Alkali-soluble resin, photosensitive resin composition, method for producing same, and use thereof

Abstract

Provided are an alkali-soluble resin and a photosensitive resin composition which are capable of providing a cured product having excellent photocurability and a high refractive index. The present invention relates to an alkali-soluble resin having an aromatic ring-containing structure represented by formula (1) and a polymerizable unsaturated bond-containing structure represented by formula (2), the equivalent weight of the polymerizable unsaturated bond being 700-8000 g / equivalent (in formula (1), R1 represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom having or not having a substituent; and R2 represents an aromatic group having or not having a substituent. And R3 represents a hydrogen atom or a group represented by formula (3). In formula (2), R4, R5 and R6 may be the same or different and each represents a hydrogen atom or a C1-6 hydrocarbon group. R7 and R8 may be the same or different and each represents a direct bond or a divalent organic group. And R9 represents a hydrogen atom or a group represented by formula (3). And at least one of R3 and R9 is a group represented by formula (3). In formula (3), R10 represents a divalent hydrocarbon group having or not having a substituent. ). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to an alkali-soluble resin, a photosensitive resin composition, a method for producing the same, and uses thereof. Specifically, the present invention relates to an alkali-soluble resin, a photosensitive resin composition, a method for producing the same, a cured product, a member for a display device using them, and a display device, which can provide a cured product having excellent photocurability and a high refractive index. Background Art

[0002] Regarding alkali-soluble resins and photosensitive resin compositions, various studies have been conducted on their applications in various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, organic insulating films, and organic protective films used in, for example, liquid crystal display devices and solid-state imaging elements, as well as various uses such as electric motors / electronic devices. Resins and resin compositions having excellent characteristics required for each use have been developed.

[0003] In recent years, with the continuous development of miniaturization, thinning, and energy saving of optical members, electric motors / electronic devices, etc., higher-quality performance has been required for various members used. In order to meet such requirements, studies have been conducted on alkali-soluble resins that are materials for various members.

[0004] So far, alkali-soluble resins that meet various requirements have been developed.

[0005] For example, Patent Document 1 describes a modified epoxy resin having excellent heat resistance, moisture resistance, and flexibility, which is obtained by reacting an epoxy resin (i) having two or more epoxy groups in one molecule, a phenol (ii) having a substituent containing an aryl group, and an unsaturated monocarboxylic acid (iii).

[0006] In addition, for example, in Patent Document 2, as a substance capable of providing a solder resist coating film having excellent heat resistance, adhesion, resolution, electroless plating resistance, electrical properties, moisture absorption resistance, etc., a photosensitive prepolymer is described, which is obtained by reacting an alcohol hydroxyl group of a reaction product of a polycarboxylic anhydride with an epoxy compound having two or more epoxy groups in one molecule, a specified phenol compound and / or naphthol compound, and a monocarboxylic acid containing an unsaturated group.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Laid-Open No. 11-49840

[0010] Patent Document 2: Japanese Patent Laid-Open No. 11-315107 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] However, these conventional alkali-soluble resins have a low refractive index. For use in optical applications that require a high refractive index, a high refractive index of about 1.60 is needed, and such requirements cannot be fully met yet.

[0013] In addition, in recent years, when alkali-soluble resins are used in optical applications such as color filter applications, higher performance such as higher brightness and higher contrast of display panels has been strongly demanded. In order to better exhibit the physical properties of the cured film, it is desired that the curing reaction proceeds sufficiently.

[0014] The present invention has been made in view of the above situation, and an object thereof is to provide an alkali-soluble resin and a photosensitive resin composition that can provide a cured product having excellent photocurability and a high refractive index.

[0015] Means for Solving the Problems

[0016] The present inventors conducted various studies on alkali-soluble resins and found that by having a specific aromatic ring-containing structure and a polymerizable unsaturated bond-containing structure, and the polymerizable unsaturated bond equivalent being in a specific range, a cured product having excellent photocurability and a high refractive index can be provided, thus completing the present invention.

[0017] That is, the present invention provides the following inventions.

[0018] [1] An alkali-soluble resin, characterized by having an aromatic ring-containing structure represented by the following formula (1) and a polymerizable unsaturated bond-containing structure represented by the following formula (2), and the polymerizable unsaturated bond equivalent being 700 to 8000 g / equivalent.

[0019] [Chemical Formula 1]

[0020]

[0021] (In formula (1), R 1 represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. R 2 represents an aromatic group with or without substituents. R 3 is a hydrogen atom or a group represented by formula (3). In formula (2), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group. R 9 is a hydrogen atom or a group represented by formula (3). R 3 and R 9At least one of them is a group represented by the formula (3). In the formula (3), R 10 represents a divalent hydrocarbon group which may or may not have a substituent.

[0022] [2] The alkali-soluble resin according to [1] above, characterized in that the acid value is 30 to 150 mgKOH / g.

[0023] [3] The alkali-soluble resin according to [1] or [2] above, characterized in that the epoxy equivalent exceeds 10,000 g / equivalent.

[0024] [4] The alkali-soluble resin according to any one of [1] to [3] above, characterized in that the main chain structure has a novolak structure.

[0025] [5] A photosensitive resin composition, characterized in that it contains the alkali-soluble resin according to any one of [1] to [4] above, a polymerizable compound, and a photoinitiator.

[0026] [6] A cured product, characterized in that it is obtained by curing the alkali-soluble resin according to any one of [1] to [4] above or the photosensitive resin composition according to [5] above.

[0027] [7] A member for a display device, characterized in that it contains the cured product according to [6] above.

[0028] [8] A display device, characterized in that it contains the member for a display device according to [7] above.

[0029] [9] A method for producing an alkali-soluble resin, which is a method for producing an alkali-soluble resin, characterized in that the production method includes: a first step of reacting a compound (b) containing an aromatic group and an unsaturated monocarboxylic acid (c) with an epoxy resin (a) having two or more epoxy groups in one molecule; and a second step of reacting a polyanhydride (d) with the reaction product obtained in the first step,

[0030] adjusting the amounts of the compound (b) containing an aromatic group and the unsaturated monocarboxylic acid (c) in the first step so that the polymerizable unsaturated bond equivalent of the obtained alkali-soluble resin is 700 to 8000 g / equivalent.

[0031]

[10] A method for producing a photosensitive resin composition, which is a method for producing a photosensitive resin composition, characterized in that the production method includes: a step of producing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 to 8000 g / equivalent by the method for producing an alkali-soluble resin according to [9] above; and a step of mixing the obtained alkali-soluble resin, a polymerizable compound, and a photoinitiator.

[0032]

[11] An alkali-soluble resin, characterized by having a structure containing an aromatic ring represented by the following formula (4) and a structure containing a polymerizable unsaturated bond represented by the following formula (2).

[0033] [Chemical formula 2]

[0034]

[0035] (In formula (4), R 23 represents an aromatic group with or without substituents. R 24 is a hydrogen atom or a group represented by formula (3). In formula (2), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group. R 9 is a hydrogen atom or a group represented by formula (3). At least one of R 24 and R 9 is a group represented by formula (3). In formula (3), R 10 represents a divalent hydrocarbon group with or without substituents.)

[0036]

[12] A resin, characterized by having a structure containing an aromatic ring represented by the following formula (1’) and a structure containing a polymerizable unsaturated bond represented by the following formula (2’), and the polymerizable unsaturated double bond equivalent is 600 to 7000 g / equivalent.

[0037] [Chemical formula 3]

[0038]

[0039] (In formula (1’), R 1 represents an oxygen atom or a sulfur atom. R 2 represents an aromatic group with or without substituents. In formula (2’), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.)

[0040]

[13] A photosensitive resin composition, characterized by comprising the resin described in the above

[12] , an alkali-soluble resin, a polymerizable compound, and a photoinitiator.

[0041]

[14] A cured product, characterized in that it is obtained by curing the photosensitive resin composition described in the above

[13] .

[0042] Effects of the Invention

[0043] The alkali-soluble resin and the photosensitive resin composition of the present invention can provide a cured product with excellent photocurability and high refractive index, a member for a display device including the above cured product, and a display device. In addition, the method for producing the alkali-soluble resin of the present invention can easily produce an alkali-soluble resin with excellent photocurability and high refractive index. Detailed Embodiments

[0044] The preferred embodiments of the present invention will be specifically described below. However, the present invention is not limited to the following description and can be appropriately modified and applied within the scope without changing the gist of the present invention. It should be noted that combining two or more of the preferred embodiments of the present invention described below also belongs to the preferred embodiments of the present invention.

[0045] In this specification, “(meth)acrylic acid” means “acrylic acid and / or methacrylic acid”, and “(meth)acrylate” means “acrylate and / or methacrylate”.

[0046] In addition, in this specification, the numerical range “Min~Max” means not less than the minimum value Min and not more than the maximum value Max. In addition, regarding the upper limit value and the lower limit value, in the case where the preferred numerical values are described step by step, the numerical range obtained by appropriately combining the separately described upper limit value and the lower limit value is also a preferred numerical range.

[0047] 1. Alkali-soluble Resin

[0048] <The First Alkali-soluble Resin>

[0049] The first alkali-soluble resin of the present invention is characterized in that it has a structure containing an aromatic ring represented by the above formula (1) and a structure containing a polymerizable unsaturated bond represented by the above formula (2), and the polymerizable unsaturated bond equivalent is 700 to 8000 g / equivalent.

[0050] The reason why the first alkali-soluble resin of the present invention has excellent photocurability and high refractive index is considered to be based on the following reasons. That is, since the first alkali-soluble resin of the present invention has a specific structure containing an aromatic ring, it can provide a cured product with a high refractive index. Furthermore, it is speculated that because a polymerizable unsaturated bond in a specified range is present in the side chain, the photocurability is excellent and the crosslinking density is high during curing, and thus a cured product with an even higher refractive index can be obtained.

[0051] In the above formula (1), R 1represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents. Examples of the above-mentioned substituents include, for example, 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 its salt, a halogen atom, a trifluoromethyl group, a benzoamino group, a boronic acid group, a hydroxyl group, a mercapto group, a thiocyanate group, an alkyl thiocyanate group, an isothiocyanate group, a thiourea group, a sulfonic acid group, a carboxyl group, an aldehyde group, a heterocyclic group, or a group formed by combining them. Among them, from the aspect of a higher refractive index, R 1 is preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom. In addition, if a sulfur atom is present, it can function as an antioxidant, so weather resistance can be imparted to the resin.

[0052] R 2 represents an aromatic group with or without substituents. The above-mentioned aromatic group only needs to have an aromatic ring structure, and can be a monocyclic ring or a polycyclic ring. In addition, it can also contain heteroatoms.

[0053] The rings of the aromatic group constituting the polycyclic ring can be fused to each other, can be bonded by a single bond, or can be connected in a form of sharing one carbon atom. In addition, the rings of the aromatic group constituting the polycyclic ring only need to contain at least an aromatic ring, and can be a group composed only of aromatic rings, or can be a group composed of aromatic rings and non-aromatic rings.

[0054] Examples of the above-mentioned aromatic group include, for example, a monovalent group obtained by removing one hydrogen atom from a benzene-based aromatic compound, a non-benzene-based aromatic compound, or a heteroaromatic compound.

[0055] Examples of the above-mentioned benzene-based aromatic compounds include hydrocarbon compounds containing a benzene ring, such as monocyclic hydrocarbon compounds such as benzene; polycyclic hydrocarbon compounds such as naphthalene, anthracene, triphenylene, pyrene; polycyclic hydrocarbon compounds such as benzenylene, fluorene, etc.

[0056] Examples of the above-mentioned non-benzene-based aromatic compounds include hydrocarbon compounds containing unsaturated cyclic compounds other than the benzene ring, such as annulene, azulene.

[0057] Examples of the above-mentioned heteroaromatic compounds include unsaturated cyclic compounds containing elements other than carbon atoms and hydrogen atoms, such as oxygen atoms, nitrogen atoms, sulfur atoms, etc., such as monocyclic heteroaromatic compounds such as furan, thiophene, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, triazole, thiazole, thiadiazole, tetrazole; polycyclic heterocyclic compounds such as carbazole, benzoxazole, purine, azulene, benzofuran, isobenzofuran, benzothiophene, benzotriazole, isobenzothiophene, indole, isoindole, benzimidazole, benzothiazole, etc.

[0058] Among them, as the above-mentioned aromatic group, a monovalent group obtained by removing one hydrogen atom from a benzene-based aromatic compound is preferred, a phenyl group, a naphthyl group, or a biphenyl group is more preferred, a phenyl group or a biphenyl group is further preferred, and a phenyl group is most preferred.

[0059] The number of carbon atoms of the above-mentioned aromatic group is preferably 1 to 30, more preferably 2 to 20, and further preferably 6 to 12.

[0060] Examples of the substituents that the above-mentioned aromatic group may have include, for example, 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 benzoamino group, a boric acid group, a hydroxyl group, a mercapto group, a thiocyanate group, an alkylthiocyanate group, an isothiocyanate group, a thiourea group, a sulfonic acid group, a carboxyl group, an aldehyde group, a heterocyclic group, or a group formed by combining them. Among them, an alkyl group is preferred.

[0061] The number of carbon atoms of the above-mentioned substituents is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6.

[0062] The above-mentioned aromatic group may have one or two or more of the above-mentioned substituents.

[0063] Specific examples of the above-mentioned aromatic group with or without substituents include, in addition to the above-mentioned specific aromatic groups, aromatic hydrocarbon groups such as tolyl group, xylyl group, benzyl group, phenethyl group, diphenylmethyl group, triphenylmethyl group, styryl group, and cinnamyl group.

