Alkali-soluble resin, light-sensitive resin composition, methods respectively for producing those, and use of those

Abstract

The present invention provides: an alkali-soluble resin having excellent photocurability and capable of providing a cured product having a high refractive index; and a light-sensitive resin composition. The present invention is 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), in which the polymerizable unsaturated bond equivalent is 700 to 8000 g / equivalent. (In formula (1), R1 represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom that may have a substituent; R2 represents an aromatic group that may have a substituent; and R3 represents a hydrogen atom, or a group represented by formula (3). In formula (2), R4, R5 and R6 are the same as or different from one another and each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; R7 and R8 are the same as or different from each other and each independently represent a direct bond or a bivalent organic group; R9 represents a hydrogen atom or a group represented by formula (3); and at least one of R3 and R9 represents a group represented by formula (3). In formula (3), R10 represents a bivalent hydrocarbon group that may have a substituent.)

Description

Alkali-soluble resin, photosensitive resin composition, manufacturing method thereof, and use thereof

[0001] The present invention relates to an alkali-soluble resin, a photosensitive resin composition, a method for producing the same, and uses thereof. More specifically, the present invention relates to an alkali-soluble resin, a photosensitive resin composition, and a method for producing the same, which have excellent photocurability and can give a cured product with a high refractive index, and a display device member and a display device using the same.

[0002] Various studies have been conducted on the application of alkali-soluble resins and photosensitive resin compositions to various uses, such as various optical members and electric / electronic devices, including color filters, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, organic insulating films, and organic protective films used in liquid crystal displays and solid-state imaging devices, and resins and resin compositions having excellent properties required for each use have been developed.

[0003] In recent years, optical components and electrical and electronic devices have become smaller, thinner, and more energy-efficient, and this has led to demands for higher performance from the various components used in them. To meet these demands, research has been conducted on alkali-soluble resins, which are used as materials for various components.

[0004] Alkali-soluble resins have been developed to meet various needs. 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 (a) having two or more epoxy groups per molecule, a phenol (b) having a substituent containing an aryl group, and an unsaturated monobasic acid (c).

[0005] Furthermore, for example, Patent Document 2 describes an alkali-developable photocurable / thermosetting composition that can provide a solder resist film that is excellent in heat resistance, adhesion, resolution, resistance to electroless plating, electrical properties, moisture absorption resistance, etc., and that contains a photosensitive prepolymer obtained by reacting a polybasic acid anhydride with an alcoholic hydroxyl group of a reaction product of an epoxy compound having two or more epoxy groups in one molecule, a predetermined phenol compound and / or naphthol compound, and an unsaturated group-containing monocarboxylic acid.

[0006] JP-A No. 11-49840 JP-A No. 11-315107

[0007] However, these conventional alkali-soluble resins have a low refractive index, and for use in optical applications requiring a high refractive index, a high refractive index of about 1.60 is required, but such a demand has not yet been fully met.

[0008] Furthermore, in recent years, when alkali-soluble resins are used in optical applications such as color filters, there has been a strong demand for higher performance, such as higher brightness and higher contrast of display panels, and in order to better exhibit the physical properties of the cured film, it is desirable that the curing reaction proceeds sufficiently.

[0009] The present invention has been made in view of the above-mentioned current situation, and aims to provide an alkali-soluble resin and a photosensitive resin composition that have excellent photocurability and can give a cured product with a high refractive index.

[0010] The present inventors have conducted extensive research into alkali-soluble resins and have found that when an alkali-soluble resin has a specific aromatic ring-containing structure and a polymerizable unsaturated bond-containing structure and has a polymerizable unsaturated bond equivalent within a specific range, it is possible to give a cured product that has excellent photocurability and a high refractive index, and have thereby completed the present invention.

[0011] That is, the present invention provides the following aspects: [1] An alkali-soluble resin having an aromatic ring-containing structure represented by the following formula (1) and a polymerizable unsaturated bond-containing structure represented by the following formula (2), and having a polymerizable unsaturated bond equivalent of 700 to 8,000 g / equivalent.

