyde compounds such as 2,6-naphthalenedicarboxyaldehyde and 2,7-naphthalenedicarboxyaldehyde; Trityl chloride compounds such as trityl chloride and 4,4'-dimethoxytrityl chloride.

[0030] Among them, R 1 As the alkyl group, 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.

[0031] R2 represents a hydrogen atom or a carboxyl group-containing group. The carboxyl group-containing group is not particularly limited as long as it is a group containing a carboxyl group, and examples thereof include -R 2a -COOH(R 2a represents a divalent organic group.

[0032] Above R 2a Examples of the divalent organic group represented by the formula (I) include a divalent hydrocarbon group which may have a substituent, or a group consisting of a combination of a divalent hydrocarbon group which may have a substituent and -O-, -CO-, -COO-, -NH-, -S-, -SO- or -SO2-. Preferably, the divalent hydrocarbon group which may have a substituent or -CO-R 2a1 -(R 2a1 represents a divalent hydrocarbon group which may have a substituent.

[0033] The divalent hydrocarbon group may be linear or cyclic, and may be a saturated or unsaturated hydrocarbon group. The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

[0034] Examples of 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, and a hexamethylene group, and alkenylene groups such as a vinylene group, a propenylene group, an isopropenylene group, a butenylene group, a butadienylene group, a pentenylene group, and a hexenylene group.

[0035] Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornylene group, and an adamantylene group; and cycloalkylidene groups such as a cyclopentylidene group and a cyclohexylidene group.

[0036] Examples of the divalent aromatic hydrocarbon group include arylene groups such as a phenylene group, a tolylene group, and a naphthylene group, a cinnamylidene group, and a biphenylene group.

[0037] Among these, 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 further preferably an alkylene group.

[0038] The divalent hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 3 to 7 carbon atoms.

[0039] Examples of the substituent that the divalent hydrocarbon group may have include a carboxyl group, a hydroxyl group, an alkoxy group, and a halogen atom.

[0040] Preferred examples of the carboxyl group-containing group include groups represented by the following formula:

[0041] [ka] (In the formula, R 2a1 represents a divalent hydrocarbon group which may have a substituent.

[0042] R 2a1 The divalent hydrocarbon group represented by the following formula (I) and the substituent that the divalent hydrocarbon group may have are as described above.

[0043] Among them, R 2 -R is a compound that can impart alkali solubility to resins. 2a It is preferably -COOH.

[0044] The resin (X) preferably further has at least one structure selected from the group consisting of the structure represented by the general formula (2) and the structure represented by the general formula (3). By having these structures, the curability of the resin and the solvent resistance and adhesion of the cured product can be improved.

[0045] R in the above general formula (2) 2 is R in the above general formula (1). 2 is the same as: R in the above general formula (2) 3 represents an organic group. R 3 Examples of the organic group represented by the formula (I) include the above-mentioned divalent organic groups which have been made monovalent by adding a hydrogen atom. R 3 The organic group represented by the following formula (1) preferably has 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and further preferably 3 to 10 carbon atoms.

[0046] Among them, R 3 The organic group represented by the formula: -CO-R b1 (R b1 represents a monovalent organic group. In terms of further improving the curability of the resin, a group represented by -CO-R b2 -CR b3 =CH2(R b2 R represents a direct bond, a divalent hydrocarbon group, or a group consisting of a combination of a divalent hydrocarbon group and -O- or -COO-. b3 represents a hydrogen atom or a methyl group. b2 is more preferably a direct bond or a divalent aliphatic hydrocarbon group. R 3 The organic group represented by the formula is more preferably -CO-CR b3 =CH2.

[0047] A preferred example of the resin (X) having an aromatic ring-containing structure represented by the above general formula (1) is a resin (X1) having a structural unit (A) represented by the following general formula (6): In this specification, the term "structural unit" refers to a repeating unit derived from a monomer or the like constituting a resin.

[0048] [ka]

[0049] (In the formula, A 2 R represents a benzene ring or a naphthalene ring. 12 R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. 13 A 2 a represents a substituent bonded to R 13 R represents the number of 13 When there are two or more R, they may be the same or different. 14 R represents a divalent group. 1 and R 2 is the same as general formula (1).

[0050] In the general formula (6), A 2 represents a benzene ring or a naphthalene ring. At the point where the refractive index is higher, A 2 is preferably a benzene ring.

[0051] R 12 The divalent hydrocarbon group represented by the formula (I) may be linear or cyclic, and may be a saturated or unsaturated hydrocarbon group. Examples of the divalent hydrocarbon group include the above-mentioned divalent aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Among them, the above R 12 The divalent hydrocarbon group represented by the following formula (I) is preferably a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, more preferably a divalent aliphatic hydrocarbon group, and further preferably an alkylene group, in that it can impart flexibility to the main chain.

[0052] Above R 12 The divalent hydrocarbon group represented by the following formula (I) preferably has 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 carbon atom.

[0053] Above R 12 In the divalent hydrocarbon group represented by the following formula (1), at least one of the atoms constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. The divalent hydrocarbon group may have a substituent such as an alkoxy group.

[0054] R 13 Examples of the substituent represented by the formula: include a hydroxyl group or an organic group having 1 to 20 carbon atoms.

[0055] The organic group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 3 carbon atoms.

[0056] The organic group includes a monovalent hydrocarbon group or a group formed by combining a monovalent hydrocarbon group with -O-, -CO-, -COO-, -NH-, -SO-, -SO2- or a divalent hydrocarbon group. Examples of the monovalent hydrocarbon group include monovalent groups in which a hydrogen atom is added to the above-mentioned divalent hydrocarbon groups, and examples of the monovalent hydrocarbon group include monovalent aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups, monovalent alicyclic hydrocarbon groups such as cycloalkyl groups, and monovalent aromatic hydrocarbon groups such as aryl groups and biphenyl groups.

[0057] Among them, R is the most popular because of its excellent curability. 13 The substituents represented by are -OH, -O-CH2-(C2H3O), -CR c1 R c2 -(C6H4)-O-CH2-(C2H3O), -CR c3 R c4 -(C6H4)-OH (wherein, R c1 ~R c4 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 is preferable, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is more preferable, an aliphatic hydrocarbon group having 1 to 10 carbon atoms is even more preferable, and a methyl group is particularly preferable.

[0058] In the above general formula (6), a is a substituent R 13 and is an integer of 0 to 5. a is preferably 0 to 3, more preferably 1 to 3, and further preferably 1. When a is 2 or more, that is, R13 If there are two or more, R 13 may be the same or different from each other.

[0059] R 14 Examples of the divalent group represented by the formula (I) include a divalent hydrocarbon group which may have a substituent, -O-, -CO-, -COO-, -NH-, -S-, -SO-, -SO2-, or a group consisting of a combination thereof.

[0060] The divalent hydrocarbon group is, for example, R 12 Examples of the divalent hydrocarbon group include the same groups as those represented by the following formula: The divalent hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0061] R 14 Examples of the substituent that the divalent group represented by the following formula may have include an alkoxy group and an alkyl group.

[0062] R 14 The divalent group represented by the formula (I) is preferably -O- or -R d1 -O-(R d1 represents a divalent organic group having 1 to 10 carbon atoms.) is preferable, and -O- is more preferable.

[0063] In the above general formula (6), R 2 is preferably a hydrogen atom.

[0064] The resin (X1) may have one or more types of the structural unit (A). When the resin (X1) has the structural unit (A), the content thereof is preferably 1 to 99 mol %, more preferably 20 to 95 mol %, and even more preferably 40 to 90 mol %, relative to 100 mol % of all structural units in the resin, in order to increase the refractive index and improve the developability.

[0065] When the resin (X1) has a structure represented by the above general formula (2), it preferably has a structural unit (B) represented by the following general formula (7).

[0066] [ka]

[0067] (In the formula, A 2 R represents a benzene ring or a naphthalene ring. 15 R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. 16 A 2 b represents a substituent bonded to R 16 R represents the number of 17 R represents a divalent group. 2 and R 3 is the same as the above general formula (2).

[0068] In the above general formula (7), A 2 is preferably a benzene ring.

[0069] In the above general formula (7), R 15 As the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (6), R 12 The same can be mentioned.

[0070] In the above general formula (7), R 16 The substituent represented by the formula (6) is R 13 The same can be mentioned.

[0071] In the above general formula (7), R 17 As the divalent group represented by the above general formula (6), 14 The same can be mentioned.

[0072] In the above general formula (7), R 2 is preferably a hydrogen atom.

[0073] In the above general formula (7), b is a substituent R 16 and is an integer of 0 to 5. b is preferably 0 to 3, more preferably 1 to 3, and further preferably 1. When b is 2 or more, that is, when R 16 If there are two or more, R 16 may be the same or different from each other.

[0074] The resin (X1) may have one or more types of the structural units (B). When the resin of the present disclosure has the structural unit (B), the content thereof is preferably 0.1 to 99 mol %, more preferably 1 to 80 mol %, and even more preferably 5 to 50 mol %, relative to 100 mol % of all structural units in the resin, in order to improve the adhesion and solvent resistance of the cured product.

[0075] When the resin (X1) has a structure represented by the above general formula (3), it preferably has a structural unit (C) represented by the following general formula (8).

[0076] [ka]

[0077] (In the formula, A 2 R represents a benzene ring or a naphthalene ring. 18 R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. 19 A 2 c represents a substituent bonded to R 19 R represents the number of 20 represents a divalent group.

[0078] In the above general formula (8), A 2 is preferably a benzene ring.

[0079] In the above general formula (8), R 18 As the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (6), R 12The same can be mentioned.

[0080] In the above general formula (8), R 19 The substituent represented by the formula (6) is R 13 The same can be mentioned.

[0081] In the above general formula (8), R 20 As the divalent group represented by the above general formula (6), 14 Among them, the divalent group is -OR e1 -(R e1 represents a divalent hydrocarbon group, preferably represents a divalent alkylene group, more preferably represents an alkylene group having 1 to 5 carbon atoms.

[0082] In the above general formula (8), c is a substituent R 19 and is an integer of 0 to 5. c is preferably 0 to 3, more preferably 1 to 3, and further preferably 1. When c is 2 or more, that is, when R 19 If there are two or more, R 19 may be the same or different from each other.

[0083] The resin (X1) may have one or more types of the structural units (C). When the resin (X1) has the structural unit (C), the content thereof is preferably 0.1 to 99 mol %, more preferably 1 to 80 mol %, and even more preferably 10 to 40 mol %, relative to 100 mol % of all structural units in the resin, from the viewpoints of the solvent resistance and storage stability of the cured product.

[0084] The resin (X1) may also have a structural unit (D) represented by the following general formula (9): By introducing the structural unit (D) to carry out chain extension, the resin can be designed to have an arbitrary molecular weight.

[0085] [ka]

[0086] In the above general formula (9), L represents a direct bond or a linking group. 21 and R 22 are the same or different and represent a substituent. d is R 21 represents the number of R 22 R represents the number of 21 and R 22 When there are a plurality of, they may be the same or different.

[0087] Examples of the linking group include an alkylene group, an arylene group, a heteroarylene group, a divalent bond such as -O-, -CO-, -S-, -SO-, -SO2- or -NH-, or a combination thereof.

[0088] 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, the alkylene group may be linear, branched, or cyclic.

[0089] The alkylene group and the arylene group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine atom, and an alkyl group.

[0090] R 21 and R 22 The substituent represented by the following formula is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and further preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0091] d is R 21 It represents the number of, and is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 2.

[0092] e is R 22 It represents the number of, and is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 2.

[0093] The structural unit (D) represented by the above formula (9) is preferably a structural unit derived from any one of bisphenol compounds 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, bisphenol Z, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 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.

[0094] The structural unit (D) is preferably a structural unit represented by the following formula (9-1), (9-2), or (9-3).

[0095] [ka]

[0096] When the resin (X1) has the structural unit (D), the content thereof 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.

[0097] The acid value of the resin (X1) is preferably less than 30 mgKOH / g. When the acid value is within the above range, the storage stability of the resin is good. In terms of further excellent storage stability, the acid value of the resin is preferably 25 mgKOH / g or less, more preferably 10 mgKOH / g or less, and even more preferably 1 mgKOH / g or less. 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 specifically, can be determined by the method described in the examples below.

[0098] Moreover, examples of the resin (X) having an aromatic ring-containing structure represented by the above general formula (1) include the resin (X2) represented by the following general formula (4). The resin (X2) is preferred in terms of its good compatibility with metal oxide particles.

[0099] [ka] (In the formula, R 1 R represents an aromatic group which may have a substituent. 2 and R 4 are the same or different and each represents a hydrogen atom or a carboxyl group-containing group. 1 R represents a divalent organic group. 5 represents an organic group. n represents 0 or 1.

[0100] R in the above general formula (4) 1 is R in the above general formula (1). 1 The same as R in the above general formula (4). 2 and R 4 is R in the above general formula (1). 2 is the same as:

[0101] R in the above general formula (4) 5 represents an organic group. 5 Examples of the organic group represented by the formula (1) include a hydrocarbon group, and a group consisting of a combination of a hydrocarbon group and -O-, -CO-, -COO-, -NH-, -S-, -SO- or -SO2-. The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 2 to 20. Among them, R 5 is preferably an epoxy group, -SR 6 or a polymerizable double bond-containing group. 6 represents an aromatic group which may have a substituent. By containing these groups, it is possible to impart photocrosslinkability or thermal crosslinkability to the resin, or to increase the refractive index of the resin. R 6 The aromatic group which may have a substituent represented by the formula (I) is the same as the above-mentioned R 1Examples of the groups include those represented by the following formula: If n is 0, R 5 preferably represents an epoxy group.