[0064] In addition, specific examples of the above-mentioned aromatic group with or without substituents include a monovalent group obtained by removing one hydrogen atom from the following aromatic compounds:

[0065] Thiocyanate compounds such as benzyl thiocyanate;

[0066] Isothiocyanate compounds such as phenyl isothiocyanate, benzyl isothiocyanate, and 3,4-difluorophenyl isothiocyanate;

[0067] Mercaptan compounds such as triphenylmethyl mercaptan, 4-aminobenzenethiol, 4-fluorobenzenethiol, 2,4-difluorobenzenethiol, 2-amino-4-(trifluoromethyl)benzenethiol hydrochloride, 3,5-dichlorobenzenethiol, bis(3,5-dichlorophenyl) disulfide, 4-methoxybenzenethiol, 3-mercapto-4-methyl-1,2,4-triazole, 4-bromobenzenethiol, 2-mercaptobenzoxazole, 2,6-dimethylbenzenethiol, 4,4’,4”-(1,3,5,2,4,6-trioxatrioxane-2,4,6-triyl) tribenzenethiol, 1,3,5-tris[3-(2-mercaptoethylthio)propyl] isocyanate, 6-amino-8-mercaptopurine, 4-mercaptobenzamide, 4-mercaptophenylboronic acid, 2-naphthalenethiol, and diphenyl disulfide;

[0068] Thiocarboxylic acid compounds such as S-phenyl thioacetate;

[0069] Sulfonyl halide compounds such as mesitylene-2-sulfonyl chloride;

[0070] Sulfonic acid compounds such as benzenesulfonic acid;

[0071] Thiourea compounds such as diphenylthiourea;

[0072] Thiadiazole compounds such as 2,5-dimercapto-1,3,4-thiadiazole, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole, 2,5-dithioacetic acid-1,3,4-thiadiazole;

[0073] Azide compounds such as 4-dodecylbenzenesulfonyl azide, 4-acetylaminobenzenesulfonyl azide, diphenylphosphoryl azide;

[0074] Tetrazole compounds such as 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;

[0075] Thiazolidine compounds such as 2,4-thiazolidinedione, 2-thio-4-thiazolidinone, 2-imino-4-thiazolidinone;

[0076] 4-Thiazolecarboxylic acid;

[0077] Ketone compounds such as 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 4-hydroxypropiophenone;

[0078] Dicarboxaldehyde compounds such as 2,6-naphthalenedicarboxaldehyde, 2,7-naphthalenedicarboxaldehyde;

[0079] Triphenylmethyl chloride compounds such as triphenylmethyl chloride, 4,4'-dimethoxytriphenylmethyl chloride.

[0080] Among them, as R 2 , it is preferably an aromatic hydrocarbon group with or without substituents, more preferably a phenyl group, naphthyl group, biphenyl group with or without substituents, and further preferably a phenyl group, biphenyl group with or without substituents.

[0082] R 3 is a hydrogen atom or a group represented by the above formula (3).

[0083] In the above formula (3), R 10 represents a divalent hydrocarbon group which may or may not have a substituent.

[0084] Examples of the divalent hydrocarbon group include divalent aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

[0085] Examples of the divalent aliphatic hydrocarbon group include, for example, alkylene groups such as methylene, ethylene, propylene, isopropylidene, butylene, isobutylene, tert-butylene, pentylene, neopentylene, hexamethylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, undecylene, dodecylene, etc.; alkenylene groups such as vinylidene, propenylene, isopropenylene, butenylene, butadienylene, pentenylene, hexenylene, heptenylene, etc.

[0086] Examples of the divalent alicyclic hydrocarbon group include, for example, cycloalkylene groups such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, norbornylidene, adamantylidene, etc.; cycloalkanefurylidene groups such as cyclopentylidene, cyclohexylidene, etc.

[0087] Examples of the divalent aromatic hydrocarbon group include, for example, arylene groups such as phenylene, tolylene, naphthylene, etc.; cinnamylidene, biphenylylidene, etc.

[0088] Among them, 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.

[0089] The number of carbon atoms of the divalent hydrocarbon group is preferably 2 to 20, more preferably 2 to 8, and further preferably 2.

[0090] Examples of the substituent that the divalent hydrocarbon group may have include a carboxyl group, a hydroxyl group, an alkoxy group, a halogen atom, a hydrocarbon group having 1 to 7 carbon atoms, etc.

[0091] In the above formula (2), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0092] The hydrocarbon group having 1 to 6 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

[0093] Among them, R 4 and R 5 are preferably hydrogen atoms, and R 6Preferably a hydrogen atom or a methyl group.

[0094] In the above formula (2), R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group. As the divalent organic group represented by R 7 and R 8 , examples thereof include a divalent hydrocarbon group, or a group formed by combining a divalent hydrocarbon group with a bond such as -O-, -CO-, -COO-, -NH-, -SO- or -SO2-. As the above divalent hydrocarbon group, the same groups as those described above can be cited. The above divalent hydrocarbon group may include two or more types.

[0095] Among them, as the above divalent organic group, a divalent hydrocarbon group, or a group formed by combining a divalent hydrocarbon group with at least one selected from the group consisting of -O-, -CO- and -COO- is preferred.

[0096] Examples of the group formed by combining the above divalent hydrocarbon group with at least one selected from the group consisting of -O-, -CO- and -COO- include, for example, -R a -COO-R b -, -R a -O-(CO)-R b -(wherein, R a and R b are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms) and the like.

[0097] R 7 and R 8 are preferably a direct bond, a divalent hydrocarbon group, or a group composed of a combination of a divalent hydrocarbon group and at least one selected from the group consisting of -O- and -COO-, more preferably a direct bond or a divalent aliphatic hydrocarbon group, and still more preferably a direct bond.

[0098] In the above formula (2), R 9 is a hydrogen atom or the group represented by the above formula (3). In addition, at least one of the above R 3 and R 9 is the group represented by the above formula (3). The group represented by the above formula (3) has a carboxyl group as an acid group. By making the resin have such a group, it becomes alkali-soluble. By adjusting the amount of such an acid group, the alkali-soluble resin becomes a resin with excellent developability.

[0099] The above first alkali-soluble resin preferably has a novolak structure in the main chain structure. The novolak structure refers to a structure in which a benzene ring or a naphthalene ring in the main chain is bonded to a divalent hydrocarbon group with or without a substituent to form a repeating unit.

[0100] As the alkali-soluble resin having an aromatic ring-containing structure represented by the above formula (1) and a polymerizable unsaturated bond-containing structure represented by the above formula (2), specifically, an alkali-soluble resin having a structural unit (A) represented by the following formula (a) and a structural unit (B) represented by the following formula (b) is preferably exemplified.

[0101] [Chemical formula 4]

[0102]

[0103] [Chemical formula 5]

[0104]

[0105] (In the formula, A represents a benzene ring or a naphthalene ring. R 1 ~R 9 are the same as above respectively. R 11 and R 14 are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms. R 12 and R 15 are the same or different and represent a substituent bonded to A. a represents the number of R 12 and is an integer of 0 to 5. b represents the number of R 15 and is an integer of 0 to 5. When R 12 and R 15 are each two or more, they may be the same or different from each other. R 13 and R 16 are the same or different and represent a direct bond or a divalent organic group.)

[0106] In this specification, a "structural unit" refers to a repeating unit that constitutes an alkali-soluble resin.

[0107] In the above formulas (a) and (b), A represents a benzene ring or a naphthalene ring. From the viewpoint of the balance between high refractive index and developability, A is preferably a benzene ring.

[0108] In the above formulas (a) and (b), R 11 and R 14 represent a divalent hydrocarbon group having 1 to 20 carbon atoms. As the above divalent hydrocarbon group, groups similar to the above divalent hydrocarbon group can be exemplified. Among them, from the aspect of easy availability, as the divalent hydrocarbon group represented by R 11 and R 14 , a divalent aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred.

[0109] As the number of carbon atoms of the above divalent hydrocarbon group, 1 to 14 is preferred, 1 to 10 is more preferred, and 1 is further preferred.

[0110] In the above divalent hydrocarbon group, 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. Further, the above divalent hydrocarbon group may have a substituent such as an alkoxy group.

[0111] R 12 and R 15 are the same or different and represent substituents bonded to A.

[0112] Examples of the substituent bonded to A include a hydroxyl group or an organic group having 1 to 20 carbon atoms.

[0113] Examples of the organic group having 1 to 20 carbon atoms include groups having 1 to 20 carbon atoms in the group obtained by making the above divalent organic group monovalent. Among them, from the viewpoint of good curability, R 12 and R 15 are preferably -OH, -O-CH2-(C2H3O), -CR c R d -(C6H4)-O-CH2-(C2H3O), -CR c R d -(C6H4)-OH (wherein R c and R d are the same or different and represent a hydrogen atom or a methyl group), or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, still more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a methyl group.

[0114] In the above formula (a), a represents the number of substituents R 12 and is an integer of 0 to 5. From the viewpoint of good developability, a is preferably 0 to 3, more preferably 1 to 3, and still more preferably 1. When a is 2 or more, that is, when there are two or more R 12 , R 12 may be the same or different from each other.

[0115] In the above formula (b), b represents the number of substituents R 15 and is an integer of 0 to 5. From the viewpoint of good developability, b is preferably 0 to 3, more preferably 1 to 3, and still more preferably 1. When b is 2 or more, that is, when there are two or more R 15 , R 15 may be the same or different from each other.

[0116] R 13 and R 16 are the same or different and represent a direct bond or a divalent organic group. Examples of the above divalent organic group include the same groups as the above divalent organic group. Among them, R 13and R 16 is preferably a direct bond.

[0117] The above-mentioned first alkali-soluble resin may have one or more than two kinds of the above-mentioned structural units (A).

[0118] The content ratio of the above-mentioned structural unit (A) in the above-mentioned alkali-soluble resin is preferably 51 to 93 mol%, more preferably 55 to 92 mol%, further preferably 60 to 91 mol%, still more preferably 60 to 90 mol%, particularly preferably 60 to 80 mol%, and most preferably 60 to 75 mol% with respect to 100 mol% of all the structural units.

[0119] The above-mentioned first alkali-soluble resin may have one or more than two kinds of the above-mentioned structural units (B).

[0120] The content ratio of the above-mentioned structural unit (B) in the above-mentioned alkali-soluble resin is preferably 7 to 49 mol%, more preferably 8 to 45 mol%, further preferably 9 to 40 mol%, and still more preferably 10 to 40 mol% with respect to 100 mol% of all the structural units.

[0121] The above-mentioned first alkali-soluble resin may further have other structural units (C) other than the above-mentioned structural units (A) and (B), and in addition, the above-mentioned alkali-soluble resin may have one or more than two kinds of structural units (C).

[0122] Examples of the above-mentioned structural unit (C) include a structural unit represented by the following formula (c).

[0123] [Chemical formula 6]

[0124]

[0125] (In the formula, A represents a benzene ring or a naphthalene ring. R 3 is the same as above. R 17 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R 18 represents a substituent bonded to A. c represents the number of R 18 , which is an integer of 0 to 5. When there are two or more R 18 , they may be the same or different from each other. R 19 represents a direct bond or a divalent organic group. R 20 represents an organic group.)

[0126] Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the above-mentioned R 17 include the same groups as the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the above-mentioned R 11 , and are preferably a divalent aliphatic hydrocarbon group, more preferably an alkylene group.

[0127] As the substituent represented by the above R 18 As the substituent represented by the above R 12 The same groups as the substituent represented by the above R can be mentioned. Preferably, they are -OH, -O-CH2-(C2H3O), -CR c R d -(C6H4)-O-CH2-(C2H3O), -CR c R d -(C6H4)-OH (wherein R c and R d are the same or different and represent a hydrogen atom or a methyl group), or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. More preferably, it is an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Further preferably, it is an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Particularly preferably, it is a methyl group.

[0128] In the above formula (c), c represents the number of substituents R 18 and is an integer from 0 to 5. From the viewpoint of good developability, c is preferably 0 to 3, more preferably 1 to 3, and further preferably 1. When c is 2 or more, that is, when there are two or more R 18 R 18 may be the same or different from each other.

[0129] R 19 represents a direct bond or a divalent organic group. As the divalent organic group represented by R 19 the same groups as the divalent organic group represented by the above R 13 can be mentioned. Among them, R 19 is preferably a direct bond.

[0130] R 20 represents an organic group. As the organic group represented by R 20 groups that make the above divalent organic group monovalent can be mentioned, etc. Among them, a group having an acid group is preferred. In addition, a group not having a double bond is also preferred. By appropriately selecting the organic group of R 20 the developability and the reactivity of the double bond can be controlled.

[0131] As the above acid group, functional groups that undergo a neutralization reaction with alkaline water such as a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, and a sulfonic acid group can be mentioned. Among them, from the viewpoint of good developability, a carboxyl group or a carboxylic anhydride group is preferred, and a carboxyl group is more preferred.

[0132] As the group having the above acid group, for example, -R e -R f (wherein R e represents a divalent organic group. R f represents an acid group) and the like can be mentioned.

[0133] As the divalent organic group described above, the same groups as the above-described organic groups can be cited. Among them, a group composed of a combination of a divalent hydrocarbon group and at least one selected from the group consisting of -O- and -COO- is preferred.

[0134] R 20 The organic group represented by is also preferably a functional group having a radical scavenging ability or an ultraviolet absorbing ability. By having such a functional group, the weather resistance of the resin can be improved. As the above functional group, a hindered phenol group, a hindered amine group, a benzotriazole group, a triazine group, a cyanoacrylate group, a melamine group, a benzoate group, etc. can be cited.

[0135] As R 20 The number of carbon atoms of the organic group represented by is preferably 1 to 20, more preferably 1 to 16, and further preferably 2 to 12. By positioning the acid group represented by the above R f at a position far from the main chain of the alkali-soluble resin, the developability can be improved.

[0136] The above first alkali-soluble resin may have one or two or more of the above structural units (C).

[0137] The content ratio of the above structural unit (C) is preferably 0 to 20 mol%, more preferably 0.1 to 20 mol%, further preferably 0.5 to 15 mol%, and even more preferably 1 to 10 mol% with respect to all the structural units of 100 mol%.

[0138] In addition, the above first alkali-soluble resin may have a structural unit (D) represented by the following formula (d). By performing chain extension by introducing the above structural unit (D), the resin can be designed to have an arbitrary molecular weight.

[0139] [Chemical formula 7]

[0140]

[0141] In the above formula (d), L represents a direct bond or a linking group. R 21 and R 22 are the same or different and represent substituents. d represents the number of R 21 and is an integer of 0 to 4. e represents the number of R 22 and is an integer of 0 to 4. When R 21 and R 22 are plural, they may be the same or different from each other.

[0142] As the above linking group, a divalent bond such as an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, -SO2-, -NH-, or a combination thereof can be cited.

[0143] The above-mentioned alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms. Additionally, it can be any of linear, branched, or cyclic forms.

[0144] The above-mentioned alkylene group and arylene group may have substituents. As the above-mentioned substituents, there is no particular limitation, and examples thereof include halogen atoms such as fluorine atom, chlorine atom, and iodine atom, or alkyl groups.