[0012]

[0013] (In formula (1), R １ represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent. ２ represents an aromatic group which may have a substituent. ３ is a hydrogen atom or a group represented by formula (3). ４ , R ５ and R ６are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. ７ and R ８ are the same or different and represent a direct bond or a divalent organic group. ９ is a hydrogen atom or a group represented by formula (3). ３ and R ９ At least one of the groups represented by formula (3) is a group represented by formula (3). １０represents a divalent hydrocarbon group which may have a substituent.) [2] The alkali-soluble resin according to [1] above, characterized in that it has an acid value of 30 to 150 mgKOH / g. [3] The alkali-soluble resin according to [1] or [2] above, characterized in that it has an epoxy equivalent of more than 10,000 g / equivalent. [4] The alkali-soluble resin according to any one of [1] to [3] above, characterized in that its main chain structure has a novolak structure. [5] A photosensitive resin composition comprising the alkali-soluble resin according to any one of [1] to [4] above, a polymerizable compound, and a photopolymerization initiator. [6] A cured product obtained by curing the alkali-soluble resin according to any one of [1] to [4] above or the photosensitive resin composition according to [5] above. [7] A member for a display device, characterized in that it comprises the cured product according to [6] above. [8] A display device, characterized in that it comprises the member for a display device according to [7] above. [9] A method for producing an alkali-soluble resin, the method comprising: a first step of reacting an epoxy resin (a) having two or more epoxy groups per molecule with an aromatic group-containing compound (b) and an unsaturated monocarboxylic acid (c), and a second step of reacting the reaction product obtained in the first step with a polybasic acid anhydride (d), wherein the amounts of the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) used in the first step are adjusted so that the resulting alkali-soluble resin has a polymerizable unsaturated bond equivalent of 700 to 8,000 g / equivalent.

[10] A method for producing a photosensitive resin composition, the method comprising: a step of producing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 to 8,000 g / equivalent by the method for producing an alkali-soluble resin according to the method described in [9] above; and a step of mixing the resulting alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

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

[0014]

[0015] (In formula (4), R ２３ represents an aromatic group which may have a substituent.２４ is a hydrogen atom or a group represented by formula (3). 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. ７ and R ８ are the same or different and represent a direct bond or a divalent organic group. ９ is a hydrogen atom or a group represented by formula (3). ２４ and R ９ At least one of the groups represented by formula (3) is a group represented by formula (3). １０ represents a divalent hydrocarbon group which may have a substituent.)

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

[0016]

[0017] (In formula (1'), R １ represents an oxygen atom or a sulfur atom. ２ represents an aromatic group which may have a substituent. 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. ７ and R ８ and are the same or different and represent a direct bond or a divalent organic group.

[13] A photosensitive resin composition comprising the resin according to

[12] above, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

[14] A cured product obtained by curing the photosensitive resin composition according to

[13] above.

[0018] The alkali-soluble resin and photosensitive resin composition of the present invention can provide a cured product having excellent photocurability and a high refractive index, and a display device member and a display device containing the cured product. Furthermore, the method for producing an alkali-soluble resin of the present invention can easily produce an alkali-soluble resin having excellent photocurability and a high refractive index.

[0019] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope that does not change the gist of the present invention. It should be noted that embodiments combining two or more of the individual preferred embodiments of the present invention described below also fall within preferred embodiments of the present invention. In this specification, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid," and "(meth)acrylate" means "acrylate and / or methacrylate." Furthermore, in this specification, the numerical range "Min to Max" means not less than the minimum value Min and not more than the maximum value Max. Furthermore, when preferred numerical values ​​are described in stages for the upper and lower limit values, a numerical range obtained by appropriately combining the separately described upper and lower limit values ​​is also a preferred numerical range.

[0020] 1. Alkali-Soluble Resin <First Alkali-Soluble Resin> The first alkali-soluble resin of the present invention is characterized by 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), and having a polymerizable unsaturated bond equivalent of 700 to 8000 g / equivalent.

[0021] The reason why the first alkali-soluble resin of the present invention has excellent photocurability and a high refractive index is believed to be as follows. That is, the first alkali-soluble resin of the present invention has a specific aromatic ring-containing structure, which allows it to give a cured product with a high refractive index. Furthermore, it has a predetermined range of polymerizable unsaturated bonds in the side chains, which allows it to have excellent photocurability and a high crosslink density upon curing, thereby giving a cured product with an even higher refractive index.