[0102] Examples of the polymerizable double bond-containing group include groups containing a polymerizable double bond group such as a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group, etc. Among these, a group containing a (meth)acryloyl group is preferred. The polymerizable double bond-containing group is preferably -R f1 -R f2 (In the formula, R f1 R represents a direct bond or a divalent group. f2 represents the above-mentioned polymerizable double bond group.) As the divalent group, the above-mentioned R 14 Examples of the divalent group include the same groups as those represented by the following formula: The polymerizable double bond-containing group is more preferably -O-CO-CR f3 =CH2(R f3 represents a hydrogen atom or a methyl group.

[0103] Above A 1 Examples of the divalent organic group represented by the formula (I) include the divalent organic groups described above. 1 is preferably a divalent hydrocarbon group which may have a substituent, or a divalent group consisting of a combination of a divalent hydrocarbon group which may have a substituent and at least one bonding group selected from the group consisting of -O-, -CO-, and -SO2-.

[0104] The divalent hydrocarbon group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group consisting of a combination thereof. The hydrocarbon group consisting of a combination may be a divalent group formed by removing two hydrogen atoms from a polycyclic compound such as biphenylene or fluorene. Examples of the substituent include the substituents described above.

[0105] Among them, the above A 1The divalent organic group represented by the following formula (5) is preferable.

[0106] [ka]

[0107] (In the formula, R 7 and R 11 R may be the same or different and represents a divalent organic group containing an aromatic group. 8 and R 10 R may be the same or different and represents a hydrogen atom or a carboxyl group-containing group. 9 represents a divalent organic group containing an aromatic group; and m represents an integer of 1 or more.

[0108] Above R 7 and R 11 Examples of the aromatic group in the divalent organic group containing an aromatic group represented by the following formula include the same groups as the aromatic groups described above.

[0109] Among them, the above R 7 and R 11 Examples of the divalent organic group containing an aromatic group represented by the following formula (10) include divalent groups represented by the following formula (10).

[0110] [ka] (In the formula, Ar represents an arylene group. R 23 R represents a direct bond or a divalent cyclic hydrocarbon group. 24 and R 25 are the same or different and each represents a substituent bonded to Ar. f and g are the same or different and each represents an integer of 0 to 4. R g1 and R g2 are the same or different and represent a direct bond or a divalent organic group.

[0111] In the above general formula (10), Ar represents an arylene group such as a phenylene group, a naphthylene group, a phenanthrylene group, etc. Among these, a phenylene group and a naphthylene group are preferred in terms of good solubility in a solvent.

[0112] Above R 23 Examples of the divalent cyclic hydrocarbon group represented by the formula (I) include a divalent alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a cyclic hydrocarbon group consisting of a combination thereof. The divalent alicyclic hydrocarbon group includes a cycloalkylene group. The divalent aromatic hydrocarbon group includes divalent groups obtained by removing two hydrogen atoms from an aromatic hydrocarbon compound such as benzene, naphthalene, or anthracene. The group formed by combining the above-mentioned divalent alicyclic hydrocarbon group and aromatic hydrocarbon group is a cyclic hydrocarbon group formed by bonding or condensing the above-mentioned alicyclic hydrocarbon group with an aromatic hydrocarbon group, and examples thereof include divalent groups formed by removing two hydrogen atoms from a condensed hydrocarbon compound such as fluorene. Among them, R 23 is preferably a divalent group formed by removing two hydrogen atoms from a condensed hydrocarbon compound such as fluorene, in that it will result in a higher refractive index, and a structure represented by the following general formula (11) is more preferred.

[0113] [ka]

[0114] In formula (11), X represents a direct bond, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, or a selenium atom. x1 and R x2 are the same or different and represent a hydrogen atom or a substituent. In the above general formula (11), X is preferably a direct bond, an oxygen atom, or a sulfur atom, and more preferably a direct bond in terms of ease of availability. R x1 and R x2Examples of the substituent represented by the formula (I) include the substituents described above. R x1 and R x2 is preferably a hydrogen atom. In the above general formula (11), * represents a bonding site with the adjacent Ar.

[0115] Above R 24 and R 25 Examples of the substituent represented by the formula (I) include the substituents mentioned above, among which a hydrocarbon group is preferable, a hydrocarbon group having 1 to 10 carbon atoms is more preferable, and an aliphatic hydrocarbon group having 1 to 5 carbon atoms is even more preferable.

[0116] f is R 24 It represents the number of, and is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 2.

[0117] g is R 25 It represents the number of, and is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 2.

[0118] R in the above general formula (10) g1 and R g2 represents a direct bond or an organic group, which may be the same or different. R g1 and R g2 Examples of the divalent organic group represented by the formula (I) include the divalent organic groups described above. Among them, a hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferred, and -(R g3 O) m -(R g3 represents an alkylene group having 1 to 10 carbon atoms. m represents an integer of 1 or more. A group represented by the following formula is more preferred. R g1 and R g2 are the same or different and are a direct bond or the above-mentioned -(R g3 O) m A group represented by - is more preferred, and a direct bond is particularly preferred.

[0119] Above R 7 and R 11The proportion of the divalent organic group containing an aromatic group represented by the following formula (1) is preferably 1 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 40 to 70 mass %, relative to 100 mass % of the resin (X2).

[0120] Above R 8 and R 10 The carboxyl group-containing group represented by the above-mentioned R 2 The carboxyl group-containing group represented by the following formula (1) is also usable.

[0121] R 9 represents a divalent organic group containing an aromatic group. Examples of the aromatic group include the same groups as those mentioned above. Among them, a divalent aromatic hydrocarbon group which may have a substituent is preferred. The divalent organic group containing an aromatic group is preferably a group containing -SO2- or -C(CH3)2- and an aromatic group, or a group containing a cardo structure, and more preferably a group represented by the following general formula (12).

[0122] [ka]

[0123] (In the formula, Y represents -SO2-, -C(CH3)2-, or a structure represented by the above general formula (11). R 26 represents an oxygen atom, -COO- or -NH-. 27 and R 28 h and i are the same or different and each represents an integer of 0 to 4. Y represents -SO2-, -C(CH3)2-, or a structure represented by the above general formula (11), and is preferably -SO2- in that the refractive index of the resin is even higher.

[0124] R 27 and R 28 The substituent represented by the formula 24 and R 25 The substituents include the same groups as those represented by the following formula: h is a substituent R 27 It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and further preferably 0 or 2. i is a substituent R 28 It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and further preferably 0 or 2.

[0125] R 9 The proportion of the divalent organic group containing an aromatic group represented by the following formula (1) is preferably 1 to 70 mass %, more preferably 3 to 50 mass %, and further preferably 5 to 20 mass %, relative to 100 mass % of the resin (X2).

[0126] In the above general formula (5), m represents an integer of 1 or more. In order that the above resin (X2) has good solubility in solvents, m is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3. m represents the average number of repeating units.

[0127] The acid value of the resin (X2) is preferably 30 mgKOH / g or more. When the acid value is in the above-mentioned range, the resin can be imparted with alkali solubility. The acid value of the resin (X2) is more preferably 40 mgKOH / g or more, even more preferably 50 mgKOH / g or more, and particularly preferably 60 mgKOH / g or more, in terms of excellent developability. In addition, the acid value is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, and even more preferably 150 mgKOH / g or less, in terms of making the exposed portion less susceptible to corrosion by an alkaline developer. The acid value can be determined in the same manner as the acid value of the resin (X1) described above.

[0128] The double bond equivalent of the resin (X) is preferably 200 to 20,000 g / equivalent. When the double bond equivalent is within the above range, solvent resistance and adhesion can be improved. From the viewpoints of curability, storage stability, solvent resistance and adhesion, the double bond equivalent of the resin is preferably 300 to 10,000 g / equivalent, more preferably 400 to 5,000 g / equivalent, and even more preferably 500 to 3,000 g / equivalent.

[0129] The double bond equivalent is the mass of the solid content of the resin solution per 1 mol of the polymerizable unsaturated bond of the resin. In this specification, the double bond means a polymerizable double bond. The mass of the solid content of the resin solution is the mass of the monomer components constituting the resin. The double bond equivalent can be obtained by dividing the mass (g) of the resin solid content of the resin solution by the amount (mol) of the polymerizable unsaturated bonds of the resin. It can also be calculated by measuring the number of ethylenic double bonds contained in 1 g of the alkali-soluble resin in accordance with the test method for iodine value described in JIS K 0070:1992.

[0130] The epoxy equivalent of the resin (X) is preferably 200 to 20,000 g / equivalent. When the epoxy equivalent is within the above range, the balance between solvent resistance and storage stability is good. From the viewpoints of storage stability, developability, and solvent resistance, the epoxy equivalent is preferably 500 to 4,000 g / equivalent, more preferably 700 to 3,000 g / equivalent, and even more preferably 900 to 2,500 g / equivalent. The epoxy equivalent can be determined by dividing the resin solid content by the number of moles of epoxy groups contained in the resin. The epoxy equivalent can also be determined by a method in accordance with JIS K7236:2001.

[0131] The weight average molecular weight of the resin (X) is preferably 1000 to 100000. The weight average molecular weight of the alkali-soluble resin is more preferably 2000 to 30000, further preferably 3000 to 20000, and particularly preferably 4000 to 10000, in terms of good solvent resistance. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

[0132] The glass transition temperature (Tg) of the resin (X) is preferably from 0 to 300°C, more preferably from 10 to 250°C, and even more preferably from 60 to 200°C, from the viewpoints of strength of the cured product and developability. The glass transition temperature can be determined by a method in accordance with JIS-K7121.

[0133] The refractive index of the resin (X) is preferably 1.60 or more, more preferably 1.62 or more, and even more preferably 1.64 or more. The refractive index can be determined by the method described in the Examples.

[0134] <Method for producing resin (X)> The method for producing resin (X) of the present disclosure is not particularly limited as long as the above-mentioned resin can be obtained. However, in terms of efficient production, it is preferable to have a step (1) of reacting an epoxy resin (a) having two or more epoxy groups in one molecule with an aromatic group-containing compound (b).

[0135] In the method for producing the resin (X), the starting 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. For example, in the case of producing the resin (X1), bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S 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, cleaved epoxy resins, etc., can be used. Novolac epoxy resins such as sol novolac epoxy resins and naphthalene-containing novolac epoxy 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 phenolic hydroxyl groups; reaction products of epichlorohydrin and polyphenol compounds obtained by addition reaction of phenolic compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene; epoxidized ring-opening polymers of 4-vinylcyclohexene-1-oxide with peracid; epoxy resins having heterocycles such as triglycidyl isocyanurate; and the like. In addition, chain-extended products obtained by bonding two or more molecules of these epoxy resins by reaction with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol can also be used. Alternatively, the epoxy resins may be homopolymers or copolymers of monomers having epoxy groups such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, novolac type epoxy resins are preferred because of their high refractive index. These epoxy resins may have a substituent such as a halogen atom, an alkyl group, an alkylene group, a cycloalkylene group, an arylene group, or a cyano group.

[0136] When producing the above resin (X2), it is preferable to use a difunctional epoxy resin as the above epoxy resin (a). Examples of the bifunctional epoxy resin include bisphenol-type bifunctional epoxy resins, fluorene-type bifunctional epoxy resins, binol-type bifunctional epoxy resins (e.g., 2,2'-diglycidyloxy-1,1'-binaphthalene (Binol, manufactured by Sugai Chemical Industry Co., Ltd.)), polyethylene glycol diglycidyl ether (e.g., Denacol EX-810, EX-810P, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-861, all manufactured by Nagase Chemtec Corporation), neopen, Examples of the epoxy resins include ethyl glycol diglycidyl ether (e.g., Denacol EX-211, EX-212, both manufactured by Nagase Chemtec Corporation), 1,4-butanediol diglycidyl ether (e.g., Denacol EX-214, manufactured by Nagase Chemtec Corporation), resorcinol diglycidyl ether (e.g., Denacol EX-201, manufactured by Nagase Chemtec Corporation), and crystalline epoxy resins (e.g., YDC-1312, YSLV-70XY, YSLV-80XY, YSLV-120TE, all manufactured by Nippon Steel Chemical & Material Co., Ltd.). The epoxy resin (a) may be used alone or in combination of two or more. Among them, in terms of high refractive index, the bifunctional epoxy resin is preferably a bisphenol-type bifunctional epoxy resin or a fluorene-type bifunctional epoxy resin, and more preferably a fluorene-type bifunctional epoxy resin.

[0137] Examples of the bisphenol-type difunctional epoxy resin include 4,4'-biphenyldiylbis(glycidyl ether), 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, and hydrogenated bisphenol A diglycidyl ether (for example, Denacol EX-252, manufactured by Nagase Chemtec Corporation).

[0138] The fluorene-type bifunctional epoxy resin may be a bifunctional epoxy resin having a fluorene skeleton, such as OGSOL PG-100, OGSOL CG-500, OGSOL EG-200, OGSOL EG-280 (all manufactured by Osaka Gas Chemical Co., Ltd.), TBIS-GG, TBIS-RXG (all manufactured by Taoka Chemical Co., Ltd.).

[0139] In addition to the above, the fluorene-type bifunctional epoxy resin may be, for example, one obtainable by reacting a bisphenol fluorene compound with epihalohydrin.

[0140] Specific examples of bisphenol fluorene compounds include, but are not limited to, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, and similar compounds thereof.

[0141] Specific examples of epihalohydrins include, but are not limited to, epichlorohydrin, epibromohydrin, and the like.

[0142] Specific examples of the fluorene-type bifunctional epoxy resin include 9,9-bis(4-glycidyloxyphenyl)fluorene and 9,9-bis(6-glycidyloxynaphthyl)fluorene.