[0145] The structural unit (D) represented by the above formula (d) is preferably a structural unit derived from any one compound selected from bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z, more preferably a structural unit derived from bisphenol S, bisphenol A, or bisphenol F, and further preferably a structural unit derived from bisphenol S.

[0146] As the above-mentioned structural unit (D), preferably, the structural units represented by the following formula (d-1), (d-2), or (d-3) can be cited.

[0147] [Chemical formula 8]

[0148]

[0149] When the above-mentioned first alkali-soluble resin has the above-mentioned structural unit (D), the content ratio of the above-mentioned structural unit (D) relative to all structural units is preferably 0.1 to 10 mol%, more preferably 0.2 to 5 mol%, and further preferably 0.5 to 2 mol% based on 100 mol%.

[0150] The polymerizable unsaturated bond equivalent of the above-mentioned first alkali-soluble resin is 700 to 8000 g / equivalent. By making the polymerizable unsaturated bond equivalent within the above range, the photocurability of the alkali-soluble resin can be improved. From the aspect of reducing the brittleness of the cured product, the polymerizable unsaturated bond equivalent of the above-mentioned alkali-soluble resin is preferably 750 to 6000 g / equivalent, more preferably 800 to 5000 g / equivalent, further preferably 900 to 4000 g / equivalent, and even more preferably 900 to 2000 g / equivalent.

[0151] The above-mentioned polymerizable unsaturated bond equivalent is the mass of the solid content of the alkali-soluble resin solution per 1 mol of polymerizable unsaturated bond of the above-mentioned alkali-soluble resin. In this specification, the above-mentioned polymerizable unsaturated bond refers to a polymerizable double bond. The mass of the solid content of the alkali-soluble resin solution refers to the mass of the monomer components constituting the above-mentioned alkali-soluble resin. The above-mentioned polymerizable unsaturated bond equivalent can be obtained by dividing the mass (g) of the solid content of the alkali-soluble resin in the alkali-soluble resin solution by the amount (mol) of the polymerizable unsaturated bond of the alkali-soluble resin. In addition, it can also be calculated by measuring the number of olefinic double bonds contained in 1 g of the alkali-soluble resin according to the test method of iodine value described in JIS K 0070:1992.

[0152] The acid value of the above-mentioned first alkali-soluble resin is preferably 30 to 150 mgKOH / g. From the aspect of further improving the developability, the above-mentioned acid value is more preferably 40 to 120 mgKOH / g, and further preferably 45 to 90 mgKOH / g.

[0153] The above-mentioned acid value is the acid value per 1 g of the resin solid content obtained by neutralization titration using a potassium hydroxide (KOH) solution, and can be obtained by the method described in the following examples.

[0154] The epoxy equivalent of the above-mentioned first alkali-soluble resin is preferably more than 10000 g / equivalent. If the epoxy equivalent is within the above range, the alkali-soluble resin of the present invention hardly has an epoxy group. Therefore, the storage stability is good. The epoxy equivalent of the above-mentioned alkali-soluble resin is more preferably more than 13000 g / equivalent.

[0155] The above-mentioned epoxy equivalent can be obtained by the method according to JIS K7236:2001. In addition, it can be obtained by dividing the mass (g) of the resin solid content by the number of moles (mol) of the epoxy group contained in the resin.

[0156] The weight average molecular weight of the above-mentioned first alkali-soluble resin is preferably 1000 to 100000. From the aspect of good curability, the weight average molecular weight of the above-mentioned alkali-soluble resin is more preferably 2000 to 50000, further preferably 3000 to 20000, still further preferably 3500 to 15000, and particularly preferably 4000 to 10000.

[0157] The above-mentioned weight average molecular weight can be obtained by gel permeation chromatography (GPC).

[0158] From the aspect of improving the film strength, the glass transition temperature (Tg) of the above-mentioned first alkali-soluble resin is preferably 40 °C or higher, more preferably 60 °C or higher, and further preferably 80 °C or higher. From the aspect of good developability, it is preferably 300 °C or lower, more preferably 250 °C or lower, and further preferably 200 °C or lower. The glass transition temperature (Tg) of the above-mentioned first alkali-soluble resin is preferably 40 to 300 °C, more preferably 60 to 250 °C, and further preferably 80 to 200 °C.

[0159] The above glass transition temperature can be determined by the method according to JIS-K7121.

[0160] <Second alkali-soluble resin>

[0161] The second alkali-soluble resin of the present invention is characterized by having a structure containing an aromatic ring represented by the following formula (4) and a structure containing a polymerizable unsaturated bond represented by the following formula (2).

[0162] [Chemical formula 9]

[0163]

[0164] (In formula (4), R 23 represents an aromatic group with or without substituents. R 24 is a hydrogen atom or a group represented by formula (3). In formula (2), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group. R 9 is a hydrogen atom or a group represented by formula (3). At least one of R 24 and R 9 is a group represented by formula (3). In formula (3), R 10 represents a divalent hydrocarbon group with or without substituents.)

[0165] It is considered that the second alkali-soluble resin of the present invention can provide a cured product with excellent photocurability and high refractive index because, by having the structure of formula (4) containing a sulfur atom and an aromatic group, the refractive index of the cured product can be increased, and by having the structure of formula (2), the photocurability can be made good.

[0166] In the above formula (4), R 23 represents an aromatic group with or without substituents. As the aromatic group with or without substituents represented by R 23 , examples thereof may include those of R in the above formula (1) 2An aromatic group with or without substituents represented by the same group.

[0167] In the above formula (4), R 24 is a hydrogen atom or a group represented by formula (3).

[0168] The group represented by the above formula (3) is the same group as the group represented by formula (3) described in the item of the above <First alkali-soluble resin>.

[0169] The structure containing a polymerizable unsaturated bond represented by the above formula (2) is the same structure as the structure containing a polymerizable unsaturated bond represented by formula (2) described in the item of the above <First alkali-soluble resin>.

[0170] Similar to the above first alkali-soluble resin, the above second alkali-soluble resin preferably has a novolak structure in the main chain structure.

[0171] As the alkali-soluble resin having the structure containing an aromatic ring represented by the above formula (4) and the structure containing a polymerizable unsaturated bond represented by the above formula (2), preferably, an alkali-soluble resin having a structural unit (E) represented by the following formula (e) and a structural unit (B) described in the item of the above <First alkali-soluble resin> can be cited.

[0172] [Chemical formula 10]

[0173]

[0174] (In the formula, A represents a benzene ring or a naphthalene ring. R 23 and R 24 are the same as above respectively. R 25 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R 26 represents a substituent bonded to A. f represents the number of R 26 and is an integer from 0 to 5. When there are two or more R 26 , they may be the same or different from each other. R 27 represents a direct bond or a divalent organic group.)

[0175] In the formula, A represents a benzene ring or a naphthalene ring, and preferably represents a benzene ring.

[0176] As the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 25 , groups similar to the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 11 in the formula (a) described in the item of the above <First alkali-soluble resin> can be cited.

[0177] As the substituent represented by R 26 , it can be cited as the same as R 12 in the above formula (a).The substituents represented are the same groups.

[0178] f represents R 26 The number of which is an integer from 0 to 5. From the aspect of good developability, f is preferably 0 to 3, more preferably 1 to 3, and preferably 1.

[0179] The above-mentioned second alkali-soluble resin may have one or more than two of the above-mentioned structural units (E).

[0180] The content ratio of the structural unit (E) in the above-mentioned second alkali-soluble resin is preferably 1 to 99 mol%, more preferably 20 to 95 mol%, further preferably 40 to 93 mol%, still further preferably 50 to 90 mol%, particularly preferably 60 to 85 mol%, and most preferably 60 to 80 mol% with respect to 100 mol% of all the structural units.

[0181] The content ratio of the structural unit (B) in the above-mentioned second alkali-soluble resin is preferably 1 to 80 mol%, more preferably 2 to 70 mol%, further preferably 3 to 50 mol%, still further preferably 5 to 40 mol%, particularly preferably 10 to 40 mol%, and most preferably 15 to 40 mol% with respect to 100 mol% of all the structural units.

[0182] In addition to the above-mentioned structural units (E) and (B), the above-mentioned second alkali-soluble resin may further have other structural units. As the above-mentioned other structural units, the structural unit (C) or the structural unit (D) described in the item of the above-mentioned <first alkali-soluble resin> can be cited.

[0183] When the above-mentioned second alkali-soluble resin has the above-mentioned structural unit (C) and / or structural unit (D), their content ratios are preferably the same as the content ratios in the above-mentioned first alkali-soluble resin.

[0184] The polymerizable unsaturated bond equivalent of the above-mentioned second alkali-soluble resin is preferably 300 to 8000 g / equivalent, more preferably 500 to 6000 g / equivalent, further preferably 700 to 5000 g / equivalent, still further preferably 800 to 4000 g / equivalent, particularly preferably 800 to 2000 g / equivalent.

[0185] The acid value, epoxy equivalent, weight-average molecular weight, and glass transition temperature of the above-mentioned second alkali-soluble resin are preferably the same as the acid value, epoxy equivalent, weight-average molecular weight, and glass transition temperature of the above-mentioned first alkali-soluble resin, respectively.

[0186] 2. Manufacturing method of the alkali-soluble resin

[0187] <Manufacturing method of the first alkali-soluble resin>

[0188] The method for producing the first alkali-soluble resin of the present invention is not particularly limited as long as the above-mentioned first alkali-soluble resin can be obtained. From the aspect of being able to efficiently produce the first alkali-soluble resin of the present invention, a production method including the following steps is preferred.

[0189] (1) The first step of reacting a compound (b) containing an aromatic group and an unsaturated monocarboxylic acid (c) with an epoxy resin (a) having two or more epoxy groups in one molecule

[0190] (2) The second step of reacting a polyanhydride (d) with the reaction product obtained in the above first step

[0191] In addition, in the above production method, by adjusting the amounts of the compound (b) containing an aromatic group and the unsaturated monocarboxylic acid (c) in the first step so that the polymerizable unsaturated bond equivalent of the obtained alkali-soluble resin is 700 to 8000 g / equivalent, the first alkali-soluble resin of the present invention can be produced.

[0192] Such a method for producing the first alkali-soluble resin is also one of the present inventions, that is, it is a method for producing an alkali-soluble resin, characterized in that the production method includes: a first step of reacting a compound (b) containing an aromatic group and an unsaturated monocarboxylic acid (c) with an epoxy resin (a) having two or more epoxy groups in one molecule; and a second step of reacting a polyanhydride (d) with the reaction product obtained in the first step, and adjusting the amounts of the compound (b) containing an aromatic group and the unsaturated monocarboxylic acid (c) in the first step so that the polymerizable unsaturated bond equivalent of the obtained alkali-soluble resin is 700 to 8000 g / equivalent.

[0193] Hereinafter, each step will be described.

[0194] In the method for producing the first alkali-soluble resin of the present invention, the epoxy resin (a) having two or more epoxy groups in one molecule as the starting material is not particularly limited, and any known epoxy resin having two or more epoxy groups in one molecule can be used. Examples include bisphenol type epoxy resins; biphenyl type epoxy resins; alicyclic epoxy resins; polyfunctional glycidylamine resins such as tetraglycidyl amino diphenyl methane; polyfunctional glycidyl ether resins such as tetraphenyl glycidyl ether ethane; phenol novolak type epoxy resins, cresol novolak type epoxy resins; reaction products of polyphenolic compounds obtained by condensation reactions of phenolic compounds such as phenol, o-cresol, m-cresol, and naphthol with aromatic aldehydes having phenolic hydroxyl groups and epichlorohydrin; reaction products of polyphenolic compounds obtained by addition reactions of phenolic compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene and epichlorohydrin; products obtained by epoxidizing the ring-opening polymer of 4-vinylcyclohexene-1-oxide with a peracid; epoxy resins having heterocycles such as triglycidyl isocyanurate; etc. In addition, chain-extended products obtained by reacting two or more molecules of these epoxy resins with chain extenders such as polybasic acids, polyphenolic compounds, polyfunctional amino compounds, or polythiols can also be used. Or, it can also be a homopolymer or copolymer of monomers having an epoxy group such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among them, in order to increase the number of olefinically unsaturated bonds (polymerizable unsaturated double bonds) in one molecule of the alkali-soluble resin and improve the photocurability, a phenol novolak type epoxy resin is preferably used as the raw material.

[0195] As the epoxy resin (a) having two or more epoxy groups in one molecule as the above-mentioned starting material, from the aspect of making the developability and photocurability of the obtained alkali-soluble resin more excellent, an epoxy resin having an epoxy equivalent of 500 g / equivalent or less is preferred. An epoxy resin having an epoxy equivalent of 400 g / equivalent or less is more preferred, and an epoxy resin having an epoxy equivalent of 300 g / equivalent or less is further preferred.

[0196] As the above-mentioned compound (b) containing an aromatic group, as long as it is a compound having an aromatic group and a group capable of reacting with an epoxy group, there is no particular limitation, and examples include the above-mentioned aromatic compounds, etc.

[0197] As the above-mentioned aromatic group, examples include the above-mentioned groups having an aromatic ring structure.

[0198] As the above-mentioned group capable of reacting with an epoxy group, examples include acidic groups, amino groups, hydroxyl groups, etc.

[0199] As the above-mentioned acidic group, examples include carboxyl groups, phenolic hydroxyl groups, mercapto groups, etc., and phenolic hydroxyl groups and mercapto groups are preferably cited.

[0200] The above-mentioned compound containing an aromatic group is preferably an aromatic group-containing acid compound having the above-mentioned aromatic group and an acidic group.

[0201] As the above-mentioned compound containing an aromatic group, there is no particular limitation as long as it can impart the above-mentioned aromatic ring structure to the resulting resin. Preferred examples include phenol derivatives such as phenylphenol, benzenethiol derivatives such as tolyl mercaptan and benzenethiol, and alcohol derivatives such as hydroxybenzeneethanol. Among them, from the aspect that the generated thioether bond can balance high refractive index and high-speed developability, benzenethiol derivatives are preferred, and benzenethiol is most preferred. They can be used alone or in combination of two or more.

[0202] In addition, if hydroxybenzeneethanol is used or combined, an acid group for chain growth can be introduced into the alkali-soluble resin by reacting a polyanhydride in the subsequent step (2). Since such an acid group is located far from the main chain, the developability and reactivity during curing become good.