[0022] In the above formula (1), R １represents an ester bond, an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent. Examples of the substituent include an alkyl group, an aralkyl group, an aryl group, a thioester group, a thioether group, a disulfide group, an alkoxy group, an amino group or a salt thereof, a halogen atom, a trifluoromethyl group, a benzamino group, a boronic acid group, a hydroxyl group, a mercapto group, a thiocyanate group, an alkylthiocyanate group, an isothiocyanate group, a thiourea group, a sulfonic acid group, a carboxyl group, an aldehyde group, a heterocyclic group, or a group combining these. Among these, R is particularly preferred in that it increases the refractive index. １ is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom. In addition, the presence of a sulfur atom can function as an antioxidant, thereby imparting weather resistance to the resin.

[0023] R ２ represents an aromatic group which may have a substituent. The aromatic group may be monocyclic or polycyclic as long as it has an aromatic ring structure. It may also contain a heteroatom. The rings constituting the polycyclic aromatic group may be condensed, bonded by a single bond, or linked in a manner that they share one carbon atom. The rings constituting the polycyclic aromatic group may also contain at least an aromatic ring, and may be a group consisting of only aromatic rings, or a group consisting of aromatic rings and non-aromatic rings.

[0024] Examples of the aromatic group include monovalent groups obtained by removing one hydrogen atom from a benzene-based aromatic compound, a non-benzene-based aromatic compound, or a heteroaromatic compound.

[0025] Examples of the benzene-based aromatic compound include hydrocarbon compounds containing a benzene ring, such as monocyclic hydrocarbon compounds such as benzene; condensed ring hydrocarbon compounds such as naphthalene, anthracene, triphenylene, and pyrene; and polycyclic hydrocarbon compounds such as biphenylene and fluorene.

[0026] Examples of the non-benzene aromatic compounds include hydrocarbon compounds containing unsaturated cyclic compounds other than a benzene ring, such as annulene and azulene.

[0027] Examples of the heteroaromatic compound include unsaturated cyclic compounds containing an element other than carbon and hydrogen atoms, such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples include monocyclic heteroaromatic compounds such as furan, thiophene, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, triazole, thiazole, thiadizole, and tetrazole; and polycyclic heteroaromatic compounds such as carbazole, benzoxazole, purine, azulene, benzofuran, isobenzofuran, benzothiophene, benzotriazole, isobenzothiophene, indole, isoindole, benzimidazole, and benzothiazole.

[0028] Among these, the aromatic group is preferably a monovalent group obtained by removing one hydrogen atom from a benzene-based aromatic compound, more preferably a phenyl group, a naphthyl group, or a biphenyl group, even more preferably a phenyl group or a biphenyl group, and most preferably a phenyl group.

[0029] The aromatic group preferably has 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.

[0030] Examples of the substituent that the aromatic group may have include an alkyl group, an aralkyl group, an aryl group, a thioester group, a thioether group, a disulfide group, an alkoxy group, an amino group or a salt thereof, a halogen atom, a trifluoromethyl group, a benzamino group, a boronic acid group, a hydroxyl group, a mercapto group, a thiocyanate group, an alkylthiocyanate group, an isothiocyanate group, a thiourea group, a sulfonic acid group, a carboxyl group, an aldehyde group, a heterocyclic group, or a combination thereof. Among these, an alkyl group is preferred. The number of carbon atoms in the substituent is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The aromatic group may have one or more of the above-mentioned substituents.

[0031] Specific examples of the aromatic group which may have the substituent include, in addition to the specific aromatic groups mentioned above, aromatic hydrocarbon groups such as a tolyl group, a xylyl group, a benzyl group, a phenethyl group, a benzhydryl group, a trityl group, a styryl group, and a cinnamyl group.