[0143] Examples of the fluorene-type bifunctional epoxy resin include bifunctional epoxy resins having a fluorene skeleton described in JP-A-10-36485, JP-A-10-45871, JP-A-2009-155256, JP-T-2020-537184, and JP-T-2018-531311.

[0144] Among them, the above-mentioned fluorene-type bifunctional epoxy resins are more preferably those having a phenylfluorene skeleton such as 9,9-bis(4-glycidyloxyphenyl)fluorene, and those having a naphthylfluorene skeleton such as 9,9-bis(6-glycidyloxynaphthyl)fluorene, in terms of having a higher refractive index, and are even more preferably those having the naphthylfluorene skeleton.

[0145] The epoxy equivalent of the bifunctional epoxy resin is preferably in the range of 150 to 500 g / equivalent, more preferably in the range of 200 to 400 g / equivalent, and further preferably in the range of 250 to 350 g / equivalent, in view of the high refractive index.

[0146] 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 thereof include the aromatic compounds described above. The aromatic group includes the aromatic groups described above which may have a substituent. Examples of the group capable of reacting with the epoxy group include an acidic group, an amino group, a hydroxyl group, etc. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, etc., and preferably a phenolic hydroxyl group or a mercapto group. The aromatic group-containing compound (b) may be used alone or in combination with two or more other compounds, but in the present disclosure, a compound having at least an acidic group containing a sulfur atom such as a mercapto group is used. Specific examples of the aromatic group-containing compound (b) include thiophenol derivatives such as benzenethiol and toluenethiol, and thionaphthol derivatives such as naphthalenethiol.

[0147] When the aromatic group-containing compound (b) is reacted with the epoxy resin (a), the amount of the aromatic group-containing compound (b) added is preferably 0.1 to 0.99 mol, more preferably 0.4 to 0.95 mol, and even more preferably 0.6 to 0.9 mol, of acid groups per chemical equivalent (molar equivalent) of the epoxy group in the epoxy resin (a).

[0148] In the reaction step (1), the epoxy resin (a) may be reacted with an acid compound such as a monocarboxylic acid, phosphoric acid, or phenol, or a basic compound such as an amine compound. The amount of epoxy groups can be adjusted by reacting the epoxy resin (a) with such a compound capable of reacting with epoxy groups. The compound capable of reacting with epoxy groups is not particularly limited, but among them, monocarboxylic acid (c) is preferred because it is easy to adjust the amount of epoxy groups.

[0149] Examples of the monocarboxylic acid (c) include alkyl monocarboxylic acid (c-1) and unsaturated monocarboxylic acid (c-2). Among them, unsaturated monocarboxylic acid (c-2) is preferable because it can introduce a polymerizable double bond into the side chain of the resin and improve the curability of the resin. For example, it can be a resin having a structure represented by the above-mentioned general formula (2) and having a polymerizable double bond at the end of the side chain.

[0150] Examples of the alkyl monocarboxylic acid (c-1) include propionic acid, acetic acid, butyric acid, decanoic acid, and 2-ethylhexyl carboxylic acid. By using the alkyl monocarboxylic acid (c-1), the double bond equivalent, epoxy equivalent, glass transition temperature, and the like of the resin can be adjusted. Among them, those having 1 to 30 carbon atoms are preferred, those having 1 to 20 carbon atoms are more preferred, and those having 2 to 10 carbon atoms are even more preferred, in terms of good reactivity.

[0151] The unsaturated monocarboxylic acid (c-2) is not particularly limited as long as it has a polymerizable unsaturated bond such as a vinyl group or an acryloyl group and a carboxyl group, but preferably has 3 to 20 carbon atoms, more preferably has 3 to 10 carbon atoms, and even more preferably has 3 to 4 carbon atoms.

[0152] Examples of the unsaturated monocarboxylic acid (c-2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, β-acryloxypropionic acid, a reaction product of a hydroxyalkyl (meth)acrylate having one hydroxyl group and one (meth)acryloyl group with a dibasic acid anhydride, and a reaction product of a polyfunctional (meth)acrylate having one hydroxyl group and two or more (meth)acryloyl groups with a dibasic acid anhydride. Among them, those having a (meth)acryloyl group such as acrylic acid and methacrylic acid are preferred. Methacrylic acid is particularly preferred from the viewpoint that the resin gives a cured product having excellent solvent resistance. These can be used alone or in combination.

[0153] The aromatic group-containing compound (b) and the monocarboxylic acid (c) may be added all at once, or in portions or successively. In terms of preventing side reactions, the portions or successively added are preferred.

[0154] In the above reaction step (1), the total amount of the aromatic group-containing compound (b) and the monocarboxylic acid (c) used is preferably 0.3 to 1.3 moles per mole of the epoxy group of the epoxy resin (a). By using them in such a ratio, the curability of the finally obtained resin and the physical properties of the cured product are easily improved. The amount is preferably 0.85 to 1.15 moles, more preferably 0.9 to 1.1 moles.

[0155] The reaction rate of the above reaction step (1) can be increased by replacing the atmosphere in the reaction tank with an inert gas such as nitrogen and lowering the oxygen concentration. The oxygen concentration in the reaction tank in the above reaction step (1) 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. In order to lower the oxygen concentration in the reaction solution, it is also preferable to bubble the solution with an inert gas such as nitrogen.

[0156] The reaction of the aromatic group-containing compound (b) with the epoxy resin (a) and the monocarboxylic acid (c) may be carried out in either order or simultaneously. These reactions can be carried out in the presence or absence of a diluent such as a polymerizable compound or a solvent described later, in the coexistence of a polymerization inhibitor such as hydroquinone or oxygen, and 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 80 to 130°C. As the reaction catalyst, tertiary phosphines are preferred from the viewpoints of reaction efficiency, stability during the reaction, and storage stability of the resin, and triphenylphosphine is particularly preferred.

[0157] The amount of the reaction catalyst is not particularly limited, but is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the epoxy resin (a) having two or more epoxy groups in one molecule.

[0158] In addition, in the above reaction step (1), a polymerization inhibitor may be used. The polymerization inhibitor is not particularly limited, and known ones can be used, for example, 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) etc.), 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-tetramethylpiperidine 1-oxyl, etc.), oxygen, etc. can be used.

[0159] When the polymerization inhibitor is used in the reaction step, 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, and more preferably 0.01 to 0.5 mass %.

[0160] The above reaction may be carried out in a solvent. Examples of the reaction solvent 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.

[0161] The reaction temperature in the above reaction step is not particularly limited as long as the reaction proceeds, but is preferably 80 to 140° C. By carrying out the reaction at such a temperature, the reaction can proceed efficiently. The reaction temperature is more preferably 85 to 135° C., and even more preferably 90 to 130° C.

[0162] Furthermore, when the resin (X1) has the structural unit (D), for example, prior to the reaction step (1), the epoxy resin (a) is reacted with a compound capable of introducing the structural unit (D) to thereby chain-extend the epoxy resin (a), and the chain-extended epoxy resin (a) is then subjected to the reaction step (1), thereby producing the resin (X1) having the structural unit (D).

[0163] Examples of compounds into which the structural unit (D) can be introduced include the bisphenol compounds from which the structural unit (D) is derived.

[0164] In addition, when the resin (X2) has a structure represented by the general formula (5), the epoxy resin (a) and the R 9 The epoxy resin (a) is chain-extended by reacting it with a compound capable of introducing R , and the chain-extended epoxy resin (a) is subjected to the above reaction step (1), whereby the resin (X2) having the above structure can be produced. 9 Examples of compounds that can introduce the above-mentioned structural unit (D) include the same compounds as the bisphenol compounds from which the structural unit (D) is derived.

[0165] In the above reaction, a reaction catalyst may be used. Examples of the reaction catalyst used in the reaction include the same catalysts as those used in the above-mentioned step (1).

[0166] In the aromatic ring-containing structure represented by the above general formula (1) or the structure represented by the above general formula (2), R 2 is a carboxyl group-containing group, or R 2 or R 4 When is a carboxyl group-containing group, the above production method preferably includes, after the above-mentioned step (1), a step (2) of reacting the reaction product obtained in the above-mentioned step (1) with a polybasic acid anhydride (d).

[0167] In step (2), the reaction product obtained in step (1) is reacted with a polybasic acid anhydride (d). In this reaction, the polybasic acid anhydride (d) reacts with the hydroxyl group present in the reaction product to obtain a resin (X) having a carboxyl group introduced therein. Such a resin (X) can be developed in an alkali, and can be used as an alkali-developable curable resin for image formation, etc.

[0168] The polybasic acid anhydride (d) used in step (2) is not particularly limited, but preferably has 3 to 30 carbon atoms, more preferably has 4 to 20 carbon atoms, and even more preferably has 4 to 10 carbon atoms.

[0169] Examples of the polybasic acid anhydride (d) include 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; and aliphatic or aromatic tetrabasic acid dianhydrides such as biphenyl tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, pyromellitic anhydride, and benzophenone tetracarboxylic acid dianhydride. One or more of these polybasic acid anhydrides can be used. Among these, it is preferable to use a dibasic acid anhydride. From the viewpoint of providing a cured product of the resulting resin (X) having particularly excellent solvent resistance, polybasic acid anhydrides, such as phthalic anhydride, which give resin (X) having a cyclic structure in its structure, are particularly preferred.

[0170] In step (2), the polybasic acid anhydride (d) is reacted in a ratio of preferably 1 to 99 mol, more preferably 20 to 80 mol, per chemical equivalent of the hydroxyl group of the reaction product obtained in step (1). By reacting the polybasic acid anhydride (d) in this manner, the addition reaction of the polybasic acid anhydride (d) can be efficiently carried out, and the carboxyl group can be suitably introduced into the resulting resin (X).

[0171] The reaction of the reaction product obtained in step (1) with the polybasic acid anhydride (d) in step (2) 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 polymerization inhibitor or reaction catalyst described above, in the same manner as the reaction in step (1). In step (2), a reaction catalyst may be used, and a tertiary phosphine is preferable, and triphenylphosphine is more preferable.

[0172] The reaction temperature in step (2) 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 further preferably 55 to 110° C.

[0173] The method for producing the resin (X) may include other steps in addition to the above-mentioned reaction step. Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, and a purification step. These steps can be carried out by known methods.

[0174] <Binder resin> The resin (X) of the present disclosure can be combined with an alkali-soluble resin to form a binder resin. The resin (X) can be used alone, but can also be used as an alkali-soluble resin by mixing with one or more alkali-soluble resins. Such a binder resin containing the above resin (X) and an alkali-soluble resin is also one of the preferred embodiments of the present disclosure.

[0175] The alkali-soluble resin is not particularly limited as long as it is a known resin that has an acid group and is soluble in an alkaline solution. In addition, an alkali-soluble resin described below may be used.

[0176] When used as a binder resin, the mixing ratio of the resin (X) and the alkali-soluble resin is not particularly limited and may be appropriately determined depending on the application, etc., but from the viewpoint of improving the refractive index of the composition, the content of the resin (X) is preferably 1 to 99 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 50 mass%, relative to 100 mass% of the total mass of the resin (X) and the alkali-soluble resin.

[0177] 2. Alkali-soluble resin In the present disclosure, an alkali-soluble resin (hereinafter also referred to as "alkali-soluble resin (Y)") having a structure represented by the following general formula (13), a double bond equivalent of more than 8000 g / equivalent, and an epoxy equivalent of more than 10000 g / equivalent, is also one of the preferred embodiments.

[0178] [ka] (In the formula, R 29 R represents an aromatic group which may have a substituent. 30 represents a divalent hydrocarbon group which may have a substituent.

[0179] The reason why the alkali-soluble resin (Y) can give a cured product with a high refractive index is believed to be that the resin has an aromatic group via a sulfur atom with a high atomic refractive index. In addition, the alkali-soluble resin (Y) has a specific range of epoxy equivalent, so that it has very few epoxy groups and is excellent in storage stability. In addition, since the double bond is in a specific range, it has the characteristic that the line thickening of the pattern after development is small.

[0180] In the above general formula (13), R 29 The aromatic group which may have a substituent represented by the formula (1) is R1 The same can be mentioned.

[0181] R 30 represents a divalent hydrocarbon group which may have a substituent. R 30 The divalent hydrocarbon group represented by the above-mentioned R 2a1 Among them, the divalent hydrocarbon group represented by R 30 From the viewpoint of good synthetic stability, the divalent hydrocarbon group represented by the following formula (I) is preferably a divalent aliphatic hydrocarbon group or a divalent alicyclic hydrocarbon group, more preferably a divalent aliphatic hydrocarbon group, and further preferably an alkylene group.

[0182] R 30 The divalent hydrocarbon group represented by the following formula (I) preferably has 2 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, and further preferably 2 carbon atoms.

[0183] R 30 Examples of the substituent that the divalent hydrocarbon group represented by the formula (I) may have include a carboxyl group, a hydroxyl group, an alkoxy group, and a halogen atom.

[0184] Preferred examples of the alkali-soluble resin (Y) having a structure represented by the above general formula (13) include resins having a structural unit (A') represented by the following general formula (14).

[0185] [ka]

[0186] (In the formula, A 3 R represents a benzene ring or a naphthalene ring. 31 R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. 32 represents a substituent bonded to A. j represents R 32 R represents the number of 33 R represents a divalent group. 29 and R 30are the same as in general formula (12).

[0187] In the above general formula (14), A 3 is preferably a benzene ring.

[0188] In the above general formula (14), R 31 As the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (6), R 12 The same can be mentioned.

[0189] In the above general formula (14), R 32 The substituent represented by the formula (6) is R 13 The same can be mentioned.