[0203] As the above-mentioned unsaturated monocarboxylic acid (c), there is no particular limitation as long as it has an unsaturated bond and a carboxyl group. Unsaturated monocarboxylic acids having 3 to 20 carbon atoms are preferred. More preferably, unsaturated monocarboxylic acids having 3 to 10 carbon atoms are used, and further preferably, unsaturated monocarboxylic acids having 3 to 4 carbon atoms are used.

[0204] Examples of the above-mentioned unsaturated monocarboxylic acid (c) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, β-acryloyloxypropionic acid, reaction products of (meth)acrylic acid hydroxyalkyl esters having one hydroxyl group and one (meth)acryloyl group with dianhydrides, reaction products of polyfunctional (meth)acrylates having one hydroxyl group and two or more (meth)acryloyl groups with dianhydrides, and the like. Among them, unsaturated monocarboxylic acids having a (meth)acryloyl group such as acrylic acid and methacrylic acid are preferred. From the aspect of providing a cured product with particularly excellent solvent resistance for the resulting alkali-soluble resin, methacrylic acid is particularly preferred. They can be used alone or in combination of two or more.

[0205] The addition of the above-mentioned compound containing an aromatic group (b) and the above-mentioned unsaturated monocarboxylic acid (c) can be carried out all at once, or in batches or sequentially. From the aspect of being able to suppress side reactions, addition in batches or sequentially is preferred.

[0206] In the method for producing the alkali-soluble resin of the present invention, in the first step of reacting a compound (b) containing an aromatic group and an unsaturated monocarboxylic acid (c) with an epoxy resin (a) having two or more epoxy groups in one molecule, the epoxy resin (a) can be reacted with the unsaturated monocarboxylic acid (c), and then the compound (b) containing an aromatic group can be reacted; alternatively, the unsaturated monocarboxylic acid (c) and the compound (b) containing an aromatic group can be reacted with the epoxy resin (a) at once; or the epoxy resin (a) can be reacted with the compound (b) containing an aromatic group, and then the unsaturated monocarboxylic acid (c) can be reacted.

[0207] In the above first step, when the compound (b) containing an aromatic group is reacted with the epoxy resin (a), regarding the addition amount of the compound (b) containing an aromatic group, relative to 1 chemical equivalent (molar equivalent) of the epoxy groups of the epoxy resin (a), it is preferably charged and reacted in such a manner that the acid group in the compound (b) containing an aromatic group is 0.51 to 0.93 moles, more preferably 0.55 to 0.92 moles, further preferably 0.6 to 0.91 moles, still further preferably 0.6 to 0.9 moles, particularly preferably 0.6 to 0.8 moles, and most preferably 0.6 to 0.75 moles.

[0208] The reaction between the epoxy resin (a) and the compound (b) containing an aromatic group can be carried out by replacing the reaction tank with an inert gas such as nitrogen to reduce the oxygen concentration, thereby accelerating the reaction rate. The oxygen concentration in the reaction tank is preferably 1% by volume or less, more preferably 0.5% by volume or less, and further preferably 0.3% by volume or less. In order to reduce the oxygen concentration in the reaction solution, it is also preferred to bubble an inert gas such as nitrogen through the solution.

[0209] In the above first step, relative to 1 mole of the epoxy groups of the epoxy resin (a), it is preferred that the total amount of the compound (b) containing an aromatic group and the unsaturated monocarboxylic acid (c) is 0.8 to 1.2 moles. By using such a ratio, it is easy to make the curability of the finally obtained alkali-soluble resin and the physical properties of the cured product good. It is preferably 0.85 to 1.15 moles, and more preferably 0.9 to 1.1 moles.

[0210] By adjusting the amounts of the compound (b) containing an aromatic group and the unsaturated monocarboxylic acid (c) in the above first step in this way, an alkali-soluble resin with a polymerizable unsaturated bond equivalent of 700 to 8000 g / equivalent can be obtained.

[0211] As described above, in the first step of the method for producing the first alkali-soluble resin of the present invention, the reaction between the compound (b) containing an aromatic group and the unsaturated monocarboxylic acid (c) and the epoxy resin (a) can be carried out for either one first, or they can be reacted simultaneously.

[0212] These reactions can be carried out in the presence or absence of diluents such as the polymerizable compounds and solvents described below, in the coexistence of polymerization inhibitors such as hydroquinone and oxygen, and reaction catalysts such as tertiary amines, tertiary phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine, lithium chloride, quaternary ammonium salts, and quaternary phosphonium salts, usually at 60 to 140 °C.

[0213] As the reaction catalyst, from the aspects of reaction efficiency, stability during the reaction, and storage stability of the alkali-soluble resin, tertiary phosphines are preferred, and triphenylphosphine is particularly preferred.

[0214] The amount of the above reaction catalyst is not particularly limited, and relative to 100 parts by mass of the epoxy resin (a) having two or more epoxy groups in one molecule, it is preferably 0.05 to 5 parts by mass. More preferably, it is 0.1 to 3 parts by mass, and still more preferably, it is 0.2 to 2 parts by mass.

[0215] In addition, in the first step, a polymerization inhibitor can be used. As the polymerization inhibitor, there is no particular limitation, and known polymerization inhibitors can be used, such as benzoquinone, hydroquinone-based compounds (such as hydroquinone, hydroquinone monomethyl ether, p-tert-butylhydroquinone, p-benzoquinone, etc.), phenol-based compounds (such as 2,6-di-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), etc.), catechol-based compounds (such as p-tert-butylcatechol, etc.), amine-based compounds (such as N,N-diethylhydroxylamine, etc.), 1,1-diphenyl-2-picrylhydrazyl, tris(p-nitrophenyl)methyl, phenothiazine, piperidine 1-oxyl radicals (such as 2,2,6,6-tetramethylpiperidine 1-oxyl radical, etc.), oxygen, etc.

[0216] When the above polymerization inhibitor is used in the first step, the amount of the polymerization inhibitor is preferably 0.001 to 1% by mass relative to 100% by mass of the epoxy resin (a) having two or more epoxy groups in one molecule. More preferably, it is 0.01 to 0.5% by mass.

[0217] The above reaction can 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, dimethyl glutarate, dimethyl succinate, and dimethyl adipate; ketones such as methyl isobutyl ketone and methyl ethyl ketone; ethers such as (di)ethylene glycol dimethyl ether, etc.

[0218] Regarding the temperature of the reaction in the above first step, there is no particular limitation as long as the reaction proceeds, and it is preferably 40 °C to 140 °C. By carrying out the reaction at such a temperature, the reaction can be carried out efficiently. The reaction temperature is more preferably 50 °C to 135 °C, and still more preferably 60 °C to 130 °C.

[0219] In addition, in the above first step, a carboxylic acid without a double bond can be reacted with a compound (b) containing an aromatic group and an unsaturated monocarboxylic acid (c) together with an epoxy resin (a). By reacting the carboxylic acid without a double bond together, the double bond equivalent, epoxy equivalent, glass transition temperature, etc. of the alkali-soluble resin can be adjusted.

[0220] Examples of the carboxylic acid without a double bond include propionic acid, acetic acid, butyric acid, capric acid, 2-ethylhexyl carboxylic acid, etc.

[0221] In the above first step, an acid compound having a functional group with radical scavenging ability or ultraviolet absorption ability can also be reacted with a compound (b) containing an aromatic group and an unsaturated monocarboxylic acid (c) together with an epoxy resin (a). By reacting such an acid compound, weather resistance can be imparted to the resin.

[0222] Examples of the functional group with radical scavenging ability or ultraviolet absorption ability include the above functional group with radical scavenging ability or ultraviolet absorption ability.

[0223] Examples of the acid group of the above acid compound include the above acid group, and among them, a carboxyl group is preferred.

[0224] Specific examples of the acid compound having a functional group with radical scavenging ability or ultraviolet absorption ability include, for example, 3,5-ditert-butyl-4-hydroxybenzoic acid, 3-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid, 3-methylsalicylic acid, trimethylhydroquinone, 3-phenylsalicylic acid, 4-hydroxy-3,5-dimethylbenzoic acid, 3,5-ditert-butylsalicylic acid, mycophenolic acid, xanthohumol, monoethyl 3,5-ditert-butyl-4-hydroxybenzylphosphonate, etc., and among them, 3,5-ditert-butyl-4-hydroxybenzoic acid and 3-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid are preferred.

[0225] In the second step of the manufacturing method of the above alkali-soluble resin, by reacting a polyanhydride (d) with the reaction product (intermediate) obtained in the above first step, the polyanhydride (d) reacts with the hydroxyl groups present in the reaction product, and an alkali-soluble resin of the present invention having a carboxyl group introduced therein can be obtained. The obtained alkali-soluble resin can be alkali-developed, and thus can be used as an alkali-developable curable resin for image formation and the like.

[0226] The polyanhydride (d) used in the above second step is not particularly limited, and a polyanhydride having 3 to 30 carbon atoms is preferred. A polyanhydride having 4 to 20 carbon atoms is more preferred, and a polyanhydride having 4 to 10 carbon atoms is further preferred.

[0227] As the above-mentioned polyanhydride (d), examples thereof include dibasic anhydrides such as phthalic anhydride, succinic anhydride, octenyl succinic anhydride, penta(dodecenyl) succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylene tetrahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic acid; aliphatic or aromatic tetracarboxylic dianhydrides such as biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride. These polyanhydrides can be used singly or in combination of two or more. Among them, dibasic anhydrides are preferably used. In addition, from the aspect that the obtained alkali-soluble resin can provide a cured product with particularly excellent solvent resistance, polyanhydrides such as phthalic anhydride, which make the alkali-soluble resin have a cyclic structure in the structure, are particularly preferred.

[0228] In the above-mentioned second step, relative to 1 chemical equivalent of the hydroxyl group of the reaction product obtained in the reaction of the first step, it is preferred that the polyanhydride (d) reacts in a proportion of 0.1 mol or more and 1.1 mol or less. By reacting the polyanhydride (d) in this way, the addition reaction of the polyanhydride (d) can be efficiently carried out, and carboxyl groups can be appropriately introduced into the obtained alkali-soluble resin.

[0229] The reaction between the reaction product obtained in the reaction of the first step in the above-mentioned second step and the polyanhydride (d) can be carried out in the presence or absence of diluents such as the following polymerizable compounds and solvents, and in the coexistence of the above-mentioned polymerization inhibitor and reaction catalyst as needed, in the same manner as the reaction of the first step.

[0230] In the above-mentioned second step, a reaction catalyst can be used, preferably a tertiary phosphine, more preferably triphenylphosphine.

[0231] Regarding the reaction temperature in the above-mentioned second step, there is no particular limitation as long as the reaction proceeds, and it is preferably 45°C to 130°C. By carrying out the reaction at such a temperature, the reaction can be efficiently carried out. The reaction temperature is more preferably 50°C to 120°C, and further preferably 55°C to 110°C.

[0232] In addition, in the case where the above-mentioned alkali-soluble resin has the above-mentioned structural unit (D), for example, before the above-mentioned first step, the epoxy resin (a) is previously reacted with a compound capable of introducing the above-mentioned structural unit (D), thereby extending the epoxy resin (a), and the extended epoxy resin (a) is supplied to the above-mentioned first step, whereby an alkali-soluble resin having the above-mentioned structural unit (D) can be produced.

[0233] Examples of the compound capable of introducing the above-mentioned structural unit (D) include bisphenol compounds that are the source of the above-mentioned structural unit (D).

[0234] In the above reaction, a reaction catalyst can be used. As the reaction catalyst used in this reaction, the same catalysts as those used in the above first step and second step can be cited.

[0235] The method for producing the above first alkali-soluble resin only needs to include the above first step and second step, and other steps can also be included.

[0236] <Method for Producing Second Alkali-Soluble Resin>

[0237] As the method for producing the above second alkali-soluble resin, in addition to using a compound containing an aromatic group and a compound containing a sulfur atom, and the polymerizable unsaturated bond equivalent of the alkali-soluble resin not being limited to 700 to 8000 g / equivalent, a method including the same first step and second step as those in the method for producing the above first alkali-soluble resin can be cited.

[0238] The compound (b') containing an aromatic group used in the method for producing the above second alkali-soluble resin preferably contains a sulfur atom. The compound (b') containing an aromatic group is preferably a compound in which the group capable of reacting with an epoxy group in the compound (b) containing an aromatic group used in the method for producing the above first alkali-soluble resin contains a sulfur atom. The compound (b') containing an aromatic group is preferably a compound containing the above aromatic group and a mercapto group.

[0239] In addition, in the first step of the method for producing the above second alkali-soluble resin, regarding the addition amount of the compound (b') containing an aromatic group, relative to 1 chemical equivalent (molar equivalent) of the epoxy group of the epoxy resin (a), it is preferably charged and reacted in such a way that the acid group in the compound (b') containing an aromatic group is 0.01 to 0.99 mol, more preferably 0.2 to 0.95 mol, further preferably 0.4 to 0.93 mol, still further preferably 0.6 to 0.9 mol, particularly preferably 0.6 to 0.85 mol, and most preferably 0.6 to 0.80 mol.

[0240] In the above second alkali-soluble resin, the polymerizable unsaturated bond equivalent is not limited, and by adjusting the amounts of the compound (b') containing an aromatic group and the unsaturated monocarboxylic acid (c) in the above first step, an alkali-soluble resin with a polymerizable unsaturated bond equivalent of 300 to 8000 g / equivalent can be obtained.

[0241] The method for producing the alkali-soluble resin of the present invention includes the above first step and second step. As the reaction product (intermediate) obtained in the above first step, preferably, a resin having a structure containing an aromatic ring represented by the following formula (1') and a structure containing a polymerizable unsaturated bond represented by the following formula (2') and a polymerizable unsaturated double bond equivalent of 600 to 7000 g / equivalent can be cited.

[0242] [Chemical Formula 11]

[0243]

[0244] (In formula (1’), R 1 represents an oxygen atom or a sulfur atom. R 2 represents an aromatic group with or without substituents. In formula (2’), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.)

[0245] Such a resin is also one of the present inventions and can provide a cured product with excellent photocurability and a high refractive index.

[0246] R 1 and R 2 in the above formula (1’) are the same as those in the above formula (1), and R 4 to R 8 in the above formula (2’) are the same as those in the above formula (2).