[0032] Specific examples of the aromatic group which may have the above substituent include monovalent groups obtained by removing one hydrogen atom from the following aromatic compounds: thiocyanate compounds such as benzyl thiocyanate; isothiocyanate compounds such as phenyl isothiocyanate, benzyl isothiocyanate, and 3,4-difluorophenyl isothiocyanate; mercaptan compounds such as trityl mercaptan, 4-aminothiophenol, 4-fluorothiophenol, 2,4-difluorothiophenol, 2-amino-4-(trifluoromethyl)thiophenol hydrochloride, 3,5-dichlorothiophenol, bis(3,5-dichlorophenyl)disulfide, 4-methoxythiophenol, 3-mercapto-4-methyl-1,2,4-triazole, 4-bromothiophenol, 2-mercaptobenzoxazole, 2,6-dimethylthiophenol, 4,4',4''-(1,3,5,2,4,6-trioxatriborinane-2,4,6-triyl)tribenzenethiol, 1,3,5-tris[3-(2mercaptoethylsulfanyl)propyl]isocyanate, 6-amino-8-mercaptopurine, 4-mercaptobenzamide, 4-mercaptophenylboronic acid, 2-naphthalenethiol, and diphenyl disulfide; Thiocarboxylic acid compounds such as thioacetic acid S-phenyl ester; sulfonyl halogen compounds such as 2-mesitylenesulfonyl chloride; sulfonic acid compounds such as benzenesulfonic acid; thiourea compounds such as diphenylthiourea; thiadiazole compounds such as 2,5-dimercapto-1,3,4-thiadiazole, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole, and 2,5-dithioacetic acid-1,3,4-thiadiazole; azide compounds such as 4-dodecylbenzenesulfonyl azide, 4-acetylaminobenzenesulfonyl azide, and diphenylphosphoric acid azide;1H-Tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-5-mercapto-1H-tetrazole, 2-methoxy-5-(5-trifluoromethyl-1H-tetrazol-1-yl) -benzaldehyde, 5,5'-bi-1H-tetrazole diammonium salt, 4,5-di(5-tetrazolyl)-[1,2,3]triazole, 5,5'-azobis-1H-tetrazole, 1-methyl-5-benzoyl-1H-tetrazole, (1-methyl-1H-tetrazol-5-yl)phenylmethanone oxime (E+Z), 5-ethylthio-1H-tetrazole, 1-benzyl-5-phenyl-1H-tetrazole and other tetrazole compounds; Thiazolidine compounds such as 2,4-thiazolidinedione, 2-thio-4-thiazolidone, and 2-imino-4-thiazolidinone; 4-thiazolecarboxylic acid; ketone compounds such as 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, and 4-hydroxypropiophenone; dicarboxaldehyde compounds such as 2,6-naphthalenedicarboxaldehyde and 2,7-naphthalenedicarboxaldehyde; trityl chloride compounds such as trityl chloride and 4,4'-dimethoxytrityl chloride;

[0033] Among them, R ２ As the alkyl group, an aromatic hydrocarbon group which may have a substituent is preferable, a phenyl group, a naphthyl group, or a biphenyl group which may have a substituent is more preferable, and a phenyl group or a biphenyl group which may have a substituent is even more preferable.

[0034] R ３ is a hydrogen atom or a group represented by the above formula (3). １０ represents a divalent hydrocarbon group which may have a substituent.

[0035] Examples of the divalent hydrocarbon group include divalent aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Examples of the divalent aliphatic hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, pentylene, neopentylene, hexamethylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, undecylene, and dodecylene, and alkenylene groups such as vinylene, propenylene, isopropenylene, butenylene, butadienylene, pentenylene, hexenylene, and heptenylene.

[0036] Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, norbornylene, and adamantylene, and cycloalkylidene groups such as cyclopentylidene and cyclohexylidene.

[0037] Examples of the divalent aromatic hydrocarbon group include arylene groups such as a phenylene group, a tolylene group, and a naphthylene group, as well as a cinnamylidene group and a biphenylene group.

[0038] Among these, the divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group or a divalent alicyclic hydrocarbon group, more preferably a divalent aliphatic hydrocarbon group, and even more preferably an alkylene group.

[0039] The divalent hydrocarbon group preferably has 2 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 carbon atoms.

[0040] Examples of the substituent that the divalent hydrocarbon group may have include a carboxyl group, a hydroxyl group, an alkoxy group, a halogen atom, and a hydrocarbon group having 1 to 7 carbon atoms.