[0190] In the above general formula (14), R 33 As the divalent group represented by the above general formula (6), 14 The same can be mentioned.

[0191] In the above general formula (14), j is a substituent R 32 and is an integer of 0 to 5. j is preferably 0 to 3, more preferably 1 to 3, and further preferably 1. When j is 2 or more, that is, when R 32 If there are two or more, R 32 may be the same or different from each other.

[0192] The alkali-soluble resin (Y) may have one or more types of the structural unit (A'). When the alkali-soluble resin (Y) has the structural unit (A'), the content thereof is preferably 10 to 99 mol %, more preferably 30 to 95 mol %, and even more preferably 60 to 80 mol %, relative to 100 mol % of all structural units in the alkali-soluble resin (Y).

[0193] The alkali-soluble resin (Y) may have a structure represented by the general formula (3) similar to that of the resin (X) in addition to the structure represented by the general formula (13) above. It may also have a structure represented by the following general formula (15).

[0194] [ka]

[0195] (In the formula, R 34 R represents a hydrogen atom or a group represented by general formula (16). 35 represents an organic group. 36 represents a divalent hydrocarbon group which may have a substituent.

[0196] R 35 As the organic group represented by the formula (2), R 3 The organic group represented by the formula (I) is the same as that represented by the formula (I).

[0197] R 36 The divalent hydrocarbon group which may have a substituent represented by the formula (13) is R 30 The groups represented by the formula (I) are the same as those represented by the formula (I).

[0198] When the alkali-soluble resin (Y) has a structure represented by the above general formula (15), it preferably has a structural unit (E) represented by the following general formula (17).

[0199] [ka]

[0200] (In the formula, A 3 R represents a benzene ring or a naphthalene ring. 37 R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. 38 A 3 k represents a substituent bonded to R 38 R represents the number of 39R represents a divalent group. 34 and R 35 is the same as general formula (15).

[0201] In the above general formula (17), A 3 is preferably a benzene ring.

[0202] In the above general formula (17), R 37 As the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (6), R 12 The same can be mentioned.

[0203] In the above general formula (17), R 38 The substituent represented by the formula (6) is R 13 The same can be mentioned.

[0204] In the above general formula (17), R 39 As the divalent group represented by the above general formula (6), 14 The same can be mentioned.

[0205] In the above general formula (17), k is a substituent R 38 represents the number of, and is an integer of 0 to 5. k is preferably 0 to 3, more preferably 1 to 3, and further preferably 1. When k is 2 or more, that is, when R 38 If there are two or more, R 38 may be the same or different from each other.

[0206] The alkali-soluble resin (Y) may have one or more types of the structural units (E). When the alkali-soluble resin (Y) has the structural unit (E), the content thereof is preferably 0.1 to 90 mol %, more preferably 2 to 70 mol %, and even more preferably 10 to 30 mol %, relative to 100 mol % of all structural units in the alkali-soluble resin (Y), in order to increase the refractive index of the resin.

[0207] When the alkali-soluble resin (Y) has a structure represented by the general formula (3), it is preferable that the resin has the same structural unit (C') as the structural unit (C) of the resin (X).

[0208] The alkali-soluble resin (Y) may have one or more types of the structural unit (C'). When the alkali-soluble resin (Y) has the structural unit (C'), the content thereof is preferably 0.1 to 80 mol %, more preferably 2 to 60 mol %, and even more preferably 10 to 30 mol %, relative to 100 mol % of all structural units in the alkali-soluble resin (Y), in terms of excellent solvent resistance.

[0209] The alkali-soluble resin (Y) may further have the same structural unit (D') as the structural unit (D) of the resin (X). By introducing the structural unit (D') to carry out chain extension, the alkali-soluble resin can be designed to have any molecular weight.

[0210] When the alkali-soluble resin (Y) has the structural unit (D'), the content thereof is preferably 0.01 to 30 mol %, more preferably 0.1 to 20 mol %, and even more preferably 0.5 to 10 mol %, relative to 100 mol % of all structural units.

[0211] The double bond equivalent of the alkali-soluble resin (Y) is more than 8000 g / equivalent. When the double bond equivalent is within the above range, the resin has excellent storage stability. From the viewpoints of curability, storage stability, solvent resistance and adhesion, the double bond equivalent is preferably 8500 to 100000 g / equivalent, more preferably 9000 to 70000 g / equivalent, and even more preferably 10000 to 50000 g / equivalent. The method for measuring the double bond equivalent is the same as the method described above.

[0212] The epoxy equivalent of the alkali-soluble resin (Y) is more than 10000 g / equivalent. When the epoxy equivalent is within the above range, the storage stability of the resin is excellent. From the viewpoints of storage stability, developability, and solvent resistance, the epoxy equivalent is preferably 11000 to 100000 g / equivalent, more preferably 12000 to 70000 g / equivalent, and even more preferably 15000 to 50000 g / equivalent. The method for measuring the epoxy equivalent is the same as the method described above.

[0213] The acid value of the alkali-soluble resin (Y) is preferably 10 to 300 mgKOH / g. When the acid value is within the above range, the storage stability and developability of the resin are improved. The acid value of the resin is preferably 20 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and even more preferably 40 to 120 mgKOH / g, in terms of further improving the storage stability and developability. The method for measuring the acid value is the same as the method described above.

[0214] The weight average molecular weight of the alkali-soluble resin (Y) is preferably 1000 to 100000. In terms of good developability, the weight average molecular weight of the alkali-soluble resin (Y) is more preferably 2000 to 50000, further preferably 3000 to 20000, and particularly preferably 4000 to 10000. The method for measuring the weight average molecular weight is the same as the method described above.

[0215] From the viewpoints of film strength and developability, the glass transition temperature (Tg) of the alkali-soluble resin (Y) is preferably 40 to 300° C., more preferably 60 to 250° C., and even more preferably 80 to 200° C. The method for measuring the glass transition temperature is the same as the method described above.

[0216] <Method for producing alkali-soluble resin (Y)> The method for producing the alkali-soluble resin (Y) is not particularly limited as long as the alkali-soluble resin (Y) described above can be obtained. However, in terms of efficient production, it is preferable that the method includes the same steps as steps (1) and (2) in the method for producing the resin (X) described above.

[0217] Furthermore, when the alkali-soluble resin (Y) has the structural unit (D'), for example, prior to the step (1), the epoxy resin (a) is reacted with a compound capable of introducing the structural unit (D') to chain-extend the epoxy resin (a), and the chain-extended epoxy resin (a) is subjected to the step (1), thereby producing an alkali-soluble resin having the structural unit (D').

[0218] Examples of compounds into which the structural unit (D') can be introduced include the bisphenol compounds from which the structural unit (D') is derived.

[0219] In the above reaction, a reaction catalyst may be used. Examples of the reaction catalyst used in the reaction include the same catalysts as those used in the above-mentioned steps (1) and (2).

[0220] The method for producing the alkali-soluble resin (Y) may include other steps in addition to the above steps (1) and (2). Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, and a purification step. These steps can be carried out by known methods.

[0221] 3. Curable resin composition The resin (X) of the present disclosure and the above-mentioned alkali-soluble resin (Y) can be combined with other components to form a curable resin composition according to the application or purpose. Preferred examples of the other components include metal oxide particles, thermal acid generators, polyfunctional thiol compounds, photoacid generators, photobase generators, photoradical polymerization initiators, thermal radical polymerization initiators, polymerizable compounds, alkali-soluble resins, and acid compounds. The above-mentioned curable resin composition may contain one or more of these components.

[0222] (metal oxide particles) By making the resin composition containing the resin and metal oxide particles, a cured product with a higher 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 the smaller the difference in refractive index between the resin and the metal oxide particles, the smaller the loss of light due to Rayleigh scattering during exposure can be reduced. Since the resolution is not impaired even when the curable resin composition is highly filled with metal oxide particles, the dielectric properties can be improved.

[0223] Examples of the metal oxide particles include oxide particles of light-transmitting metals having a high refractive index, 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. Among them, the metal oxide particles preferably contain at least one metal element selected from the group consisting of Ti, Al, Zr, Zn, Sn, Ce, and Si, in that a cured product having a higher refractive index can be provided, and more preferably contain Zr from the viewpoint of providing a cured film having a high relative dielectric constant, and more preferably contain Si from the viewpoint of providing a cured film having a high hardness.

[0224] The metal oxide may be an oxide of a single metal, a solid solution of two or more oxides, or a composite oxide. Examples of single metal oxides include aluminum oxide (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), indium oxide (In2O3), zinc oxide (ZnO), tin oxide (SnO2), lanthanum oxide (La2O3), yttrium oxide (Y2O3), cerium oxide (CeO2), magnesium oxide (MgO), and silicon oxide (SiO2). Examples of solid solutions of two or more oxides include ITO and ATO. Examples of composite oxides include barium titanate (BaTiO3), perovskite (CaTiO3), and spinel (MgAl2O4). Among these, 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.

[0225] The metal oxide particles are preferably surface-modified metal oxide particles, since they can have improved dispersibility in the curable 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.

[0226] The metal oxide particles may be used alone or in combination of two or more kinds. The content of the metal oxide particles is preferably 0.1 to 99 mass %, more preferably 1 to 80 mass %, and even more preferably 10 to 40 mass %, relative to 100 mass % of the total solid content of the resin. In this specification, the term "total solid content" refers to the total amount of components that form the cured product (components excluding the solvent and the curing catalyst that volatilize during the formation of the cured product).

[0227] (Thermal acid generator) By preparing a resin composition containing the above resin and a thermal acid generator, the curability of the above resin can be improved. The thermal acid generator is not particularly limited, and any compound known as a thermal acid generator that can be blended with a resin can be used. Preferred examples include TA-100 and TA-120 manufactured by San-Apro Co., Ltd.

[0228] The thermal acid generators may be used alone or in combination of two or more. The content of the thermal acid generator is preferably 0.3 to 15 mass %, more preferably 0.5 to 10 mass %, and further preferably 1 to 8 mass %, relative to 100 mass % of the total solid content of the resin composition.

[0229] (Multifunctional thiol compounds) By forming a resin composition containing the resin and a polyfunctional thiol compound, the curability of the resin can be improved. When the resin contains a polymerizable unsaturated bond in the side chain, the resin composition containing a polyfunctional thiol compound can cause an enethiol reaction to occur simultaneously during exposure or heating, improving the crosslink density. In particular, when an acrylate-type polymerizable unsaturated bond is present in the resin, the enethiol reaction proceeds well. In addition, an addition reaction proceeds between a resin having an epoxy group in the side chain and a polyfunctional monomer.

[0230] 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 particularly preferably a tri- to penta-functional secondary thiol. By adding such a polyfunctional thiol compound to the curable resin composition, the curability and storage stability can be further improved.

[0231] Specific examples of the polyfunctional thiol compound include mercaptopropionic acid derivatives such as butanediol bisthiopropionate, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate) (KarenzPE-1), 1,4-bis(3-mercaptobutyryloxy)butane (KarenzBD-1), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (KarenzNR-1). Note that, as the polyfunctional thiol compound, a compound having no hydroxyl group and / or aromatic ring in the molecule is preferable.

[0232] Commercially available products of the above-mentioned polyfunctional thiol compounds can also be used. Examples of such compounds include "Thiokalcol 20" manufactured by Kao Corporation, "KarenzMT PE1", "KarenzMT BD1", "KarenzMT NR1", "TPMB", and "TEMB" manufactured by Showa Denko K.K., and "TMMP", "TEMPIC", "PEMP", "EGMP-4", "DPMP", "TMMP II-20P", and "PEMP II-20P" manufactured by SC Organic Chemical Co., Ltd.

[0233] The polyfunctional thiol compounds may be used alone or in combination of two or more kinds. The content of the polyfunctional thiol compound is preferably 0.3 to 15 mass%, more preferably 0.5 to 10 mass%, and further preferably 1 to 8 mass%, relative to 100 mass% of the total solid content of the curable resin composition.

[0234] (Photoacid generator) By preparing a resin composition containing the above resin and a photoacid generator, the curability of the curable resin composition can be further improved. The photoacid generator is a compound that generates an acid when exposed to active energy rays such as radiation, and examples thereof include strong acids such as toluenesulfonic acid or boron tetrafluoride, onium salts such as sulfonium salts, ammonium salts, phosphonium salts, iodonium salts or selenium salts; iron-allene complexes; silanol-metal chelate complexes; sulfonic acid derivatives such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoin sulfonates, and the like; organic halogen compounds.

[0235] The photoacid generators may be used alone or in combination of two or more kinds. The content of the photoacid generator is preferably 0.3 to 20 mass %, more preferably 0.5 to 10 mass %, and further preferably 1 to 8 mass %, relative to 100 mass % of the total solid content of the curable resin composition.

[0236] (Photobase Generator) By using a resin composition containing the above resin and a photoacid generator, epoxy polymerization is easily induced by light irradiation, and the curability and solvent resistance of the curable resin composition can be further improved.