[0247] The polymerizable unsaturated bond equivalent of the above resin is not particularly limited, and is preferably 650 to 6000 g / equivalent, more preferably 700 to 5000 g / equivalent, and further preferably 750 to 4000 g / equivalent.

[0248] As the resin having a structure containing an aromatic ring represented by the above formula (1’), preferably, a resin having a structural unit (A’) in which “-CH-O-R 3 ” in the above formula (a) is “-CH-OH” can be cited.

[0249] As the content ratio of the structural unit (A’) in the above resin, preferably, the same range as the content ratio of the above structural unit (A) can be cited.

[0250] As the resin having a structure containing a polymerizable unsaturated bond represented by the above formula (2’), preferably, a resin having a structural unit (B’) in which “-CH-O-R 9 ” in the above formula (b) is “-CH-OH” can be cited.

[0251] As the content ratio of the structural unit (B’) in the above resin, preferably, the same range as the content ratio of the above structural unit (B) can be cited.

[0252] The above resin may further have the above structural unit (C) and structural unit (D).

[0253] 3. Photosensitive resin composition

[0254] A photosensitive resin composition containing the first and / or second alkali-soluble resin, a polymerizable compound, and a photoinitiator of the present invention is also one of the present inventions. Since the photosensitive resin composition of the present invention contains the above-mentioned alkali-soluble resin, a cured product having excellent photocurability and a high refractive index can be provided. Hereinafter, the first alkali-soluble resin and the above-mentioned second alkali-soluble resin of the present invention are also collectively referred to as the alkali-soluble resin of the present invention.

[0255] The content of the above-mentioned first and / or second alkali-soluble resin is not particularly limited and can be appropriately set according to uses, blending of other components, etc. For example, relative to 100% by mass of the total solid content of the photosensitive resin composition, it is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, further preferably 15 to 75% by mass, and particularly preferably 15 to 70% by mass.

[0256] It should be noted that in this specification, the "total solid content" refers to the total amount of components that form a cured product (components other than solvents and curing catalysts that volatilize during the formation of the cured product).

[0257] (Polymerizable compound)

[0258] The above-mentioned polymerizable compound is a low-molecular 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 (such as infrared rays, ultraviolet rays, X-rays, etc.), and electron rays. Examples thereof include monofunctional compounds having 1 polymerizable unsaturated group in the molecule and polyfunctional compounds having 2 or more polymerizable unsaturated groups in the molecule.

[0259] Examples of the above-mentioned monofunctional compounds include N-substituted maleimide monomers; (meth)acrylates; (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. In addition, monomers having an active methylene or active methylene group can also be used.

[0260] Examples of the above-mentioned polyfunctional compounds include the following compounds, etc.

[0261] 2-functional (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, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate;

[0262] 3-functional or higher polyfunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane) tetra(meth)acrylate, glycerol 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 adduct trimethylolpropane tri(meth)acrylate, ethylene oxide adduct bis(trimethylolpropane) tetra(meth)acrylate, ethylene oxide adduct pentaerythritol tetra(meth)acrylate, ethylene oxide adduct dipentaerythritol hexa(meth)acrylate, propylene oxide adduct trimethylolpropane tri(meth)acrylate, propylene oxide adduct bis(trimethylolpropane) tetra(meth)acrylate, propylene oxide adduct pentaerythritol tetra(meth)acrylate, propylene oxide adduct dipentaerythritol hexa(meth)acrylate, ε-caprolactone adduct trimethylolpropane tri(meth)acrylate, ε-caprolactone adduct bis(trimethylolpropane) tetra(meth)acrylate, ε-caprolactone adduct pentaerythritol tetra(meth)acrylate, ε-caprolactone adduct dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinate-modified product, pentaerythritol triacrylate succinate-modified product, dipentaerythritol pentaacrylate phthalate-modified product, pentaerythritol triacrylate phthalate-modified product, the modified products of dipentaerythritol hexaacrylate represented by the following formula:

[0263] [Chemical formula 12]

[0264]

[0265] and so on;

[0266] Polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, bis(trimethylolpropane) tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide adduct of trimethylolpropane trivinyl ether, ethylene oxide adduct of bis(trimethylolpropane) tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, ethylene oxide adduct of dipentaerythritol hexavinyl ether, etc.;

[0267] (Meth)acrylate esters containing vinyl ether groups such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, etc.;

[0268] Polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butanediol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, bis(trimethylolpropane) tetraallyl ether, glycerol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide adduct of trimethylolpropane triallyl ether, ethylene oxide adduct of bis(trimethylolpropane) tetraallyl ether, ethylene oxide adduct of pentaerythritol tetraallyl ether, ethylene oxide adduct of dipentaerythritol hexaallyl ether, etc.;

[0269] Allyl (meth)acrylate and other allyl group-containing (meth)acrylate esters; polyfunctional (meth)acryloyl group-containing isocyanuric acid esters such as tris(acryloyloxyethyl) isocyanurate, tris(methacryloyloxyethyl) isocyanurate, alkylene oxide adduct tris(acryloyloxyethyl) isocyanurate, and alkylene oxide adduct tris(methacryloyloxyethyl) isocyanurate; polyfunctional allyl group-containing isocyanuric acid esters such as triallyl isocyanurate; polyfunctional urethane (meth)acrylate esters obtained by reacting polyfunctional isocyanates such as toluene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxy group-containing (meth)acrylate esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; polyfunctional aromatic vinyls such as divinylbenzene; etc. These polymerizable compounds can be used alone or in combination of two or more.

[0270] Among the above polymerizable compounds, from the aspect of further improving the curability of the photosensitive resin composition, it is preferable to use polyfunctional polymerizable compounds. As the functional number of the above polyfunctional polymerizable compounds, it is preferably 3 or more, more preferably 4 or more. In addition, the above functional number is preferably 10 or less, more preferably 8 or less. The above functional group number is preferably 3 to 10, more preferably 4 to 8.

[0271] There is no particular limitation on the molecular weight of the above polymerizable compounds. From the aspect of handling, for example, it is preferably 2000 or less.

[0272] Among the above polyfunctional polymerizable compounds, from the aspects of reactivity, economy, availability, etc., preferably, polymerizable compounds having a (meth)acryloyl group such as polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and (meth)acryloyl group-containing isocyanuric acid ester compounds can be cited, and more preferably, polyfunctional (meth)acrylate compounds can be cited. By including a compound having a (meth)acryloyl group, the photosensitivity and curability of the above photosensitive resin composition are more excellent, and a cured product with higher hardness and higher transparency can be obtained. As the above polyfunctional polymerizable compound, it is further preferable to use a polyfunctional (meth)acrylate compound having 3 or more functional groups.

[0273] The content of the above polymerizable compound is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass based on the total solid content of the photosensitive resin composition of 100% by mass.

[0274] (Photoinitiator)

[0275] Specific examples of the above-mentioned photoinitiators include, for example: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (“IRGACURE (registered trademark) 907”, manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (“IRGACURE 369”, manufactured by BASF), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one (“IRGACURE 379”, manufactured by BASF) and other aminoketone compounds; 2,2-dimethoxy-1,2-diphenylethane-1-one (“IRGACURE 651”, manufactured by BASF), methyl phenylglyoxylate (“DAROCUR MBF”, manufactured by BASF) and other benzyl ketal compounds; 1-hydroxycyclohexyl phenyl ketone (“IRGACURE 184”, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one (“DAROCUR 1173”, manufactured by BASF), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE 2959”, manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropan-1-one (“IRGACURE 127”, manufactured by BASF), 1-hydroxycyclohexyl phenyl ketone + benzophenone (“IRGACURE 500”, manufactured by BASF) and other hydroxyketone compounds; etc., and other alkylbenzophenone compounds exemplified in paragraphs

[0084] to

[0086] of Japanese Patent Application Laid-Open No. 2013-227485; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime) (“OXE01”, manufactured by BASF), acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (“OXE02”, manufactured by BASF), 1,2-octanedione, 1-[4-(phenylthio)-, 2-, (O-benzoyl oxime)] (“OXE03”, manufactured by BASF), acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (“OXE04”, manufactured by BASF) and other oxime ester compounds; benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; imidazole compounds; titanocene compounds; benzoate compounds; acridine compounds; etc.; phosphine oxide compounds; etc. Among them, aminoketone compounds and oxime ester compounds are preferred. The above-mentioned photoinitiators may be used alone or in combination of two or more.

[0276] The content of the above photoinitiator is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 8% by mass with respect to the total solid content of the photosensitive resin composition of 100% by mass.

[0277] The photosensitive resin composition of the present invention contains at least the above alkali-soluble resin, polymerizable compound, and photoinitiator, and may further contain one or more other components as needed. In addition, each of the contained components may be used singly or in combination of two or more.

[0278] Hereinafter, other components will be described.

[0279] (Polyfunctional thiol compound)

[0280] The above photosensitive resin composition may further contain a polyfunctional thiol compound. When the above alkali-soluble resin having a polymerizable unsaturated bond in the side chain and a polyfunctional thiol compound are contained, the ene-thiol reaction occurs simultaneously upon exposure or heating, and the crosslinking density can be increased. Particularly, in the case where an acrylate-based polymerizable unsaturated bond is present in the resin, the ene-thiol reaction proceeds well.

[0281] As the above polyfunctional thiol compound, a compound having two or more mercapto groups in one molecule and a molecular weight of 200 to 1000 is preferred, and a 3- to 5-functional secondary thiol is particularly preferred. By adding such a polyfunctional thiol compound to the above photosensitive resin composition, the curability and storage stability can be further improved.

[0282] Examples of the above polyfunctional thiol compound include mercaptopropionic acid derivatives such as butanediol bis(thiopropionate), ethylene glycol bis(thiopropionate), trimethylolpropane tris(thiopropionate), pentaerythritol tetrakis(thiopropionate), pentaerythritol tetra(3-mercaptobutyrate) (Karenz (registered trademark) PE-1), 1,4-bis(3-mercaptobutyryloxy)butane (Karenz BD-1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Karenz NR-1).

[0283] It should be noted that as the above polyfunctional thiol compound, a compound having no hydroxyl group and / or aromatic ring in the molecule is preferred.

[0284] Commercially available products of the above-mentioned polyfunctional thiol compounds can also be used. Examples thereof include "Thiokalcol 20" manufactured by Kao Corporation, "Karenz MT (registered trademark) PE1", "Karenz MT BD1", "Karenz MT NR1", "TPMB", "TEMB" manufactured by Showa Denko K.K., "TMMP", "TEMPIC", "PEMP", "EGMP-4", "DPMP", "TMMP II-20P", "PEMP II-20P" manufactured by SC Organic Chemistry Co., Ltd., and the like.

[0285] The content of the above-mentioned polyfunctional thiol compound is preferably 0.3 to 15% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 8% by mass with respect to the total solid content of the photosensitive resin composition of 100% by mass.

[0286] (Metal oxide particles)

[0287] The above-mentioned photosensitive resin composition preferably further contains metal oxide particles. By including metal oxide particles in the above-mentioned photosensitive resin composition, a cured product with a high refractive index can be provided. In addition, the photosensitivity and dielectric properties are improved. The reason therefor has not been determined yet, but it is speculated that if the refractive index difference between the resin and the metal oxide particles becomes smaller, the light loss caused by Rayleigh scattering and the like can be reduced during exposure. Even when the metal oxide particles are highly filled in the photosensitive resin composition, the resolution is not impaired, and thus the dielectric properties can be improved.

[0288] Examples of the above-mentioned metal oxide particles include oxide particles of a light-transmitting metal with a high refractive index containing 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, Te, etc. Among them, from the aspect of being able to provide a cured product with a higher refractive index, the above-mentioned metal oxide particles more preferably contain at least one metal element selected from the group consisting of Ti, Al, Zr, Zn, Sn, Ce, and Si. In addition, from the aspect of being able to provide a cured film with a high relative dielectric constant, Zr is more preferably contained, and from the aspect of being able to provide a cured film with high hardness, Si is more preferably contained.

[0289] The above metal oxides can be oxides of a single metal, solid solutions of two or more oxides, or composite oxides. Examples of single-metal oxides include, for example, 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), silicon oxide (SiO2), etc. Examples of solid solutions of two or more oxides include, for example, ITO, ATO, etc. Examples of composite oxides include, for example, barium titanate (BaTiO3), perovskite (CaTiO3), spinel (MgAl2O4), etc. Among them, from the aspect of being able to provide a cured product with a high refractive index, a high relative dielectric constant, or high hardness, zirconia particles (ZrO2 particles) and / or silica particles (SiO2 particles) are preferred.

[0290] From the aspect of being able to improve the dispersibility in the photosensitive resin composition, the above metal oxide particles are preferably surface-modified metal oxide particles. The surface modification of the above metal oxide particles can be obtained by known methods such as a method of mixing the above metal oxide particles and a surface modifier in a solvent, a method of performing a hydrothermal reaction in the presence of water, etc.

[0291] As the above surface modifier, there is no particular limitation, and examples include known coupling agents, surfactants, carboxylic acid compounds, etc. The surface modifier can be used alone or in combination of two or more.

[0292] Among them, from the aspect of further improving the dispersibility of the above metal oxide particles, as the above surface modifier, carboxylic acid compounds are preferred.

[0293] Examples of the above carboxylic acid compounds include carboxylic acids with or without substituents, (meth)acrylic acid. Examples of the above substituents include an ester group, an ether group, an amide group, a thioester group, a thioether group, a carbonate group, a urethane group, or a urea group, etc. In addition, examples of the above carboxylic acid compounds include aliphatic carboxylic acids such as acetic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, salicylic acid, naphthenic acid, capric acid, lauric acid, etc., and cyclic carboxylic acids.

[0294] As the above metal oxide particles, the metal oxide particles described in Japanese Patent Laid-Open No. 2013-216858 are preferred.

[0295] The crystallite diameter of the above metal oxide particles is preferably 1 to 20 nm, more preferably 1 to 15 nm, and further preferably 1 to 10 nm. The crystallite diameter can be determined by X-ray diffraction analysis.

[0296] The number-average primary particle diameter of the above metal oxide particles is preferably less than 30 nm, more preferably 1 to 25 nm, further preferably 3 to 20 nm, still further preferably 5 to 20 nm, and particularly preferably 5 to 15 nm. The number-average primary particle diameter can be determined as follows: The metal oxide particles are magnified and observed using a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a field emission scanning electron microscope (FE-SEM), etc. 100 particles are randomly selected, the length in the major axis direction is measured, and the arithmetic average is obtained.