[0041] In the above formula (2), R ４ , R ５ and R ６are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group having 1 to 6 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. ４ and R ５ is preferably a hydrogen atom, and R ６ is preferably a hydrogen atom or a methyl group.

[0042] 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. ７ and R ８ The divalent organic group represented by the formula (I) is a divalent hydrocarbon group, or a divalent hydrocarbon group and -O-, -CO-, -COO-, -NH-, -SO- or -SO ２ Examples of the divalent hydrocarbon group include groups in which a divalent hydrocarbon group is combined with a bond such as -. Examples of the divalent hydrocarbon group include the same groups as those described above. The divalent hydrocarbon group may contain two or more types. Among these, the divalent organic group is preferably a divalent hydrocarbon group or a group in which a divalent hydrocarbon group is combined with at least one bond selected from the group consisting of -O-, -CO-, and -COO-. Examples of the group in which a divalent hydrocarbon group is combined with at least one bond 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.

[0043] R ７ and R ８ is preferably a direct bond, a divalent hydrocarbon group, or a group formed by combining a divalent hydrocarbon group with at least one bond selected from the group consisting of —O— and —COO—, more preferably a direct bond or a divalent aliphatic hydrocarbon group, and even more preferably a direct bond.

[0044] In the above formula (2), R ９ is a hydrogen atom or a group represented by the above formula (3). ３ and R ９ At least one of the above is a group represented by the above formula (3). The group represented by the above formula (3) has a carboxyl group, which is an acid group. When a resin has such a group, it becomes alkali-soluble. By adjusting the amount of such acid groups, the alkali-soluble resin also becomes a resin with excellent developability.

[0045] The first alkali-soluble resin preferably has a novolac structure as a main chain structure, which is a structure in which a benzene ring or a naphthalene ring is bonded to an optionally substituted divalent hydrocarbon group in the main chain to form a repeating unit.

[0046] Specific examples of alkali-soluble resins having an aromatic ring-containing structure represented by the above formula (1) and a polymerizable unsaturated bond-containing structure represented by the above formula (2) include alkali-soluble resins having a structural unit (A) represented by the following formula (a) and a structural unit (B) represented by the following formula (b):

[0047]

[0048]

[0049] (In the formula, A represents a benzene ring or a naphthalene ring. R １ ~R ９ are the same as those described above. １１ and R １４ are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms. １２ and R １５ are the same or different and represent a substituent bonded to A. a is R １２ and is an integer of 0 to 5. １５ and is an integer from 0 to 5. １２ and R １５ When there are two or more of each of R, they may be the same or different. １３ and R １６ are the same or different and represent a direct bond or a divalent organic group.

[0050] In this specification, the term "structural unit" refers to a repeating unit that constitutes an alkali-soluble resin.

[0051] In the formulas (a) and (b), A represents a benzene ring or a naphthalene ring. From the viewpoint of the balance between a high refractive index and developability, A is preferably a benzene ring.

[0052] In the above formulas (a) and (b), R １１ and R １４ represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the divalent hydrocarbon group include the same groups as the divalent hydrocarbon groups described above. Among them, R １１ and R １４ The divalent hydrocarbon group represented by the formula (I) is preferably a divalent aliphatic hydrocarbon group, more preferably an alkylene group.

[0053] The divalent hydrocarbon group preferably has 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 carbon atom.

[0054] At least one of the atoms constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom, and the divalent hydrocarbon group may have a substituent such as an alkoxy group.

[0055] R １２ and R １５ are the same or different and represent a substituent bonded to A. Examples of the substituent bonded to A include a hydroxyl group and an organic group having 1 to 20 carbon atoms.

[0056] Examples of the organic group having 1 to 20 carbon atoms include those obtained by converting the divalent organic groups described above into monovalent groups, and having a carbon number of 1 to 20. Among these, R １２ and R １５ The substituent represented by is —OH, —O—CH ２ -(C ２ H ３ O), -CR ｃ R ｄ -(C ６ H ４ )-O-CH ２-(C ２ H ３ O), -CR ｃ R ｄ -(C ６ H ４ )-OH (wherein, R ｃ and R ｄ are the same or different and represent a hydrogen atom or a methyl group.) or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, even more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a methyl group.