[0237] Examples of the photobase generator include compounds that generate a base upon irradiation with light, such as 2-(9-oxoxanthen-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 2-(9-oxoxanthen-2-yl)propionic acid, acetophenone O-benzoyloxime, 2-nitrobenzyl cyclohexylcarbamate, 1,2-bis(4-methoxyphenyl)-2-oxoethyl cyclohexylcarbamate, (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium=tetrakis(3-fluorophenyl)borate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). WPBG-345), 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium=2-(3-benzoylphenyl)propionate (WPBG-266, Fujifilm Wako Pure Chemical Industries, Ltd.), 9-anthrylmethyl N,N-diethylcarbamate (WPBG-018, Fujifilm Wako Pure Chemical Industries, Ltd.), 1-(anthraquinone-2-yl)ethyl N-cyclohexylcarbamate (WPBG-174, Fujifilm Wako Pure Chemical Industries, Ltd.), 9-anthrylmethyl piperidine-1-carboxylate (WPBG-015, Fujifilm Wako Pure Chemical Industries, Ltd.), 9-anthrylmethyl N,N-dicyclohexylcarbamate (WPBG-015, Fujifilm Wako Pure Chemical Industries, Ltd.) WPBG-172), 1-(anthraquinone-2-yl)ethyl imidazole-1-carboxylate (WPBG-140, Fuji Film Wako Pure Chemical Industries, Ltd.), cyclohexylammonium 2-(3-benzoylphenyl)propionate (WPBG-168, Fuji Film Wako Pure Chemical Industries, Ltd.), (E)-N-cyclohexyl-3-(2-hydroxyphenyl)acrylamide (WPBG-025, Fuji Film Wako Pure Chemical Industries, Ltd.), dicyclohexylammonium 2-(3-benzoylphenyl)propionate (WPBG-167, Fuji Film Wako Pure Chemical Industries, Ltd.), 1,2-dicyclohexyl-4,4,5,Examples of suitable 5-tetramethylbiguanidium=n-butyltriphenylborate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. WPBG-300), 4-hydroxypiperidine-1-carboxylate (2-nitrophenyl)methyl (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. WPBG-158), 4-(methacryloyloxy)piperidine-1-carboxylate (2-nitrophenyl)methyl (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. WPBG-165), guanidium 2-(3-benzoylphenyl)propionate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. WPBG-082), (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. WPBG-027), and the like. Among these, 1-(anthraquinone-2-yl)ethyl imidazole-1-carboxylate or (2-nitrophenyl)methyl 4-hydroxypiperidine-1-carboxylate is preferred, and (2-nitrophenyl)methyl 4-hydroxypiperidine-1-carboxylate is more preferred, because they have good storage stability.

[0238] The photobase generators may be used alone or in combination of two or more kinds. The content of the photobase generator is preferably 0.01 to 20 mass%, more preferably 0.02 to 10 mass%, and further preferably 0.1 to 3 mass%, relative to 100 mass% of the total solid content of the curable resin composition.

[0239] (Photoradical polymerization initiator) The photoradical polymerization initiator is not particularly limited, and a known photoradical polymerization initiator can be used. Specific examples include aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907", manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE369", manufactured by BASF), and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one ("IRGACURE379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE651", manufactured by BASF), phenylglyoxylic acid methyl ester ("DAROCURE benzyl ketal compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR1173", BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE2959", BASF), 2-hydroxy -Hydroketone compounds such as 1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one ("IRGACURE 127", manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE 500", manufactured by BASF), etc., as well as other alkylphenone compounds exemplified in paragraphs

[0084] to

[0086] of JP 2013-227485 A;1,2-Octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) ("OXE01", manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) ("OXE02", manufactured by BASF), 1,2-Octanedione, 1-[4-(phenylthio)-, 2-, (O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), 1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ("OXE04", manufactured by BASF) and other oxime ester compounds; benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; titanocene compounds; benzoic acid ester compounds; acridine compounds; and phosphine oxide compounds. Among these, aminoketone compounds and oxime ester compounds are preferred. The photoradical polymerization initiator may be used alone or in combination of two or more.;

[0240] The content of the photoradical polymerization initiator is preferably 0.01 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 1 to 10 mass %, relative to 100 mass % of the total solid content of the resin.

[0241] (Thermal radical polymerization initiator) The thermal radical polymerization initiator is not particularly limited, and a known thermal radical polymerization initiator can be used. Specific examples include organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, and t-butylperoxy-2-ethylhexanoate; azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate); and the like. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used in combination.

[0242] The content of the thermal radical polymerization initiator is preferably 0.01 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 1 to 10 mass %, relative to 100 mass % of the total solid content of the resin.

[0243] (polymerizable compound) 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. 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.

[0244] Examples of the monofunctional compound 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, etc. Also usable are monomers having an active methylene group or an active methine group.

[0245] Examples of the polyfunctional compound 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;

[0246] Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid modified product, pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol triacrylate phthalic acid modified product,

[0247] [ka]

[0248] a polyfunctional (meth)acrylate compound having three or more functional groups, such as a modified product of dipentaerythritol hexaacrylate represented by the formula:

[0249] Polyfunctional 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 pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether;

[0250] vinyl ether group-containing (meth)acrylic acid esters 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;

[0251] 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 polyfunctional allyl ethers such as ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether;

[0252] 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 (meth)acrylate; polyfunctional aromatic vinyls such as divinylbenzene; etc. These polymerizable compounds may be used alone or in combination of two or more.

[0253] Among the above polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further increasing the curability of the curable resin composition. The number of functionalities of the above polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more. In addition, the number of functionalities is preferably 10 or less, more preferably 8 or less. The molecular weight of the above polymerizable compound is not particularly limited, but from the viewpoint of handling, it is preferably, for example, 2000 or less.

[0254] As the polyfunctional polymerizable compound, from the viewpoints of reactivity, economic efficiency, availability, etc., preferably, 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 more preferably, a polyfunctional (meth)acrylate compound. By including a compound having a (meth)acryloyl group, the curable resin composition has better photosensitivity and curability, and a cured product having higher hardness and transparency can be obtained. As the polyfunctional polymerizable compound, it is more preferable to use a polyfunctional (meth)acrylate compound having three or more functional groups.

[0255] The content of the polymerizable compound is preferably 1 to 99 mass %, more preferably 2 to 80 mass %, and further preferably 10 to 60 mass %, relative to 100 mass % of the total solid content of the curable resin composition.

[0256] (alkali soluble resin) The alkali-soluble resin is not particularly limited, and may be any known alkali-soluble resin that has an acid group and is soluble in an alkaline solution.

[0257] The content of the alkali-soluble resin may be appropriately set depending on the application of the curable resin composition and the blending of other components, and is, for example, preferably 0.1 to 99 mass%, more preferably 1 to 60 mass%, even more preferably 5 to 50 mass%, and still more preferably 10 to 40 mass%, relative to 100 mass% of the total solid content of the curable resin composition.

[0258] (acid compound) The acid compound is a compound having a pKa of 4.2 or less. When the curable resin composition contains an acid compound having a pKa of 4.2 or less, the reaction between the epoxy group and the acid group such as a carboxyl group of the component contained in the curable resin composition is suppressed, and the storage stability can be improved. The reason why the storage stability can be improved is considered to be that the presence of an acid compound having a stronger acid strength than the acid group reduces the anionicity of the acid group of the resin, thereby suppressing the reactivity of the acid group with the epoxy group. In addition, when a basic compound is present in the curable resin composition, the basic compound that formed a salt with the carboxyl group is supplemented by an acid compound having a pKa of 4.2 or less, and the nucleophilic force of the carboxyl group in the copolymer is reduced, and the reactivity of the acid group with the epoxy group can be suppressed.

[0259] The reason why the pKa is 4.2 or less is that the pKa value of the monomer capable of introducing an acid group is set as the threshold value. Examples of the pKa value of the monomer include acrylic acid (pKa 4.35), methacrylic acid (pKa 4.26), succinic acid mono(2-acryloyloxyethyl) (pKa 4.35), succinic acid mono(2-methacryloyloxyethyl) (pKa 4.35), etc.

[0260] The pKa of the acid compound is preferably 3 or less, and more preferably 2 or less. The lower limit of the pKa of the acid compound is not particularly limited, but is preferably −3 or more, and more preferably 0 or more.

[0261] pKa (acid dissociation constant) refers to the negative common logarithm (reciprocal logarithm) of the equilibrium constant Ka in the dissociation reaction in which hydrogen ions are released from an acid, and specifically refers to the value in water at 25°C. For pKa values, reference can be made to literature such as Chemistry Handbook, Basics II (Revised 5th Edition, Maruzen Co., Ltd.), and values ​​not listed in the literature can be calculated by the method described in the literature.

[0262] Specific examples of acid compounds having a pKa of 4.2 or less include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid derivatives, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, thiosulfuric acid, dimethyl sulfurous acid, diethyl sulfurous acid, dipropyl sulfurous acid, dibutyl sulfurous acid, diphenyl sulfurous acid, dimethyl sulfuric acid, diethyl sulfuric acid, dipropyl sulfuric acid, dibutyl sulfuric acid, diphenyl sulfuric acid, benzenesulfinic acid, toluenesulfinic acid, naphthalenesulfinic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, diisobutylnaphthalenesulfonic acid, and other aromatic sulfonic acids, methylsulfonic acid, ethylsulfonic acid, propylsulfonic acid, and other alkylsulfonic acids, α-olefinsulfonic acids, sulfonated polystyrenes, methyl acrylate-sulfonated styrene copolymers, and derivatives thereof. Phosphoric acid derivatives are particularly preferred.

[0263] Preferred examples of the phosphoric acid derivative include phosphoric acid ester, phosphorous acid ester, phosphorous acid, hypophosphorous acid, phosphonic acid, and phosphinic acid, and more preferred examples include phosphoric acid ester, phosphonic acid, and phosphinic acid.

[0264] Examples of the ester group of the phosphate ester or phosphite ester include an alkyl ester group, an aryl ester group, an aralkyl ester group, and an ester group having a polymerizable double bond. Examples of the alkyl of the alkyl ester group include methyl, ethyl, octyl, and 2-ethylhexyl. Examples of the aryl of the aryl ester group include phenyl, tolyl, and naphthyl. Examples of the aralkyl of the aralkyl ester group include benzyl. Examples of the ester group having a polymerizable double bond include a 2-acryloyloxyethyl ester group and a 2-methacryloyloxyethyl ester group.

[0265] Specific examples of the phosphoric acid ester include monoalkyl phosphates such as methyl phosphate; dialkyl phosphates such as dibutyl phosphate; trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris(2-chloroethyl)phosphate, and tris(2,3-dichloropropyl)phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; monoaryl phosphates; diaryl phosphates; triphenyl phosphate, tricresyl phosphate, and tris Examples of the phosphate ester include triaryl phosphates such as (nonylphenyl)phosphate and 2-ethylphenyl diphenyl phosphate; phosphate esters containing an ester group having a polymerizable double bond, such as 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, 3-methacryloyloxypropyl acid phosphate, methacryloyloxypolyoxyethylene glycol acid phosphate and methacryloyloxypolyoxypropylene glycol acid phosphate; alkyl phosphonic acids such as methylphosphonic acid; aryl phosphonic acids such as phenylphosphonic acid; alkyl phosphinic acids such as methylphosphinic acid; and aryl phosphinic acids such as phenylphosphinic acid.

[0266] Among them, the phosphoric acid ester is preferably a phosphoric acid ester containing an ester group having a polymerizable double bond. When the phosphoric acid ester containing an ester group having a polymerizable double bond is used, a crosslinked structure is formed together with the resin and the polymerizable compound during curing of the curable resin composition, and the volatilization and elution of the components contained therein are suppressed, and the occurrence of problems such as contamination of the reaction system and deterioration of electrical insulation can be significantly suppressed. The phosphoric acid ester preferably contains two or more polymerizable double bonds.

[0267] As the phosphate ester containing an ester group having a polymerizable double bond, for example, commercially available products such as Light Ester P-1M, Light Ester P-2M (both manufactured by Kyoeisha Chemical), and Hosmer M (manufactured by Unichemical Co., Ltd.) may be used. Among them, Light Ester P-2M is preferred.

[0268] The molecular weight of the acid compound is preferably 400 or less, and more preferably 350 or less. The molecular weight of the acid compound is preferably 150 or more, and more preferably 250 or more.

[0269] The above acid compounds may be used alone or in combination of two or more kinds. The content of the acid compound is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.1 to 3 mass %, relative to 100 mass % of the total solid content of the curable resin composition.

[0270] Among them, the curable resin composition preferably includes a curable resin composition containing the above-mentioned resin (X) and at least one selected from the group consisting of metal oxide particles, a photoradical polymerization initiator, a thermal radical polymerization initiator, a thermal acid generator, a photoacid generator, and a photobase generator. Such a curable resin composition is also one of the present disclosure.

[0271] In the curable resin composition, the content of the resin (X) is not particularly limited and may be appropriately set depending on the application and the blending of other components. For example, the content is preferably 0.1 to 99 mass%, more preferably 1 to 60 mass%, even more preferably 5 to 50 mass%, and still more preferably 10 to 40 mass%, relative to 100 mass% of the total solid content of the curable resin composition.

[0272] The curable resin composition may further contain other components other than the above-mentioned components as necessary. Examples of 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, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoaming agents, antistatic agents, slip agents, surface modifiers, thixotropic agents, thixotropic assistants, quinone diazide compounds, polyhydric phenol compounds, and cationic polymerizable compounds. 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.

[0273] <Preparation of Curable Resin Composition> The method for preparing the curable resin composition 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 step is not particularly limited, and may be performed by a known method. In addition, other steps that are usually performed may be further included.

[0274] <Photosensitive resin composition> One of the preferred forms of the curable resin composition is a photosensitive resin composition (hereinafter also referred to as "photosensitive resin composition (x)") that contains the above-mentioned resin (X), a photoradical polymerization initiator, an alkali-soluble resin, and a polymerizable compound. Such a photosensitive resin composition can be particularly suitably used as a negative resist, and enables the formation of a fine pattern. Such a photosensitive resin composition (x) is also one aspect of the present disclosure.