[0297] The refractive index of the above metal oxide particles is preferably 1.70 to 2.70, more preferably 1.90 to 2.70.

[0298] The specific surface area of the above metal oxide particles is preferably 10 to 400 m 2 / g, more preferably 20 to 200 m 2 / g, further preferably 30 to 150 m 2 / g.

[0299] The content of the above metal oxide particles is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and further preferably 20 to 80% by mass relative to the total solid content of the alkali-soluble resin composition of 100% by mass.

[0300] The above photosensitive resin composition may further contain other components other than the above components as needed. Examples of the above other components include solvents; colorants (pigments, dyes); dispersants; heat resistance improvers; leveling agents; developing aids; coupling agents such as silane-based, aluminum-based, and titanium-based coupling agents; fillers, phenolic resins, polyvinylphenol, epoxy compounds, epoxy resins, etc. thermosetting resins; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants; matting agents; defoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinonediazide compounds; polyphenol compounds; cationic polymerizable compounds; thermal acid generators; etc. They may be used alone or in combination of two or more. These other components can be appropriately selected from known substances, and their amounts can also be appropriately set.

[0301] In addition, a photosensitive resin composition (also referred to as photosensitive resin composition (x)) containing a resin, an alkali-soluble resin, a polymerizable compound, and a photoinitiator, which is a reaction product (intermediate) of the above first step, is also one of the present inventions.

[0302] The alkali-soluble resin contained in the above photosensitive resin composition (x) is not particularly limited, and known alkali-soluble resins can be used, or the alkali-soluble resin of the present invention described above can also be used.

[0303] As the polymerizable compound and the photopolymerization initiator contained in the photosensitive resin composition (x) described above, the same substances as those described above can be cited. The content of each of these components can be the same as that described above.

[0304] The photosensitive resin composition (x) may further contain other components. As the other components, the same components as those of the above photosensitive resin composition can be cited. The content of each of these components can be set appropriately.

[0305] 4. Method for producing photosensitive resin composition

[0306] As a method for producing the photosensitive resin composition of the present invention, there is no particular limitation, and a known method can be used. For example, a method of mixing and dispersing the above-mentioned respective components using various mixers and dispersers can be cited. The mixing / dispersing step is not particularly limited and can be carried out by a known method. In addition, other steps that are usually carried out may also be included.

[0307] Among them, as a method for producing the photosensitive resin composition, a method including the following steps is preferred: a step of producing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 to 8000 g / equivalent or, when R 1 is a sulfur atom, producing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 300 to 8000 g / equivalent by the above-mentioned method for producing an alkali-soluble resin; and a step of mixing the obtained alkali-soluble resin, polymerizable compound, and photopolymerization initiator. Such a method for producing a photosensitive resin composition is also one of the present inventions.

[0308] When using the alkali-soluble resin or the photosensitive resin composition of the present invention, a cured product having a high refractive index and excellent curability can be provided. Such an alkali-soluble resin of the present invention or a cured product obtained by curing the photosensitive resin composition is also one of the present inventions.

[0309] In addition, the photosensitive resin composition (x) can also provide a cured product having a high refractive index and excellent curability. Such a cured product of the photosensitive resin composition (x) is also one of the present inventions.

[0310] When the cured product is a cured film, its film thickness is preferably 0.1 to 50 μm, more preferably 0.5 to 40 μm, and further preferably 1 to 30 μm.

[0311] The method for obtaining the above-mentioned cured product is not particularly limited, and known methods can be used. For example, the following methods can be cited: coating or molding the above-mentioned alkali-soluble resin or photosensitive resin composition on a substrate, and curing it by heating, irradiation with active energy rays such as ultraviolet rays, or a combination thereof to obtain a cured product. Among them, as a method for manufacturing a cured product, a method including the following steps is preferred: a step of coating the above-mentioned photosensitive resin composition on a substrate to form a coating film; a step of irradiating light on the formed coating film; and a step of heating the coating film after light irradiation.

[0312] As the above-mentioned substrate, there is no particular limitation, and it can be appropriately selected according to the purpose and use. For example, substrates made of various materials such as glass plates and plastic plates can be cited.

[0313] As a method for coating the above-mentioned photosensitive resin composition on a substrate to form a coating film, there is no particular limitation, and known methods such as spin coating, slit coating, roll coating, and casting coating can be used.

[0314] It is preferred to dry the coated material after coating the above-mentioned photosensitive resin composition on a substrate to form a coating film. The above drying can be carried out by using known methods. For example, a hot plate, an IR oven, a convection oven, etc. can be used. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the dryer, etc., and usually it is preferably carried out at a temperature of 50 to 160 °C for 10 seconds to 300 seconds.

[0315] As a method for irradiating light on the formed coating film, there is no particular limitation, and known methods can be used. As a light source for the active light used for light irradiation, for example, 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 arc lamps, and fluorescent lamps, and laser sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers can be cited.

[0316] When irradiating light on the above-mentioned coating film, light irradiation can be carried out through a photomask. As the photomask, a mask formed with a light-shielding portion according to the target pattern can be used.

[0317] It may also have a step of performing a development treatment with a developer after irradiating light through a photomask to remove the unirradiated portion. By light irradiation, the irradiated portion is cured, and the cured product is insoluble or hardly soluble in the developer. On the other hand, the unirradiated portion is dissolved in the developer and is thus removed by the development treatment, and a patterned cured film can be obtained. The development treatment can usually be carried out by methods such as dipping development, spray development, brush development, and ultrasonic development at a development temperature of 10 to 50 °C.

[0318] The above-mentioned developer is not particularly limited as long as it can dissolve the above-mentioned photosensitive resin composition. Usually, organic solvents and alkaline aqueous solutions are used, and mixtures thereof can also be used. It should be noted that when an alkaline aqueous solution is used as the developer, it is preferably washed with water after development. Examples of the organic solvents and alkaline aqueous solutions include the same organic solvents and alkaline aqueous solutions as those described in Japanese Patent Application Laid-Open No. 2015-157909.

[0319] After the above light irradiation, it is preferable to heat the coating film at 160 °C or lower. The heating temperature of the coating film is more preferably 150 °C or lower. As the lower limit of the heating temperature, from the aspect of maintaining curability, it is preferably 70 °C or higher, more preferably 80 °C or higher. The above heating temperature is preferably 70 to 160 °C, more preferably 80 to 150 °C.

[0320] The heating time is not particularly limited. For example, it is preferably 5 to 60 minutes. In addition, the heating method is not particularly limited. For example, known heating devices such as hot plates, convection ovens, and high-frequency heating machines can be used for heating.

[0321] 5. Use

[0322] The alkali-soluble resin and the photosensitive resin composition of the present invention can obtain a cured product having excellent curability and a high refractive index. Therefore, the above alkali-soluble resin and photosensitive resin composition can be suitably used for applications requiring curability and a high refractive index.

[0323] The alkali-soluble resin and the photosensitive resin composition of the present invention can also be suitably used for applications requiring a fast development speed and developability. Therefore, it is suitable for use as an optical material, and particularly suitable for use as a resist. The photosensitive resin composition of the present invention can be suitably used as a negative type or a positive type.

[0324] The alkali-soluble resin and photosensitive resin composition of the present invention having a high refractive index can be widely applied to various uses such as magnetic recording materials, catalyst materials, ultraviolet absorption materials, dental materials, contact lenses, intraocular lenses, high refractive index lenses for glasses, optical computer devices, optical storage media, antireflection films, conformal coatings, microlens arrays, top coatings for automobiles, coatings, coating agents, hair cosmetics, gradient refractive index optical components and dynamic gradient refractive index components, nanoimprint materials, photocurable plastics, polymerizable compounds for holographic 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), optical waveguides (both planar and "fiber" geometries), semiconductor elements, light diffusing members, prism sheets, hard coating materials, optical wiring members, diffraction gratings, encapsulation materials for LEDs, etc., pressure-sensitive adhesives, protective films for the surfaces of glasses, films and sheets used in sensor elements such as CCD / CMOS or display elements such as display screens, photocurable resins (OCR) for bonding liquid crystal and other image display members to plastic cover plates, reflective protective films for transparent electrodes, etc., refractive index matching layers for preventing the transparency of ITO electrodes of touch panels, anti-adhesion layers, antireflection films for display screens, interlayer insulating films for semiconductors, etc. Among them, the alkali-soluble resin and photosensitive resin composition of the present invention are suitable as curable resins or resin compositions for forming semiconductor members or optical materials, and are particularly suitable as curable resins or resin compositions for optical materials.

[0325] In the present invention, the "optical material" refers to a material used in components constituting devices in the optical field, the electrical / electronic field, etc. For example, it refers to a material used as a material in color filters, light extraction layers, black matrices, light spacers, black column spacers, photoresists, overcoats, planarization layers for TFTs, insulating films for TFTs, surface coatings of optical lenses, etc. used in liquid crystals, organic ELs, quantum dots, small / micro LED display devices / solid-state imaging elements / touch panel display devices, etc. From the aspect of having alkali solubility, the alkali-soluble resin of the present invention is also suitable for uses applying lithography, and can form a cured film having high refraction, high hardness, and high transparency. Therefore, the photosensitive resin composition of the present invention is most preferably a curable resin composition for color filters, light extraction layers, and color conversion layers for organic EL display devices. As a high refractive index member capable of performing lithography and having high transparency, the alkali-soluble resin of the present invention can be appropriately used.

[0326] Among them, the above alkali-soluble resin and photosensitive resin composition are preferably for display devices, and display device members and display devices including cured products of the above photosensitive resin composition are also one of the present invention.

[0327] The above alkali-soluble resin and photosensitive resin composition can also be suitably used for various optical members such as inks, printed wiring boards, insulating films, films, organic protective films, and constituent members of electric / magnetic devices, etc.

[0328] Examples

[0329] Hereinafter, examples are given to illustrate the present invention in more detail, but the present invention is not limited to these examples.

[0330] The various evaluation methods used in this example are as follows.

[0331] <Weight-average molecular weight>

[0332] The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are as follows.

[0333] Apparatus: Gel permeation chromatography apparatus HLC-8320GPC (manufactured by Tosoh Corporation)

[0334] Column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation)

[0335] Detector: RI detector for liquid chromatography

[0336] Measurement temperature: 40 °C

[0337] Solvent: THF (tetrahydrofuran)

[0338] Sample concentration: 0.05 g / 10 cc

[0339] Sample side flow rate: 0.6 ml / minute

[0340] <Acid value>

[0341] Precisely weigh 3 g of the resin solution, dissolve it in a mixed solvent of 90 g of acetone and 10 g of water, and titrate it using 0.1 N KOH aqueous solution as the titrant. The titration is carried out using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of the solid component (mgKOH / g) is calculated based on the acid value of the resin solution and the solid content of the resin solution.

[0342] It should be noted that the solid content of the resin solution is determined by the following method. That is, measure about 1 g of the resin solution in an aluminum cup, add about 3 g of acetone to dissolve it, and then dry it naturally at room temperature. Then, dry it in a vacuum dryer (manufactured by EYELA, trade name: VOS-301SD) at 140 °C under vacuum for 1.5 hours, and then cool it naturally in a desiccator, and measure the mass. Based on the mass reduction, calculate the solid content (mass %) of the resin solution.

[0343] <Equivalent weight of polymerizable unsaturated bond>

[0344] It is obtained by dividing the mass (g) of the resin solid component by the amount (mol) of polymerizable unsaturated bonds in the resin.

[0345] <Epoxy equivalent>

[0346] The solid content conversion value is obtained by the method according to JIS K7236:2001.

[0347] <Refractive index (resin)>

[0348] Using a spin coater (manufactured by MIKASA Co., Ltd., 1H-D7), the resin solution in Table 1 was uniformly coated on a 5 cm square glass substrate (soda-lime glass AS-2K, manufactured by ToShin Riko Co., Ltd.). The coated plate was dried at 90 °C for 3 minutes to obtain a laminate. After removing the resin composition attached to the ends of the glass substrate, the obtained laminate was heat-treated at 95 °C for 60 minutes using a perfect oven thermostat (manufactured by Espec Corporation), cooled to room temperature, and a laminate with a coating film thickness of 0.5 μm was obtained. Using the obtained laminate as a measurement sample, with the following device, from the measured reflectance based on film interference, the reflectance of the coating film was simulated according to the Fresnel formula, and thus the refractive index value of the coating film at a light wavelength of 589 nm was calculated.

[0349] Device: Film thickness measurement system F-20 manufactured by Filmetrics.

[0350] Standard fiber stage SS-1 (spot diameter 1.5 mm).

[0351] <Refractive index (photosensitive resin composition)>

[0352] Using a spin coater (manufactured by MIKASA Co., Ltd., 1H-D7), the photosensitive resin composition based on the ratios in Table 2 and Table 4 was uniformly coated on a 5 cm square glass substrate (soda-lime glass AS-2K, manufactured by ToShin Riko Co., Ltd.). After drying the coated plate at 90 °C for 3 minutes, it was exposed with a high-pressure mercury lamp at 100 mJ, and thus a laminate with a coating film formed on the glass substrate was obtained. After removing the resin composition attached to the ends of the glass substrate, the obtained laminate was heat-treated at 95 °C for 60 minutes using a perfect oven thermostat (manufactured by Espec Corporation), cooled to room temperature, and a laminate with a coating film thickness of 0.5 μm was obtained. Using the obtained laminate as a measurement sample, the refractive index value was obtained by the same method as the refractive index of the above resin.

[0353] <Solvent resistance>

[0354] The photosensitive resin composition based on the formulation in Table 3 was spin-coated on a glass substrate measuring 5 cm square. After drying at 100 °C for 3 minutes, it was exposed using a high-pressure mercury lamp at 200 mJ, and then heat-treated (post-cured) at 150 °C for 40 minutes to obtain a cured film with a film thickness of 2 μm. Then, the cured film was immersed in 20 g of propylene glycol monomethyl ether (PGME) at 40 °C for 10 minutes and then taken out. For the immersion liquid (PGME) after taking out the cured film, the absorbance was measured using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The larger the value of the absorbance, the more the colorant dissolves in the immersion liquid, and the lower the solvent resistance of the photosensitive resin composition is evaluated.