[0057] In the above formula (a), a is a substituent R １２ and is an integer of 0 to 5. In terms of good developability, a is preferably 0 to 3, more preferably 1 to 3, and even more preferably 1. When a is 2 or more, that is, when R １２ If there are two or more, R １２ may be the same as or different from each other.

[0058] In the above formula (b), b is a substituent R １５ represents the number of R １５ If there are two or more, R １５ may be the same as or different from each other.

[0059] R １３ and R １６ are the same or different and represent a direct bond or a divalent organic group. Examples of the divalent organic group include the same groups as the divalent organic groups described above. Among them, R １３ and R １６ is preferably a direct bond.

[0060] The first alkali-soluble resin may have one or more types of the structural unit (A). The content of the structural unit (A) in the alkali-soluble resin is preferably 51 to 93 mol%, more preferably 55 to 92 mol%, even more preferably 60 to 91 mol%, still more preferably 60 to 90 mol%, particularly preferably 60 to 80 mol%, and most preferably 60 to 75 mol%, relative to 100 mol% of all structural units.

[0061] The first alkali-soluble resin may have one or more types of the structural unit (B). The content of the structural unit (B) in the alkali-soluble resin is preferably 7 to 49 mol%, more preferably 8 to 45 mol%, even more preferably 9 to 40 mol%, and still more preferably 10 to 40 mol%, relative to 100 mol% of all structural units.

[0062] The first alkali-soluble resin may further have a structural unit (C) other than the structural units (A) and (B) described above. The alkali-soluble resin may have one or more structural units (C).

[0063] An example of the structural unit (C) is a structural unit represented by the following formula (c):

[0064]

[0065] (In the formula, A represents a benzene ring or a naphthalene ring. R ３ is the same as above. １７ represents a divalent hydrocarbon group having 1 to 20 carbon atoms. １８ represents a substituent bonded to A. c represents R １８ and is an integer from 0 to 5. １８ When there are two or more R １９ represents a direct bond or a divalent organic group. ２０ represents an organic group.)

[0066] The above R １７ The divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is the same as the above-mentioned R１１ The alkylene group is preferably a divalent aliphatic hydrocarbon group, and more preferably an alkylene group.

[0067] The above R １８ The substituent represented by the formula (I) is the same as the above-mentioned R １２ and preferably, —OH, —O—CH ２ -(C ２ H ３ O), -CR ｃ R ｄ -(C ６ H ４ )-O-CH ２ -(C ２ H ３ O), -CR ｃ R ｄ -(C ６ H ４ )-OH (wherein, R ｃ and R ｄ are the same or different and represent a hydrogen atom or a methyl group.), or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, still more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a methyl group.

[0068] In the above formula (c), c is a substituent R １８ and is an integer of 0 to 5. In terms of good developability, c is preferably 0 to 3, more preferably 1 to 3, and even more preferably 1. When c is 2 or more, that is, when R １８ If there are two or more, R １８ may be the same as or different from each other.

[0069] R １９ represents a direct bond or a divalent organic group. １９ The divalent organic group represented by the formula (I) is the same as the above-mentioned R １３ Among them, groups similar to the divalent organic group represented by R １９ is preferably a direct bond.

[0070] R ２０ represents an organic group. ２０Examples of the organic group represented by R include the above-mentioned divalent organic groups converted to monovalent groups, and among these, groups having an acid group are preferred. It is also preferred that the group does not have a double bond. ２０ By appropriately selecting the organic group, it is possible to control the developability and the reactivity of the double bond.

[0071] Examples of the acid group include 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, a sulfonic acid group, etc. Among these, a carboxyl group or a carboxylic anhydride group is preferred, and a carboxyl group is more preferred, in terms of good developability.

[0072] Examples of the group having an acid group include —R ｅ -R ｆ (In the formula, R ｅ represents a divalent organic group. ｆ represents an acid group. ) and the like. Examples of the divalent organic group include the same groups as the organic groups described above. Among them, a group formed by combining a divalent hydrocarbon group with at least one selected from the group consisting of -O- and -COO- is preferred.

[0073] R ２０ The organic group represented by the formula (I) preferably also has 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. Examples of the functional group include a hindered phenol group, a hindered amine group, a benzotriazole group, a triazine group, a cyanoacrylate group, a melamine group, and a benzoate group.