[0275] In the photosensitive resin composition (x), the content of the above-mentioned resin (X) is not particularly limited and may be appropriately set depending on the application and the blending of other components, and is, for example, preferably 0.1 to 99 mass%, more preferably 1 to 60 mass%, even more preferably 5 to 50 mass%, and still more preferably 10 to 40 mass%, relative to 100 mass% of the total solid content of the photosensitive resin composition (x).

[0276] Another preferred embodiment of the curable resin composition is a photosensitive resin composition (hereinafter also referred to as "photosensitive resin composition (y)") containing the alkali-soluble resin (Y), a photoradical polymerization initiator, and a polymerizable compound. Such a photosensitive resin composition is also one aspect of the present disclosure. Another preferred embodiment is one in which the photosensitive resin composition (y) further contains the resin (X).

[0277] The content of the alkali-soluble resin (Y) is not particularly limited and may be appropriately set depending on the application and the blending of other components, and is, for example, preferably 0.1 to 99 mass%, more preferably 1 to 60 mass%, even more preferably 5 to 50 mass%, and still more preferably 10 to 40 mass%, relative to 100 mass% of the total solid content of the photosensitive resin composition.

[0278] When the photosensitive resin composition (y) contains the resin (X), the content of the resin (X) is not particularly limited and may be appropriately set depending on the application and the blending of other components, and is, for example, preferably 1 to 99 mass%, more preferably 10 to 80 mass%, even more preferably 20 to 70 mass%, and still more preferably 30 to 60 mass%, relative to 100 mass% of the total solid content of the photosensitive resin composition (y).

[0279] 4.Cured product By using the resin (X) and / or the alkali-soluble resin (Y), or a curable resin composition containing the same, a cured product with a high refractive index can be obtained. The refractive index of the cured product is preferably 1.60 or more. The present disclosure also includes a cured product obtained by curing the above-mentioned resin (X), the curable resin composition, or the photosensitive resin composition, and having a refractive index of 1.60 or more.

[0280] The refractive index of the cured product is preferably 1.60 or more, and more preferably 1.62 or more. The refractive index can be determined by the method described in the Examples.

[0281] The method for obtaining the cured product using the resin or curable resin composition of the present disclosure is not particularly limited, and any known method may be used, for example, a method in which the above-mentioned resin or curable resin composition is applied or molded onto a substrate, and then cured by heating, irradiating with active energy rays such as ultraviolet rays, or a combination of these. Among these, a method for producing a cured product is preferably a method including a step of applying the curable 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 light-irradiated coating film.

[0282] The substrate is not particularly limited and may be appropriately selected depending on the purpose and application. Examples of the substrate include substrates made of various materials such as a glass plate and a plastic plate.

[0283] The method for applying the curable resin composition to a substrate to form a coating film is not particularly limited, and may be a known method such as spin coating, slit coating, roll coating, or cast coating.

[0284] After the curable resin composition is applied onto a substrate, it is preferable to dry the applied product to form a coating film. 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 component contained, the type of curable 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.

[0285] The method of irradiating the formed coating film with light is not particularly limited, and can be performed by a known method. Examples of the light source of the actinic ray 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.

[0286] When the coating film is irradiated with light, the irradiation may be performed through a photomask. As the 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. On the other hand, the unirradiated parts dissolve in the developer, and are removed by 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.

[0287] The developer is not particularly limited as long as it dissolves the curable resin composition, but usually, an organic solvent or an alkaline aqueous solution is used, and a mixture of these may be used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. Examples of organic solvents and alkaline aqueous solutions include those described in JP-A-2015-157909.

[0288] After the above-mentioned light irradiation, the coating film is preferably heated at 300° C. or lower. The heating temperature of the coating film is preferably 50 to 250° C., more preferably 60 to 180° C., and further preferably 70 to 100° C.

[0289] The heating time is not particularly limited and is preferably, for example, 5 to 60 minutes. The heating method is also not particularly limited and can be performed using known heating devices such as a hot plate, a convection oven, or a high-frequency heater.

[0290] When the cured product is a cured film, the film thickness is preferably 0.1 to 50 μm, more preferably 0.5 to 40 μm, and even more preferably 1 to 30 μm, in order to fully exhibit the high refractive index characteristics.

[0291] 5.Applications The resin (X), the alkali-soluble resin (Y) and the curable resin composition containing them of the present disclosure can give a cured product with a high refractive index. Therefore, the resin, the alkali-soluble resin and the curable resin composition of the present disclosure can be suitably used in applications requiring a high refractive index.

[0292] The alkali-soluble resin (Y) and the curable resin composition containing the same can be suitably used in applications requiring developability, and are therefore suitably used for optical materials, particularly for resists.

[0293] The resin (X) of the present disclosure, which has a high refractive index, the alkali-soluble resin (Y), and the curable resin composition containing them can be used for, 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 top coats, 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.), and the like. It can be widely applied to various applications such as: anodes, light guides (both planar and "fiber" geometric shapes), semiconductor elements, light diffusion members, prism sheets, hard coat materials, optical wiring members, diffraction gratings, sealing materials for LEDs, etc., pressure-sensitive adhesives, glass used in sensor elements such as CCD / CMOS and display elements of display devices such as micro LED displays, protective films used on the surfaces of films and sheets, photocurable resins (OCR) used to bond image display members such as liquid crystals and plastic cover panels, reflective protective films used in transparent electrodes, etc., index matching for preventing bones from appearing in ITO electrodes of touch panels, antiblocking layers, antireflective films for displays, and films for insulating interlayers of semiconductors. Among them, it is suitable as a curable resin or resin composition for forming semiconductor members or optical materials, and is particularly suitable as a curable resin or resin composition for optical materials.

[0294] In the present disclosure, the term "optical material" refers to a material used in the 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 electroluminescence, quantum dot, mini / micro LED displays, solid-state imaging devices, touch panel displays, etc. The resin of the present disclosure can be suitably used in applications where photolithography is applied because of its alkali solubility, and can become a cured film having high refraction, high hardness, and high transparency. The curable resin composition of the present disclosure (particularly, the photosensitive resin composition) is most preferably a resin composition for color filters, light extraction layers, and color conversion layers for organic electroluminescence displays.

[0295] The resin (X), the alkali-soluble resin (Y) of the present disclosure, and the curable resin composition containing them can also be suitably used for various optical components such as inks, printed wiring boards, insulating films, films, and organic protective films, and components of electric and electronic devices. EXAMPLES

[0296] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples. In addition, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0297] The various evaluation methods used in the present examples are as follows.

[0298] <Weight average molecular weight> The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance under the following measurement conditions: Apparatus: Gel permeation chromatography apparatus HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperHZM-M (Tosoh Corporation) Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF (tetrahydrofuran) Sample concentration: 0.05g / 10cc Sample flow rate: 0.6 ml / min

[0299] <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 (mgKOH / 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. That is, about 1 g of the resin solution was weighed out in an aluminum cup, about 3 g of acetone was added to dissolve it, and then it was naturally dried at room temperature. Then, it was dried at 140°C under vacuum for 1.5 hours using a vacuum dryer (EYELA, product name: VOS-301SD), and then it was cooled in a desiccator and the mass was measured. The solid content (mass%) of the resin solution was calculated from the amount of mass loss.

[0300] <Double bond equivalent> It was determined by dividing the mass (g) of the resin solid content by the amount (mol) of polymerizable double bonds in the resin.

[0301] <Epoxy equivalent> The solid content was calculated using a method in accordance with JIS K7236:2001.

[0302] <Refractive index (without exposure)> The obtained resin solution or curable resin composition was uniformly applied onto a glass substrate (Matsunami slide glass S9111, Matsunami Glass Industry Co., Ltd.) using a spin coater (Mikasa Co., Ltd., 1H-D7). The applied plate was dried at 85°C for 3 minutes to obtain a laminate in which a coating film was formed on the glass substrate. After removing the resin adhering to the edge of the glass substrate, the obtained laminate was subjected to a heat treatment at 85°C for 30 minutes using a Perfect Oven Thermostat (Espec Co., Ltd.) and cooled to room temperature to obtain a laminate in which a thin film with a thickness of 0.5 μm was formed. The obtained laminate was used as a measurement sample, and the reflection spectrum was measured using the device described below. A thin film reflectance simulation was performed based on the measured reflectance due to thin film interference based on the Fresnel equation to calculate the refractive index of the thin film at 589 nm. Equipment: Filmetrics film thickness measurement system F-20. Standard fiber stage SS-1 (spot diameter 1.5 mm).

[0303] <Refractive index (exposure 100mJ)> The obtained resin solution, photosensitive resin composition, or curable resin composition was uniformly coated on a glass substrate (Matsunami slide glass S9111, Matsunami Glass Industry Co., Ltd.) using a spin coater (Mikasa Co., Ltd., 1H-D7). The coated plate was dried at 85°C for 3 minutes, and then irradiated with 100 mJ / cm2 using a UV aligner (Dainippon Kaken Co., Ltd., product name "MA-1100") equipped with a 2.0 kW ultra-high pressure mercury lamp. 2 (365 nm illuminance equivalent) to obtain a laminate in which a coating film was formed on a glass substrate. After removing the resin adhering to the end of the glass substrate, the obtained laminate was heat-treated at 85°C for 30 minutes using a Perfect Oven Thermostat (manufactured by Espec Corporation) and cooled to room temperature to obtain a laminate in which a thin film with a thickness of 0.5 μm was formed. Except for using the obtained laminate as a measurement sample, the reflection spectrum was measured in the same manner as in the case of no exposure described above to obtain the refractive index value.

[0304] <Thickening rate> The viscosity of the resin solution or the photosensitive resin composition was measured at 25° C. using a viscometer (VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.). After storage at 40° C. for one month, the viscosity was measured again, and the viscosity increase rate was calculated by the following formula. Viscosity increase rate (%) = (viscosity after storage - viscosity before storage) / viscosity before storage x 100

[0305] <Solvent resistance> The photosensitive resin composition was spin-coated on a 5 cm square glass substrate, dried at 100°C for 3 minutes, exposed to 200 mJ using a high-pressure mercury lamp, and heat-treated (post-cured) at 85°C for 30 minutes to obtain a cured film with a thickness of 2 μm. The mass of the cured film was then measured, and the cured film was immersed in 20 g of propylene glycol monomethyl ether acetate (PGMEA) at 40°C for 10 minutes, then removed, and the mass of the cured film was measured again to determine the mass ratio (%) of the cured film after immersion to that before immersion. The larger the mass ratio, the smaller the weight loss rate of the cured film after immersion, and the higher the solvent resistance is evaluated to be.

[0306] <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 composition was irradiated with 60 mJ / cm 2 through a photomask with 30 μm line-and-space openings at a distance of 50 μm from the coating film, 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. 2 (converted into 365 nm illuminance), 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 the developability. Specifically, the coating film developed through a photomask as described above was observed with a surface roughness meter (manufactured by Ryoka Systems Co., Ltd., product name "VertScan2.0"), and the development time was determined as the spraying time of 0.05% potassium hydroxide aqueous solution required for the unexposed areas to flow.

[0307] <Minimum contact pattern> A line and space pattern was formed in the same manner as in the development speed test, except that the time for spraying the potassium hydroxide solution was changed to twice the development time obtained in the development speed test. The size of the smallest pattern that could be formed was observed with an optical microscope and taken as the minimum adhesion pattern. The closer the minimum adhesion pattern is to 1, the better it is judged to be.

[0308] <Thickened lines> 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 composition was irradiated with 60 mJ / cm 2 through a photomask with 30 μm line-and-space openings at a distance of 50 μm from the coating film, 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. 2 (converted into 365 nm illuminance), 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 the developability. Specifically, 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 "VertScan2.0") to evaluate line thickening from 30 μm. The smaller the value, the less the pattern line thickening and the better the miniaturization.

[0309] <Measurement of mass loss rate> The coated zirconium oxide particles were heated from room temperature to 800°C at a rate of 10°C / min in an air atmosphere using a TG-DTA (thermogravimetry-differential thermal analysis) device, and the mass loss rate of the particles was measured. From this mass loss rate, the proportion of the carboxylate compound coating the metal oxide particles and the proportion of the metal oxide can be known.

[0310] (Example 1) Preparation of resin solution (A-1) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dripping vessel inlet, 102.1 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac epoxy resin (YDCN-704A, epoxy equivalent 207.8 g / equivalent (eq), manufactured by Nippon Steel Chemical & Material Co., Ltd.) were charged, heated to 100 ° C. and held for 30 minutes to dissolve the epoxy resin. After lowering the temperature of the reaction vessel to 70 ° C., the reaction vessel was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration in the reaction vessel was 0.5 vol % or less, and 53.0 g of benzenethiol (BT) and 0.1 g of triphenylphosphine (TPP) were added to carry out an addition reaction, reacted for 5 hours, heated to 120 ° C. and held for 30 minutes to complete the reaction, and a resin solution (A-1) was obtained. Various physical properties of the obtained resin solution (A-1) are shown in Table 1.

[0311] (Example 2) Preparation of resin solution (A-2) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 95.4 g of propylene glycol monomethyl ether acetate and 100.0 g of NC-7000-L (naphthalene-containing novolac type epoxy resin, epoxy equivalent 231 g / equivalent, manufactured by Nippon Kayaku Co., Ltd.) were charged, heated to 100 ° C. and held for 30 minutes to dissolve the epoxy resin. After lowering the temperature of the reaction vessel to 70 ° C., the system was substituted by nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 42.9 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, reacted for 5 hours, heated to 120 ° C. and held for 30 minutes to complete the reaction, and a resin solution (A-2) was obtained. Table 1 shows various physical properties of the obtained resin solution (A-2).