[0355] <Development rate>

[0356] The photosensitive resin composition was coated on a glass substrate measuring 10 cm square by spin coating. After heat treatment (90 °C, 3 minutes), through a photomask with an opening having a line width and pitch of 30 μm at a distance of 50 μm from the coated film, using a UV aligner (manufactured by Dainippon Scientific Co., Ltd., trade name "MA-1100") equipped with a 2.0 kW ultra-high pressure mercury lamp, 2 it was exposed with an exposure dose of 60 mJ / cm

[0357] (in terms of 365 nm illuminance conversion). A 0.05% aqueous potassium hydroxide solution was spread using a rotary developer, the unexposed portion was dissolved and removed, and the remaining exposed portion was washed with pure water for 10 seconds to perform development, thereby evaluating the developability.

[0358] ◎: Development time is less than 20 seconds

[0359] 〇: Development time is 20 seconds or more and less than 30 seconds

[0360] △: Development time is 30 seconds or more and less than 40 seconds

[0361] ×: Development time is 40 seconds or more

[0362] <Weather resistance>

[0363] Using a spin coater (manufactured by MIKASA Corporation, 1H-D7), the photosensitive resin composition solution in Table 4 was uniformly coated on a 5 cm square glass substrate (soda-lime glass AS-2K, manufactured by ToShin Riko Co., Ltd.). The coated plate was dried at 100 °C for 3 minutes to obtain a laminate. After removing the resin composition attached to the ends of the glass substrate, the obtained laminate was exposed using a high-pressure mercury lamp at 100 mJ. Using a perfect oven thermostat (manufactured by Espec Corporation), heat treatment was performed at 230 °C for 30 minutes, and then cooled to room temperature to obtain a laminate with a coating film thickness of 2 μm. The obtained laminate was used as a measurement sample, and a weather resistance test was carried out using the following apparatus, conditions, and evaluation method.

[0364] Apparatus: Xenon weather resistance tester X25 (manufactured by Suga Test Instruments Co., Ltd.)

[0365] Conditions: Tank temperature 50 °C, tank humidity 17%, irradiance 0.45 kW / m 2 , 200 hours

[0366] Evaluation method: Using a film thickness measurement system F-20 manufactured by Filmetrics, the film thickness reduction rate (%) before and after the test was measured. In the case of a small value, it was evaluated as having good weather resistance.

[0367] <Measurement of mass reduction rate>

[0368] Using a TG-DTA (thermogravimetry-differential thermal analysis) apparatus, in an air atmosphere, the zirconia particles were heated from room temperature to 800 °C at 10 °C / minute, and the mass reduction rate of the particles was measured. Based on this mass reduction rate, the ratio of the compound that surface-modified the zirconia particles and the ratio of the zirconia particles were determined.

[0369] (Example of synthesis 1) Manufacture of alkali-soluble resin (A-1)

[0370] Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, 132.1 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy groups) of cresol novolac type epoxy resin (trade name "YDCN-704A", manufactured by NIPPON STEEL Chemical & Material Co., Ltd., epoxy equivalent 206 g / equivalent) were charged, and the temperature was raised to 120 °C by heating. After the temperature of the reaction vessel reached 120 °C, while maintaining this temperature, the system was purged with nitrogen bubbling until the oxygen concentration was 0.5 vol% or less, 102.1 g (0.6 mole) of o-phenylphenol and 1 g of triphenylphosphine were added, and an addition reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 28.8 g (0.4 mole) of acrylic acid, 0.7 g of triphenylphosphine, 0.3 g of ANTAGE W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor, and 12.4 g of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 41.9 g (0.42 mole) of succinic anhydride and 108.2 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100 °C for 7 hours to complete the reaction. Further, 771.7 g of propylene glycol monomethyl ether was added to obtain an alkali-soluble resin solution (A-1). Various physical properties of the obtained alkali-soluble resin (A-1) are shown in Table 1.

[0371] (Example of Synthesis 2) Production of alkali-soluble resin (A-2)

[0372] 138.7 g of propylene glycol monomethyl ether acetate and 206 g (1 mol of epoxy groups) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, and the temperature was raised to 120°C by heating. After the temperature of the reaction vessel reached 120°C, while maintaining this temperature, the system was purged with nitrogen bubbling until the oxygen concentration was 0.5 vol% or less, and 110.6 g (0.65 mol) of o-phenylphenol, 6.9 g (0.05 mol) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added for an addition reaction. The reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 21.6 g (0.3 mol) of acrylic acid, 0.7 g of triphenylphosphine, 0.3 g of ANTAGE W-400, and 9.3 g of propylene glycol monomethyl ether acetate were added for an addition reaction. The reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 42.9 g (0.43 mol) of succinic anhydride and 110.8 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100°C for 7 hours to complete the reaction. Further, 790.5 g of propylene glycol monomethyl ether was added to obtain an alkali-soluble resin solution (A-2). Various physical properties of the obtained alkali-soluble resin (A-2) are shown in Table 1.

[0373] (Synthesis Example 3) Preparation of alkali-soluble resin (A-3)

[0374] 142.9 g of propylene glycol monomethyl ether acetate and 206 g (1 mol of epoxy groups) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, and the temperature was raised to 120°C by heating. After the temperature of the reaction vessel reached 120°C, while maintaining this temperature, the system was purged with nitrogen bubbling until the oxygen concentration was 0.5 vol% or less, and 126.0 g (0.74 mol) of o-phenylphenol, 1.4 g (0.01 mol) of p-hydroxyphenyl-2-ethanol, and 1.1 g of triphenylphosphine were added for an addition reaction. The reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 18.0 g (0.25 mol) of acrylic acid, 0.7 g of triphenylphosphine, 0.4 g of ANTAGE W-400, and 7.7 g of propylene glycol monomethyl ether acetate were added for an addition reaction. The reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 43.7 g (0.44 mol) of succinic anhydride and 112.8 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100°C for 7 hours to complete the reaction. Further, 804.7 g of propylene glycol monomethyl ether was added to obtain an alkali-soluble resin solution (A-3). Various physical properties of the obtained alkali-soluble resin (A-3) are shown in Table 1.

[0375] (Synthesis Example 4) Production of alkali-soluble resin (A-4)

[0376] 134.3 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, and the temperature was raised to 120°C. After the temperature of the reaction vessel reached 120°C, while maintaining this temperature, the system was purged with nitrogen bubbling until the oxygen concentration was 0.5% by volume or less, and 93.6 g (0.55 mole) of o-phenylphenol, 13.8 g (0.1 mole) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added for an addition reaction. The reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 25.2 g (0.35 mole) of acrylic acid, 0.7 g of triphenylphosphine, 0.3 g of ANTAGE W-400, and 10.8 g of propylene glycol monomethyl ether acetate were added for an addition reaction. The reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 29.6 g (0.3 mole) of succinic anhydride and 100.3 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100°C for 7 hours to complete the reaction. Further, 750.1 g of propylene glycol monomethyl ether was added to obtain an alkali-soluble resin solution (A-4). Various physical properties of the obtained alkali-soluble resin (A-4) are shown in Table 1.

[0377] (Synthesis Example 5) Production of alkali-soluble resin (A-5)

[0378] 116.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, and the temperature was raised to 120°C. After the temperature of the reaction vessel reached 120°C, while maintaining this temperature, the system was purged with nitrogen bubbling until the oxygen concentration was 0.5% by volume or less, and 66.1 g (0.6 mole) of benzenethiol and 0.9 g of triphenylphosphine were added for an addition reaction. The reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 28.8 g (0.4 mole) of acrylic acid, 0.6 g of triphenylphosphine, 0.3 g of ANTAGE W-400, and 12.4 g of propylene glycol monomethyl ether acetate were added for an addition reaction. The reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 37.4 g (0.37 mole) of succinic anhydride and 96.6 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100°C for 7 hours to complete the reaction. Further, 689.2 g of propylene glycol monomethyl ether was added to obtain an alkali-soluble resin solution (A-5). Various physical properties of the obtained alkali-soluble resin (A-5) are shown in Table 1.

[0379] (Synthesis Example 6) Production of alkali-soluble resin (A-6)

[0380] Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a condenser tube, and a dropping tank inlet, 203.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy groups) of the same cresol novolak type epoxy resin "YDCN-704A" as used in Example 1 were charged, and the temperature was raised to 100 °C by heating. After the temperature of the reaction vessel reached 100 °C, it was maintained for 30 minutes to dissolve the resin. While cooling the temperature to 70 °C, the inside of the system was purged with nitrogen. 99.2 g (0.9 mole) of benzenethiol and 0.2 g of triphenylphosphine were added for an addition reaction, and the reaction was carried out for 5 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 7.2 g (0.1 mole) of acrylic acid, 1.3 g of triphenylphosphine, and 0.3 g of ANTAGE W-400 were added for an addition reaction, and the reaction was carried out at 120 °C for 16 hours to complete the reaction. After cooling to room temperature, 27.5 g (0.275 mole) of succinic anhydride and 23.5 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 110 °C for 7 hours to complete the reaction. Further, 284.9 g of propylene glycol monomethyl ether acetate was added to obtain an alkali-soluble resin solution (A-6). Various physical properties of the obtained alkali-soluble resin (A-6) are shown in Table 1.

[0381] (Synthesis Example 7) Production of alkali-soluble resin (A-7)

[0382] Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a condenser tube, and a dropping tank inlet, 215.9 g of propylene glycol monomethyl ether acetate and 231 g (1 mole of epoxy groups) of NC-7000-L (naphthalene-containing novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 231.0 g / equivalent) were charged, and the temperature was raised to 100 °C by heating. After the temperature of the reaction vessel reached 100 °C, it was maintained for 30 minutes to dissolve the resin. While cooling the temperature to 70 °C, the inside of the system was purged with nitrogen. 92.5 g (0.84 mole) of benzenethiol and 0.2 g of triphenylphosphine were added for an addition reaction, and the reaction was carried out for 5 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 11.5 g (0.16 mole) of acrylic acid, 1.3 g of triphenylphosphine, and 0.3 g of ANTAGE W-400 were added for an addition reaction, and the reaction was carried out at 120 °C for 16 hours to complete the reaction. After cooling to room temperature, 27.5 g (0.275 mole) of succinic anhydride and 27.2 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 110 °C for 7 hours to complete the reaction. Further, 303.9 g of propylene glycol monomethyl ether acetate was added to obtain an alkali-soluble resin solution (A-7). Various physical properties of the obtained alkali-soluble resin (A-7) are shown in Table 1.

[0383] (Synthesis Example 8) Production of alkali-soluble resin (A-8)

[0384] 135.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mol of epoxy group) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, and the temperature was raised to 120°C by heating. After the temperature of the reaction vessel reached 120°C, while maintaining this temperature, the system was purged with nitrogen, 108.9 g (0.64 mol) of p-phenylphenol, 1.4 g (0.01 mol) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added for an addition reaction, and the reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 25.2 g (0.35 mol) of acrylic acid, 0.7 g of triphenylphosphine, 0.3 g of ANTAGE W-400, and 10.8 g of propylene glycol monomethyl ether acetate were added for an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 102.3 g (0.67 mol) of tetrahydrophthalic anhydride and 149.5 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100°C for 10 hours to complete the reaction. Further, 904.1 g of propylene glycol monomethyl ether was added to obtain an alkali-soluble resin solution (A-8). Various physical properties of the obtained alkali-soluble resin (A-8) are shown in Table 1.

[0385] (Synthesis Example 9) Production of alkali-soluble resin (A-9)

[0386] 135 g of propylene glycol monomethyl ether acetate and 206 g (1 mol of epoxy group) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, and the temperature was raised to 120°C by heating. After the temperature of the reaction vessel reached 120°C, while maintaining this temperature, the system was purged with nitrogen, 102.1 g (0.6 mol) of o-phenylphenol, 6.9 g (0.05 mol) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added for an addition reaction, and the reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 30.1 g (0.35 mol) of methacrylic acid, 0.7 g of triphenylphosphine, 0.3 g of ANTAGE W-400, and 12.9 g of propylene glycol monomethyl ether acetate were added for an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 57.5 g (0.57 mol) of succinic anhydride and 120.5 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100°C for 8 hours to complete the reaction. Further, 820.2 g of propylene glycol monomethyl ether was added to obtain an alkali-soluble resin solution (A-9). Various physical properties of the obtained alkali-soluble resin (A-9) are shown in Table 1.

[0387] (Synthesis Example 10) Production of alkali-soluble resin (A-10)

[0388] 310.5 g of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet. After purging with nitrogen, the temperature was raised to 90 °C. On the other hand, as dropping tank (A), a stirred mixture of 70.0 g of methyl methacrylate (MMA), 142.2 g of glycidyl methacrylate (GMA) (1 mol of epoxy group), and 4.2 g of tert-butyl peroxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by NOF Corporation) was prepared in a beaker, and a stirred mixture of 2.1 g of n-dodecyl mercaptan (nDM) and 7.8 g of propylene glycol monomethyl ether acetate was prepared in dropping tank (B). After the temperature of the reaction vessel reached 90 °C, the dropping was started from the dropping tank over 3 hours while maintaining this temperature, and polymerization was carried out. After the completion of dropping, the reaction vessel was maintained at 90 °C for 1 hour and then heated to 115 °C for 90 minutes for aging. Thereafter, it was cooled to room temperature, and 74.9 g (0.68 mol) of benzenethiol and 0.9 g of triphenylphosphine were charged under nitrogen bubbling for an addition reaction, and the reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 23.1 g (0.32 mol) of acrylic acid, 0.5 g of triphenylphosphine, and 0.5 g of ANTAGE W-400 were charged for an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 38.7 g (0.39 mol) of succinic anhydride was charged, and the reaction was carried out at 100 °C for 7 hours to complete the reaction, obtaining an alkali-soluble resin solution (A-10). Various physical properties of the obtained alkali-soluble resin (A-10) are shown in Table 1.

[0389] (Synthesis Example 11) Production of resin intermediate (A-11)

[0390] Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, 116.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy groups) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged, and the temperature was raised to 120 °C by heating. After the temperature of the reaction vessel reached 120 °C, while maintaining this temperature, the system was purged with nitrogen bubbling until the oxygen concentration was 0.5 vol% or less, and 66.1 g (0.6 mole) of benzenethiol and 0.9 g of triphenylphosphine were added for an addition reaction. The reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 28.8 g (0.4 mole) of acrylic acid, 0.6 g of triphenylphosphine, 0.3 g of ANTAGE W-400, and 12.4 g of propylene glycol monomethyl ether acetate were added for an addition reaction. The reaction was carried out for 16 hours to complete the reaction, and a resin intermediate (A-11) was obtained. Various physical properties of the obtained resin intermediate (A-11) are shown in Table 1.