[0312] (Example 3) Preparation of resin solution (A-3) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 91.5 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, and the epoxy resin was dissolved by heating to 100 ° C and holding for 30 minutes. After lowering the temperature of the reaction vessel to 70 ° C, the system was substituted by nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol % or less, and 37.1 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to react for 5 hours, and the reaction was completed by raising the temperature to 120 ° C and holding for 30 minutes to obtain a resin solution (A-3). Table 1 shows various physical properties of the obtained resin solution (A-3).

[0313] (Example 4) Preparation of resin solution (A-4) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, 98.6 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, and the epoxy resin was dissolved by heating to 100°C and holding for 30 minutes. After lowering the temperature of the reaction vessel to 70°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 47.7 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to proceed for 5 hours, and the reaction was completed by raising the temperature to 120°C and holding for 30 minutes. Then, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 3.5 g of acrylic acid (AA), 0.6 g of triphenylphosphine, and 0.3 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added and the addition reaction was carried out at 120°C, and the reaction was completed for 16 hours to obtain a resin solution (A-4). The various physical properties of the obtained resin solution (A-4) are shown in Table 1.

[0314] (Example 5) Preparation of resin solution (A-5) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, 96.5 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, and the epoxy resin was dissolved by heating to 100°C and holding for 30 minutes. After lowering the temperature of the reaction vessel to 70°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 37.1 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to proceed for 5 hours, and the reaction was completed by raising the temperature to 120°C and holding for 30 minutes. Then, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 10.4 g of acrylic acid (AA), 0.6 g of triphenylphosphine, and 0.2 g of Antage W-400 (mentioned above) as a polymerization inhibitor were added and the addition reaction was carried out at 120°C, and the reaction was completed for 16 hours to obtain a resin solution (A-5). The various physical properties of the obtained resin solution (A-5) are shown in Table 1.

[0315] (Example 6) Preparation of resin solution (A-6) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, 96.5 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, and the epoxy resin was dissolved by heating to 100°C and holding for 30 minutes. After lowering the temperature of the reaction vessel to 70°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 37.1 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to proceed for 5 hours, and the reaction was completed by raising the temperature to 120°C and holding for 30 minutes. Then, 10.7 g of propionic acid (PA) and 0.6 g of triphenylphosphine were added and subjected to an addition reaction at 120° C., and the reaction was completed for 16 hours to obtain a resin solution (A-6). The various physical properties of the obtained resin solution (A-6) are shown in Table 1.

[0316] (Example 7) Preparation of resin solution (A-7) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dripping vessel inlet, 87.9 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, and the epoxy resin was dissolved by heating to 100°C and holding for 30 minutes. After lowering the temperature of the reaction vessel to 70°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 31.8 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to proceed for 5 hours, and the reaction was completed by raising the temperature to 120°C and holding for 30 minutes. Then, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 6.9g of acrylic acid (AA), 0.6g of triphenylphosphine, and 0.2g of Antage W-400 (mentioned above) as a polymerization inhibitor were added and the addition reaction was carried out at 120°C, and the reaction was completed for 16 hours to obtain a resin solution (A-7). The various physical properties of the obtained resin solution (A-7) are shown in Table 1.

[0317] (Example 8) Preparation of resin solution (A-8) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dripping vessel inlet, 86.3 g of propylene glycol monomethyl ether acetate and 100.0 g of bisphenol A type epoxy resin (trade name "jER834"; manufactured by Mitsubishi Chemical; epoxy equivalent 248.0 g / equivalent) were charged, and the epoxy resin was dissolved by heating to 100 ° C and holding for 30 minutes. After lowering the temperature of the reaction vessel to 70 ° C, the system was substituted by nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol % or less, and 29.4 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to react for 5 hours, and the reaction was completed by raising the temperature to 120 ° C and holding for 30 minutes to obtain a resin solution (A-8). Table 1 shows various physical properties of the obtained resin solution (A-8).

[0318] (Example 9) Preparation of resin solution (A-9) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, 91.5 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, and the epoxy resin was dissolved by heating to 100°C and holding for 30 minutes. After lowering the temperature of the reaction vessel to 70°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 37.1 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to proceed for 5 hours, and the reaction was completed by raising the temperature to 120°C and holding for 30 minutes. Thereafter, 10.7 g of propionic acid (PA) and 0.6 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 16 hours until the reaction was completed. After that, it was cooled to room temperature, and then 33.7 g of succinic anhydride (SAH) and 24.9 g of propylene glycol monomethyl ether acetate were added and kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-9). The various physical properties of the obtained resin solution (A-9) are shown in Table 1.

[0319] (Example 10) Preparation of resin solution (A-10) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, 90.5 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, and the epoxy resin was dissolved by heating to 100°C and holding for 30 minutes. After lowering the temperature of the reaction vessel to 70°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 35.6 g of benzenethiol (BT) and 0.1 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to proceed for 5 hours, and the reaction was completed by raising the temperature to 120°C and holding for 30 minutes. While blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 5.5 g of acrylic acid (AA), 0.6 g of triphenylphosphine, and 0.2 g of Antage W-400 (mentioned above) as a polymerization inhibitor were added and an addition reaction was carried out at 120°C. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 14.4 g of succinic anhydride (SAH) and 12.0 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 60° C. for 12 hours to complete the reaction, thereby obtaining a resin solution (A-10). The various physical properties of the obtained resin solution (A-10) are shown in Table 1.

[0320] (Example 11) Preparation of resin solution (A-11) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 135.9 g of propylene glycol monomethyl ether acetate and 100.0 g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After lowering the temperature of the reaction vessel to 70°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 52.7 g of benzenethiol (BT) and 0.5 g of triphenylphosphine were added to carry out an addition reaction. The reaction was carried out for 5 hours, and the reaction was completed by raising the temperature to 120°C and holding for 30 minutes. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 4.8 g of acrylic acid (AA), 0.3 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was maintained at 120°C to carry out an addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 20.2 g of tetrahydrophthalic anhydride (THPA), 16.8 g of propylene glycol monomethyl ether acetate, and 0.4 g of triphenylphosphine were added and the reaction was completed by maintaining at 110°C for 7 hours to obtain a resin solution (A-11). Various physical properties of the obtained resin solution (A-11) are shown in Table 1.

[0321] (Example 12) Preparation of resin solution (A-12) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 133.8g of propylene glycol monomethyl ether acetate and 100.0g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5vol% or less, and 33.3g of bisphenol S (BPS) and 0.5g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., and 23.4 g of benzenethiol (BT) and 0.5 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 4.8 g of acrylic acid (AA), 1.0 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out the addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 13.3 g of succinic anhydride (SAH), 0.4 g of triphenylphosphine, and 17.0 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-12). The various physical properties of the obtained resin solution (A-12) are shown in Table 1.

[0322] (Example 13) Preparation of resin solution (A-13) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 117.1 g of propylene glycol monomethyl ether acetate and 100.0 g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 16.6 g of bisphenol S (BPS) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., and 38.1 g of benzenethiol (BT) and 0.3 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 4.8 g of acrylic acid (AA), 1.0 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out the addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 13.3 g of succinic anhydride (SAH), 0.4 g of triphenylphosphine, and 31.3 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-13). The various physical properties of the obtained resin solution (A-13) are shown in Table 1.

[0323] (Example 14) Preparation of resin solution (A-14) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 117.1 g of propylene glycol monomethyl ether acetate and 100.0 g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 16.6 g of bisphenol S (BPS) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., and 38.1 g of benzenethiol (BT) and 0.5 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 5.7 g of methacrylic acid (MAA), 1.0 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out the addition reaction. The reaction was carried out for 16 hours to complete the reaction. After that, after cooling to room temperature, 26.6 g of succinic anhydride (SAH), 0.4 g of triphenylphosphine, and 45.3 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-14). The various physical properties of the obtained resin solution (A-14) are shown in Table 1.

[0324] (Example 15) Preparation of resin solution (A-15) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 117.1 g of propylene glycol monomethyl ether acetate and 100.0 g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 16.6 g of bisphenol S (BPS) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., and 29.3 g of benzenethiol (BT) and 0.4 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 10.5 g of acrylic acid (AA), 1.0 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out the addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 13.3 g of succinic anhydride (SAH), 0.4 g of triphenylphosphine, and 29.5 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-15). The various physical properties of the obtained resin solution (A-15) are shown in Table 1.

[0325] (Example 16) Preparation of resin solution (A-16) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet, 122.1 g of propylene glycol monomethyl ether acetate and 100.0 g of fluorene-type bifunctional epoxy resin (9,9-bis(4-glycidyloxyphenyl)fluorene. Epoxy equivalent: 250.0 g / equivalent) were charged, heated to 100°C, and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 25.0 g of bisphenol S (BPS) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., and 17.6 g of benzenethiol (BT) and 0.3 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 3.6 g of acrylic acid (AA), 0.8 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out the addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 10.0 g of succinic anhydride (SAH), 0.3 g of triphenylphosphine, and 7.6 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-16). The various physical properties of the obtained resin solution (A-16) are shown in Table 1.

[0326] (Example 17) Preparation of resin solution (A-17) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 133.8g of propylene glycol monomethyl ether acetate and 100.0g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5vol% or less, and 33.3g of bisphenol S (BPS) and 0.3g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 5 hours until the reaction was completed. Thereafter, the temperature was lowered to 40° C., and 20.5 g of benzenethiol (BT) and 0.4 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. After that, after cooling to room temperature, 13.3 g of succinic anhydride (SAH), 0.3 g of triphenylphosphine, and 9.5 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 60°C for 12 hours to complete the reaction, thereby obtaining a resin solution (A-17). The various physical properties of the obtained resin solution (A-17) are shown in Table 1.

[0327] (Example 18) Preparation of resin solution (A-18) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 117.1 g of propylene glycol monomethyl ether acetate and 100.0 g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 33.3 g of bisphenol S (BPS) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., and 23.4 g of benzenethiol (BT) and 0.3 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, 4.9 g of propionic acid (PA), 1.0 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120° C. to carry out an addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, it was cooled to room temperature, and then 38.9 g of succinic anhydride (SAH), 0.4 g of triphenylphosphine, and 39.0 g of propylene glycol monomethyl ether acetate were added and kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-18). Various physical properties of the obtained resin solution (A-18) are shown in Table 1.

[0328] (Example 19) Preparation of resin solution (A-19) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 120.4 g of propylene glycol monomethyl ether acetate and 100.0 g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 20.0 g of bisphenol S (BPS) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., and 24.0 g of benzenethiol (BT) and 0.3 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Then, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 12.1 g of acrylic acid (AA), 0.9 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out an addition reaction, which was then completed after 16 hours of reaction to obtain a resin solution (A-19). The various physical properties of the obtained resin solution (A-19) are shown in Table 1.

[0329] (Example 20) Preparation of resin solution (A-20) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 125.1 g of propylene glycol monomethyl ether acetate and 100.0 g of biphenyl type bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl. Epoxy equivalent: 188.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 24.6 g of bisphenol S (BPS) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. After that, the temperature was lowered to 40°C, 21.7 g of benzenethiol (BT) and 0.3 g of triphenylphosphine were added, and the reaction was completed at 40°C for 3 hours to obtain a resin solution (A-20). Various physical properties of the obtained resin solution (A-20) are shown in Table 1.

[0330] (Example 21) Preparation of resin solution (A-21) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dripping vessel inlet, 104.1 g of propylene glycol monomethyl ether acetate and 100.0 g of fluorene-type bifunctional epoxy resin (9,9-bis(6-glycidyloxynaphthyl)fluorene. Epoxy equivalent: 305.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 12.3 g of bisphenol S (BPS) and 0.45 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., 21.7 g of benzenethiol (BT) was added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 3.0 g of acrylic acid (AA), 0.8 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out the addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 15.7 g of succinic anhydride (SAH), 0.3 g of triphenylphosphine, and 14.8 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-21). The various physical properties of the obtained resin solution (A-21) are shown in Table 1.

[0331] (Example 22) Preparation of resin solution (A-22) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dropping vessel inlet, 98.4g of propylene glycol monomethyl ether acetate and 100.0g of fluorene-type bifunctional epoxy resin (9,9-bis(6-glycidyloxynaphthyl)fluorene. Epoxy equivalent: 305.0g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5vol% or less, and 6.2g of bisphenol S (BPS) and 0.43g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., 21.7 g of benzenethiol (BT) was added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 6.5 g of acrylic acid (AA), 0.8 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out the addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 15.7 g of succinic anhydride (SAH), 0.3 g of triphenylphosphine, and 14.8 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-22). The various physical properties of the obtained resin solution (A-22) are shown in Table 1.

[0332] (Example 23) Preparation of resin solution (A-23) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dropping vessel inlet, 122.1 g of propylene glycol monomethyl ether acetate and 100.0 g of fluorene-type bifunctional epoxy resin (9,9-bis(4-glycidyloxyphenyl)fluorene. Epoxy equivalent: 250.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 7.5 g of bisphenol S (BPS) and 0.4 g of triphenylphosphine were added to carry out an addition reaction, which was then completed after 5 hours of reaction. Thereafter, the temperature was lowered to 40° C., 26.4 g of benzenethiol (BT) was added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. After that, after cooling to room temperature, 29.2 g of tetrahydrophthalic anhydride (THPA), 0.5 g of triethylamine, and 27.4 g of propylene glycol monomethyl ether acetate were added and maintained at 110°C for 7 hours to complete the reaction, and 1.9 g of Light Ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.) was added to obtain a resin solution (A-23). ​​Various physical properties of the obtained resin solution (A-23) are shown in Table 1.