[0391] (Synthesis Example 12) Preparation of alkali-soluble resin (A-12)

[0392] Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, 181.5 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy groups) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged, and the temperature was raised to 120 °C by heating. After the temperature of the reaction vessel reached 120 °C, while maintaining this temperature, the system was purged with nitrogen bubbling until the oxygen concentration was 0.5 vol% or less, and 66.1 g (0.6 mole) of benzenethiol and 0.9 g of triphenylphosphine were added for an addition reaction. The reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 28.1 g (0.39 mole) of acrylic acid, 2.8 g (0.01 mole) of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 0.6 g of triphenylphosphine, 0.3 g of ANTAGE W-400, and 16.6 g of propylene glycol monomethyl ether acetate were added for an addition reaction. The reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 37.4 g (0.37 mole) of succinic anhydride and 24.3 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100 °C for 7 hours to complete the reaction. Further, 290.8 g of propylene glycol monomethyl ether was added to obtain an alkali-soluble resin solution (A-12). Various physical properties of the obtained alkali-soluble resin (A-12) are shown in Table 1.

[0393] (Comparative Synthesis Example 1) Preparation of comparative alkali-soluble resin (B-1)

[0394] Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, 117.5 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy groups) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged, and the temperature was raised to 120 °C by heating. After the temperature of the reaction vessel reached 120 °C, while maintaining this temperature, the system was purged with nitrogen, 68.1 g (0.4 mole) of o-phenylphenol and 1 g of triphenylphosphine were added for an addition reaction, and the reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 43.2 g (0.6 mole) of acrylic acid, 0.6 g of triphenylphosphine, 0.3 g of ANTAGE W-400, and 18.5 g of propylene glycol monomethyl ether acetate were added for an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 39.5 g (0.39 mole) of succinic anhydride and 101.9 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100 °C for 7 hours to complete the reaction. Further, 726.8 g of propylene glycol monomethyl ether was added to obtain a comparative alkali-soluble resin solution (B-1). Various physical properties of the obtained alkali-soluble resin (B-1) are shown in Table 1.

[0395] (Comparative Synthesis Example 2) Preparation of Comparative Alkali-Soluble Resin (B-2)

[0396] Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet, 157.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy groups) of the same cresol novolac type epoxy resin "YDCN-704A" as used in Example 1 were charged, and the temperature was raised to 120 °C by heating. After the temperature of the reaction vessel reached 120 °C, while maintaining this temperature, the system was purged with nitrogen, 161.7 g (0.95 mole) of o-phenylphenol and 1.1 g of triphenylphosphine were added for an addition reaction, and the reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 3.6 g (0.05 mole) of acrylic acid, 0.7 g of triphenylphosphine, 0.4 g of ANTAGE W-400, and 1.5 g of propylene glycol monomethyl ether acetate were added for an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 46.2 g (0.46 mole) of succinic anhydride and 119.2 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 100 °C for 10 hours to complete the reaction. Further, 850.4 g of propylene glycol monomethyl ether was added to obtain a comparative alkali-soluble resin solution (B-2). Various physical properties of the obtained alkali-soluble resin (B-2) are shown in Table 1.

[0397] (Examples 1 to 12, Comparative Examples 1 to 2)

[0398] Using the resins of Synthesis Examples 1 to 12 and Comparative Synthesis Examples 1 to 2, a photosensitive resin composition was prepared at the ratios shown in Table 2, and the refractive index of the resin was measured by the above method. The results are shown in Table 2.

[0399] (Examples 13 to 39, Comparative Examples 3 to 6)

[0400] The resin solutions obtained in the synthesis examples and comparative synthesis examples, dipentaerythritol hexaacrylate, a photopolymerization initiator (Irgacure (registered trademark) OXE-02, manufactured by BASF), a pigment dispersion 1 or a zirconia particle dispersion, and propylene glycol monomethyl ether acetate were mixed at the ratios (solid component amounts) shown in Table 3 or Table 4 to obtain photosensitive resin compositions 1 to 31. The above pigment dispersion 1 and zirconia particle dispersion were prepared by the following methods.

[0401] (Preparation of Pigment Dispersion 1)

[0402] 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 part of Disparlon DA-7301 as a dispersant, 2.25 parts of C.I. Pigment Green 58 and 1.5 parts of C.I. Pigment Yellow 138 as colorants were mixed and dispersed for 3 hours using a paint stirrer to obtain Pigment Dispersion 1.

[0403] (Preparation of Zirconia Particle Dispersion)

[0404] Production Example 1

[0405] (Production of Coated Zirconia Nanoparticles Coated with 2-Ethylhexanoic Acid and / or a Carboxylic Acid Ester Derived from 2-Ethylhexanoic Acid (Coated ZrO2 Particles 1))

[0406] Pure water (268 g) was mixed into a zirconium 2-ethylhexanoate mineral spirit solution (782 g, zirconium 2-ethylhexanoate content 44% by mass, manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.). The resulting mixed solution was put into an autoclave equipped with a stirrer, and the atmosphere in the autoclave was replaced with nitrogen. Then, the mixed solution was heated to 180°C and maintained at this temperature for 16 hours (the pressure in the autoclave was 0.94 MPa) to carry out a reaction to form zirconia particles. Next, the reaction mixture was taken out, the precipitate accumulated at the bottom was filtered out, washed with acetone, and then dried. 100 g of the dried precipitate was dispersed in toluene (800 mL), resulting in a turbid solution. Then, as a purification step, it was filtered again using a quantitative filter paper (manufactured by ADVANTEC Toyo Co., Ltd., No. 5C) to remove coarse particles and the like in the precipitate. Furthermore, the filtrate was concentrated under reduced pressure to remove toluene, thereby recovering white zirconia nanoparticles 1 (coated ZrO2 particles 1).

[0407] The crystal structure of the coated ZrO₂ particles 1 obtained was confirmed using an XRD diffraction pattern. As a result, diffraction lines attributed to the tetragonal and monoclinic crystals were detected. Based on the intensity of the diffraction lines, the ratio of the tetragonal crystal to the monoclinic crystal was 54 / 46, and its particle size (crystallite diameter) was 5 nm.

[0408] The average particle size (number-average primary particle size) of the coated ZrO₂ particles 1 measured by an electron microscope (FE-TEM JEM-2100F TEM manufactured by JEOL Ltd., magnification 600,000 times) was 12 nm. In addition, the coated ZrO₂ particles 1 obtained were analyzed by infrared absorption spectroscopy. As a result, absorption from C-H and absorption from COOH could be confirmed. It is considered that this absorption is attributed to 2-ethylhexanoic acid and / or a carboxylic acid ester derived from 2-ethylhexanoic acid on the coated surface of the coated ZrO₂ particles 1.

[0409] In addition, 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 can be known that 2-ethylhexanoic acid and / or a carboxylic acid ester derived from 2-ethylhexanoic acid on the coated surface of the coated ZrO₂ particles 1 is 12% by mass of the entire coated ZrO₂ particles 1.

[0410] Production Example 2

[0411] (Production of zirconia nanoparticles (coated ZrO₂ particles 2) coated with 2-ethylhexanoic acid and / or a carboxylic acid ester derived from 2-ethylhexanoic acid and 2-acryloyloxyethyl succinate)

[0412] 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. Then, n-hexane (36 g) was added, whereby the dispersed particles aggregated, the solution became turbid, and the aggregated particles were separated from the turbid solution using a filter paper. Then, the separated aggregated particles were added to n-hexane (36 g), stirred for 10 minutes, and the aggregated particles were separated using a filter paper. The obtained particles were vacuum-dried at room temperature to prepare zirconia nanoparticles (coated ZrO₂ particles 2) surface-treated with 2-ethylhexanoic acid and / or a carboxylic acid ester derived from 2-ethylhexanoic acid and 2-acryloyloxyethyl succinate.

[0413] The obtained coated ZrO₂ particles 2 were dispersed in deuterated chloroform to prepare a measurement sample, and analyzed by 1 ¹H-NMR. As a result, it was found that the molar ratio of the presence of 2-ethylhexanoic acid and / or a carboxylic acid ester derived from 2-ethylhexanoic acid to 2-acryloyloxyethyl succinate was 24:76.

[0414] 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 can be known that 2-ethylhexanoic acid and / or carboxylic acid esters derived from 2-ethylhexanoic acid and 2-acryloyloxyethyl succinate covering the coated zirconia particles are 18% by mass of the whole coated zirconia particles.

[0415] The coated ZrO2 particles 2 (7 g) obtained above, methyl ethyl ketone (3 g), and DISPER BYK-111 (manufactured by BYK Chemie Japan Co., 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.

[0416] Using the obtained photosensitive resin compositions 1 to 15, the development rate and solvent resistance were evaluated by the above method. The results are shown in Table 3.

[0417] Using the obtained photosensitive resin compositions 16 to 31, the development rate, refractive index, and weather resistance were evaluated by the above method. The results are shown in Table 4.

[0418]

[0419] The descriptions in Table 1 represent the following substances.

[0420] YDCN-704A: Cresol novolak type epoxy resin (epoxy equivalent 206 g / equivalent) NC-7000-L: Naphthalene-containing novolak type epoxy resin, epoxy equivalent 231.0 / equivalent)

[0421]

[0422]

[0423]

[0424] According to Tables 1 to 4, the cured products of the alkali-soluble resins and the photosensitive resin compositions containing the alkali-soluble resins of the examples having a specified aromatic ring-containing structure and a polymerizable unsaturated bond-containing structure and a polymerizable unsaturated bond equivalent of 700 to 8000 g / equivalent all have a high refractive index of about 1.6. In particular, resins having a structure containing a sulfur atom and a benzene ring have a high refractive index. By mixing metal oxide particles, the development rate deteriorates slightly, but the refractive index is further increased. In addition, the solvent resistance and developability of the alkali-soluble resins of the examples are also good. The weather resistance of the photosensitive resin compositions using resins having a structure containing a sulfur atom and a benzene ring is good, and very good results are obtained when using resins further having a functional group with a free radical scavenging ability.

[0425] In addition, the resin intermediate (A-11) of Synthesis Example 11 is a synthesis intermediate of the resin (A-5) of Synthesis Example 5. Since it does not have alkali solubility, when this resin is used alone, it does not have developability in preparing a photosensitive resin composition, but it can impart high refractive index and high solvent resistance to the photosensitive resin composition. When used in combination with other alkali-soluble resins, a photosensitive resin composition with excellent developability can be prepared.

Claims

1. An alkali-soluble resin, characterized in that, It has an aromatic ring-containing structure represented by the following formula (1) and a polymerizable unsaturated bond-containing structure represented by the following formula (2), with a polymerizable unsaturated bond equivalent of 700 g / equivalent to 8000 g / equivalent, [Chemical formula 1] In formula (1), R 1 represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom with or without substituents; R 2 represents an aromatic group with or without substituents; R 3 is a hydrogen atom or a group represented by formula (3); in formula (2), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group; R 9 is a hydrogen atom or a group represented by formula (3); at least one of R 3 and R 9 is a group represented by formula (3); in formula (3), R 10 represents a divalent hydrocarbon group with or without substituents.

2. The alkali-soluble resin according to claim 1, wherein and an acid value of 30 mgKOH / g to 150 mgKOH / g.

3. The alkali-soluble resin according to claim 1 or 2, wherein The epoxy equivalent exceeds 10,000 g / equivalent.

4. The alkali-soluble resin according to any one of claims 1 to 3, characterized in that, The main chain structure has a novolak structure.

5. A photosensitive resin composition, characterized in that, It contains the alkali-soluble resin, polymerizable compound, and photoinitiator described in any one of claims 1 to 4.

6. A cured product, characterized in that, It is formed by curing the alkali-soluble resin described in any one of claims 1 to 4 or the photosensitive resin composition described in claim 5.

7. A component for a display device, characterized in that, It contains the cured product described in claim 6.

8. A display device, characterized in that, It contains the component for a display device described in claim 7.

9. A method for manufacturing an alkali-soluble resin, which is a method for manufacturing an alkali-soluble resin, characterized in that this manufacturing method includes: a first step of reacting a compound (b) containing an aromatic group and an unsaturated monocarboxylic acid (c) with an epoxy resin (a) having two or more epoxy groups in one molecule; and a second step of reacting a polybasic acid anhydride (d) with the reaction product obtained in the first step, adjusting the amounts of the compound (b) containing an aromatic group and the unsaturated monocarboxylic acid (c) in the first step so that the polymerizable unsaturated bond equivalent of the obtained alkali-soluble resin is 700 g / equivalent to 8000 g / equivalent.

10. A method for manufacturing a photosensitive resin composition, which is a method for manufacturing a photosensitive resin composition, characterized in that this manufacturing method includes: a step of manufacturing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 g / equivalent to 8000 g / equivalent by the method for manufacturing an alkali-soluble resin described in claim 9; and a step of mixing the obtained alkali-soluble resin, polymerizable compound, and photoinitiator.

11. An alkali-soluble resin, characterized in that, It has an aromatic ring-containing structure represented by the following formula (4) and a polymerizable unsaturated bond-containing structure represented by the following formula (2), [Chemical formula 2] In formula (4), R 23 represents an aromatic group with or without substituents; R 24 is a hydrogen atom or a group represented by formula (3); in formula (2), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group; R 9 is a hydrogen atom or a group represented by formula (3); R 24 and at least one of R 9 is a group represented by formula (3); in formula (3), R 10 represents a divalent hydrocarbon group with or without substituents.

12. A resin, characterized in that, It has an aromatic ring-containing structure represented by the following formula (1') and a polymerizable unsaturated bond-containing structure represented by the following formula (2'), with a polymerizable unsaturated double bond equivalent of 600 g / equivalent to 7000 g / equivalent, [Chemical formula 3] In formula (1’), R 1 represents an oxygen atom or a sulfur atom; R 2 represents an aromatic group with or without substituents; in formula (2’), R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; R 7 and R 8 are the same or different and represent a direct bond or a divalent organic group.

13. A photosensitive resin composition, characterized in that, It contains the resin, alkali-soluble resin, polymerizable compound, and photoinitiator described in claim 12.

14. A cured product, characterized in that, It is formed by curing the photosensitive resin composition described in claim 13.

Images