[0333] (Example 24) Preparation of resin solution (A-24) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube and a dropping vessel inlet, 107.3 g of propylene glycol monomethyl ether acetate and 100.0 g of fluorene-type bifunctional epoxy resin (9,9-bis(4-glycidyloxyphenyl)fluorene. Epoxy equivalent: 250.0 g / equivalent) were charged, heated to 100°C and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 6.8 g of bisphenol A (BPA) and 0.4 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 5 hours until the reaction was completed. Thereafter, the temperature was lowered to 40° C., and 30.8 g of benzenethiol (BT) and 0.3 g of triphenylphosphine were added, and the reaction was carried out at 40° C. for 3 hours to complete the reaction. Thereafter, while blowing in a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, 6.5 g of acrylic acid (AA), 0.9 g of triphenylphosphine, and 0.2 g of Antage W-400 (Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added, and the temperature was raised to 120°C to carry out the addition reaction. The reaction was continued for 16 hours to complete the reaction. After that, after cooling to room temperature, 28.0 g of succinic anhydride (SAH), 0.3 g of triphenylphosphine, and 19.1 g of propylene glycol monomethyl ether acetate were added and the mixture was kept at 110°C for 7 hours to complete the reaction, thereby obtaining a resin solution (A-24). The various physical properties of the obtained resin solution (A-24) are shown in Table 1.

[0334] (Comparative Example 1) Preparation of resin solution (B-1) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dripping vessel inlet, 88.7 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, heated to 100°C, and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen while maintaining the same temperature, and 35.6 g of propionic acid (PA) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to proceed for 12 hours to obtain a resin solution (B-1). The various physical properties of the obtained resin solution (B-1) are shown in Table 1.

[0335] (Comparative Example 2) Preparation of resin solution (B-2) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dripping vessel inlet, 88.5 g of propylene glycol monomethyl ether acetate and 100.0 g of cresol novolac type epoxy resin (mentioned above) were charged, heated to 100°C, and held for 30 minutes to dissolve the epoxy resin. After raising the temperature of the reaction vessel to 120°C, the system was substituted with nitrogen while maintaining the same temperature, and 32.7 g of propionic acid (PA) and 0.5 g of triphenylphosphine were added to carry out an addition reaction, which was allowed to proceed for 12 hours to obtain a resin solution (B-2). The various physical properties of the obtained resin solution (B-2) are shown in Table 1.

[0336] (Comparative Example 3) Preparation of resin solution (B-3) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dripping vessel inlet was charged with 219.8 g of propylene glycol monomethyl ether acetate, and after replacing with nitrogen, it was heated to 90 ° C. On the other hand, as the dripping vessel (A), 87.0 g of methyl methacrylate (MMA), 13.0 g of methacrylic acid (MAA), 2.0 g of t-butyl peroxy-2-ethylhexanoate, and 10.0 g of propylene glycol monomethyl ether acetate were prepared in a beaker, and as the dripping vessel (B), 2.0 g of n-dodecyl mercaptan and 3.5 g of propylene glycol monomethyl ether acetate were prepared by stirring. After the temperature of the reaction vessel reached 90 ° C, the dripping vessel was started to drip from the dripping vessel over a period of 3 hours while maintaining the same temperature, and polymerization was performed. After the dripping was completed, the temperature was maintained at 90 ° C for 30 minutes, and then the temperature was increased to 115 ° C, and aging was performed for 90 minutes. After cooling to room temperature, 7.4g of glycidyl methacrylate (GMA), 0.3g of triethylamine, and 0.2g of Antage W-400 were added, and the mixture was reacted at 115°C for 7 hours while bubbling oxygen / nitrogen mixed gas adjusted to an oxygen concentration of 7% at 20ml / min to obtain a resin solution (B-3). The physical properties of the obtained resin solution are shown in Table 2.

[0337] (Comparative Example 4) Preparation of resin solution (B-4) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube and a dripping vessel inlet, 153.9g of propylene glycol monomethyl ether acetate and 65.9g of propylene glycol monomethyl ether were charged, and after nitrogen replacement, the temperature was raised to 90 ° C. by heating. On the other hand, as the dripping vessel (A), 70.0g of methyl methacrylate (MMA), 30.0g of methacrylic acid (MAA), 2.0g of t-butyl peroxy-2-ethylhexanoate, and 10.0g of propylene glycol monomethyl ether acetate were prepared in a beaker by stirring, and in the dripping vessel (B), 2.0g of n-dodecyl mercaptan and 3.5g of propylene glycol monomethyl ether acetate were prepared by stirring. After the temperature of the reaction vessel reached 90 ° C., while maintaining the same temperature, dripping was started from the dripping vessel over 3 hours, and polymerization was carried out. After the dropwise addition, the mixture was kept at 90°C for 30 minutes, then heated to 115°C and aged for 90 minutes. After cooling to room temperature, 16.9g of glycidyl methacrylate (GMA), 0.3g of triethylamine, and 0.2g of Antage W-400 were added, and the mixture was reacted at 115°C for 7 hours while bubbling oxygen / nitrogen mixed gas adjusted to an oxygen concentration of 7% at 20ml / min to obtain a resin solution (B-4). The various physical properties of the obtained resin solution are shown in Table 2.

[0338] (Examples 25 to 61, Comparative Examples 5 to 9) The resin solution obtained above was mixed with dipentaerythritol hexaacrylate, a photoradical polymerization initiator (Irgacure OXE-02, manufactured by BASF), a thermal radical polymerization initiator (Perbutyl O, manufactured by NOF Corporation), metal oxide particles, a photoacid generator (CPI-100P, manufactured by San-Apro Co., Ltd.), a photobase generator (WPBG-140, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), a thermal acid generator (TA-100, manufactured by San-Apro Co., Ltd.), or propylene glycol monomethyl ether acetate in the formulation (solid content) shown in Tables 3 to 5 to obtain photosensitive resin compositions 1 to 30 and curable resin compositions 1 to 12. The metal oxide particles were prepared by the method shown below.

[0339] <Preparation of Metal Oxide Particles> Manufacturing Example 1 (Production of Coated Zirconium Oxide Particles (Coated ZrO2 Particles 1) Coated with 2-Ethylhexanoic Acid and / or Carboxylate Derived from 2-Ethylhexanoic Acid) A 2-ethylhexanoate zirconium mineral spirit solution (782 g, 2-ethylhexanoate content of 44% by mass, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) was mixed with pure water (268 g). The resulting mixture was placed in an autoclave equipped with a stirrer, and the atmosphere in the autoclave was replaced with nitrogen gas. 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. Next, as a purification step, the mixture was filtered again with a quantitative filter paper (manufactured by Advantec Toyo Co., Ltd., No. 5C) to remove coarse particles in the precipitate. Furthermore, the filtrate was concentrated under reduced pressure to remove the toluene, and white zirconium oxide particles (coated ZrO2 particles 1) were recovered.

[0340] When the crystal structure of the obtained coated ZrO2 particle 1 was confirmed by 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.

[0341] The average particle diameter (number average primary particle diameter) of the coated ZrO2 particles 1 obtained by measurement with an electron microscope (JEOL Ltd., FE-TEM JEM-2100F, 600,000 times magnification) was 12 nm. Furthermore, when the obtained coated ZrO2 particles 1 were analyzed by infrared absorption spectroscopy, absorption derived from CH 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 that coats the surface of the coated ZrO2 particles 1. Furthermore, 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 amount of 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid that coated the surfaces of the coated ZrO2 particles 1 was 12% by mass of the entire coated ZrO2 particles 1.

[0342] Manufacturing Example 2 (Production of zirconium oxide particles 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. Next, 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), and after stirring for 10 minutes, the aggregated particles were separated using filter paper. The obtained particles were vacuum-dried at room temperature to prepare zirconium oxide particles (coated ZrO2 particles 2) surface-treated with 2-ethylhexanoic acid and / or a carboxylate derived from 2-ethylhexanoic acid and 2-acryloyloxyethyl succinate.

[0343] The obtained coated ZrO2 particles 2 were dispersed in deuterated chloroform to prepare a measurement sample. 1 Analysis by H-NMR revealed that the molar ratio of 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid to 2-acryloyloxyethyl succinate was 24:76.

[0344] The mass reduction rate of the coated ZrO2 particles 2 measured according to the above <Measurement of Mass Reduction Rate> was 18% by mass. Therefore, it was found that 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.

[0345] The coated ZrO2 particles 2 (7 g) obtained above, methyl ethyl ketone (3 g), and DISPER BYK-111 (manufactured by BYK-Chemie Japan, 0.14 g) 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.

[0346] Various evaluations were carried out on the obtained photosensitive resin compositions 1 to 30 and curable resin compositions 1 to 12. The results are shown in Tables 3 to 5.

[0347] [Table 1]

[0348] [Table 2]

[0349] [Table 3]

[0350] [Table 4]

[0351] [Table 5]

[0352] From Table 1, it was confirmed that the resins of Examples 1 to 24 having an aromatic ring-containing structure represented by the above general formula (1) exhibit a higher refractive index than the resins of Comparative Examples 1 to 2 not having the above aromatic ring-containing structure. In particular, by using the epoxy resins having a fluorene skeleton shown in Examples 16, 21 to 24 as starting materials, alkali-soluble resins having a very high refractive index could be synthesized. However, since the resins of Examples 10, 17, and 23 have both epoxy groups and acid groups, the storage stability was inferior to the resins of other Examples. Since the resin of Example 23 contains an acid compound with a pKa of 4.2 or less, the storage stability was improved compared to the resins of Examples 10 and 17.

[0353] From Table 3, it was confirmed that the cured product of the photosensitive resin composition to which the resin of the Example was added also exhibited a high refractive index. Moreover, from Example 35, it was confirmed that a higher refractive index was exhibited by using metal oxide particles in combination. Moreover, the photosensitive resin composition of the Example had a faster development speed than the photosensitive resin composition of the Comparative Example. This is because the resin of the Example has a thioether bond.

[0354] The photosensitive resin compositions of the examples also have good solvent resistance, which is presumably due to the π-π interactions of the aromatic units that form a dense cured film. The presence of epoxy groups and double bonds (especially epoxy groups) can further improve the solvent resistance.

[0355] The photosensitive resin compositions of the examples also had good adhesion, which is presumably due to the improved adhesion to the substrate caused by the thioether bond. The adhesion can be further improved by the presence of a double bond or an epoxy group (especially a double bond).

[0356] The resin of Example 9, which has the structure of the above general formula (1) and is alkali-soluble, has an epoxy equivalent of more than 10,000 g / equivalent and a double bond equivalent of more than 8,000 g / equivalent because it does not have a double bond equivalent. In a photosensitive resin composition containing such a resin, excessive curing does not occur due to heat or light, so a pattern with small line thickening could be formed. In addition, the photosensitive resin compositions containing the resins of Examples 11 to 24, which were made from bifunctional epoxy resins as starting materials, had relatively fast development speeds due to the flexibility of the skeleton. The resins (Examples 16, 21 to 24) made from epoxy resins having a fluorene skeleton as starting materials had slightly slower development speeds than the resins (Examples 11 to 15, 17 to 20) made from epoxy resins having biphenyl groups as starting materials. The resins of Examples 1 to 8 and Examples 19 to 20 are not alkali-soluble, and therefore require the use of another alkali-soluble resin in combination for development, which makes them inferior to the resins of the other Examples.

[0357] From Table 4, it was confirmed that the cured product of the curable resin composition to which the resin of the Example was added also exhibited a high refractive index. The curing of the resin having an epoxy group was promoted by the addition of a photoacid generator, a photobase generator, or a thermal acid generator, and the refractive index of the cured product was improved. The curing of the resin having a double bond was promoted by the addition of a photoradical polymerization initiator or a thermal radical polymerization initiator, and the refractive index of the cured product was improved.

[0358] From Table 5, it can be seen that when a resin made from a bifunctional epoxy resin is included, aggregation is controlled by the linear structure, and storage stability with metal oxide particles is improved.

Claims

1. A resin characterized by having an aromatic ring-containing structure represented by the following general formula (1): 【Chemistry 1】 (In the formula, R １ R represents an aromatic group which may have a substituent. ２ represents a hydrogen atom or a carboxyl group-containing group.

2. The resin according to claim 1, further comprising at least one structure selected from the group consisting of a structure represented by the following general formula (2) and a structure represented by the following general formula (3): 【Chemistry 2】 (In the formula, R ２ represents a hydrogen atom or a carboxyl group-containing group. ３ represents an organic group.) 【Chemistry 3】

3. The resin according to claim 1, characterized in that it is represented by the following general formula (4). 【Chemistry 4】 (In the formula, R １ R represents an aromatic group which may have a substituent. ２ and R ４ are the same or different and each represents a hydrogen atom or a carboxyl group-containing group. １ represents a divalent organic group. ５ represents an organic group; and n represents 0 or 1.

4. The above A １ The resin according to claim 3 , wherein the divalent organic group represented by the following formula (5) is a divalent group represented by the following formula (5): 【Chemistry 5】 (In the formula, R ７ and R １１ R may be the same or different and represents a divalent organic group containing an aromatic group. ８ and R １０ R may be the same or different and represents a hydrogen atom or a carboxyl group-containing group. ９ represents a divalent organic group containing an aromatic group; and m represents an integer of 1 or more.

5. A curable resin composition comprising the resin according to claim 1 and at least one selected from the group consisting of metal oxide particles, a photoradical polymerization initiator, a thermal radical polymerization initiator, a thermal acid generator, a photoacid generator, and a photobase generator.

6. A photosensitive resin composition comprising the resin according to claim 1, an alkali-soluble resin, a photoradical polymerization initiator, and a polymerizable compound.

7. A cured product obtained by curing the resin according to claim 1, the curable resin composition according to claim 5, or the photosensitive resin composition according to claim 6, The cured product has a refractive index of 1.60 or more.

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