[0074] R ２０ The number of carbon atoms in the organic group represented by the formula (I) is preferably 1 to 20, more preferably 1 to 16, and even more preferably 2 to 12. ｆ By positioning the acid group represented by the formula (I) at a position away from the main chain of the alkali-soluble resin, the developability can be improved.

[0075] The first alkali-soluble resin may have one or more types of the structural unit (C). The content of the structural unit (C) is preferably 0 to 20 mol%, more preferably 0.1 to 20 mol%, even more preferably 0.5 to 15 mol%, and even more preferably 1 to 10 mol%, relative to 100 mol% of all structural units.

[0076] The first alkali-soluble resin may also have a structural unit (D) represented by the following formula (d): By introducing the structural unit (D) to perform chain extension, the resin can be designed to have any molecular weight.

[0077]

[0078] In the above formula (d), L represents a direct bond or a linking group. ２１ and R ２２ are the same or different and represent a substituent. ２１ and is an integer of 0 to 4. ２２ and is an integer from 0 to 4. ２１ and R ２２ When there are a plurality of, they may be the same or different.

[0079] Examples of the linking group include an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, and -SO ２ Examples include divalent bonds such as - and -NH-, and combinations thereof.

[0080] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms. The alkylene group may be linear, branched, or cyclic.

[0081] The alkylene group and arylene group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, or an iodine atom, or an alkyl group.

[0082] The structural unit (D) represented by the above formula (d) is preferably a structural unit derived from any one compound selected from bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z, more preferably a structural unit derived from bisphenol S, bisphenol A, or bisphenol F, and even more preferably a structural unit derived from bisphenol S.

[0083] Preferred examples of the structural unit (D) include structural units represented by the following formula (d-1), (d-2), or (d-3).

[0084]

[0085] When the first alkali-soluble resin has the structural unit (D), the content of the structural unit (D) is preferably 0.1 to 10 mol %, more preferably 0.2 to 5 mol %, and even more preferably 0.5 to 2 mol %, relative to 100 mol % of all structural units.

[0086] The polymerizable unsaturated bond equivalent of the first alkali-soluble resin is 700 to 8000 g / equivalent. By having the polymerizable unsaturated bond equivalent in this range, the photocurability of the alkali-soluble resin can be improved. From the viewpoint of reducing the brittleness of the cured product, the polymerizable unsaturated bond equivalent of the alkali-soluble resin is preferably 750 to 6000 g / equivalent, more preferably 800 to 5000 g / equivalent, even more preferably 900 to 4000 g / equivalent, and even more preferably 900 to 2000 g / equivalent.

[0087] The polymerizable unsaturated bond equivalent is the mass of the solid content of the alkali-soluble resin solution per 1 mol of polymerizable unsaturated bonds in the alkali-soluble resin. In this specification, the 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 alkali-soluble resin. The polymerizable unsaturated bond equivalent can be determined by dividing the mass (g) of the alkali-soluble resin solid content in the alkali-soluble resin solution by the amount (mol) of polymerizable unsaturated bonds in the alkali-soluble resin. Alternatively, it may be calculated by measuring the number of ethylenic double bonds contained per 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070:1992.

[0088] The acid value of the first alkali-soluble resin is preferably 30 to 150 mgKOH / g. In terms of further improving developability, the acid value is more preferably 40 to 120 mgKOH / g, and even more preferably 45 to 90 mgKOH / g. The acid value is the acid value per 1 g of resin solid content obtained by measurement by neutralization titration using a potassium hydroxide (KOH) solution, and can be determined by the method described in the Examples below.

[0089] The epoxy equivalent of the first alkali-soluble resin is preferably greater than 10,000 g / equivalent. When the epoxy equivalent is within the above range, the alkali-soluble resin of the present invention has almost no epoxy groups. Therefore, the storage stability is good. The epoxy equivalent of the alkali-soluble resin is more preferably greater than 13,000 g / equivalent. The epoxy equivalent can be determined by a method in accordance with JIS K7236:2001, and can be determined by dividing the mass (g) of the resin solid content by the number of moles (mol) of epoxy groups contained in the resin.

[0090] The weight average molecular weight of the first alkali-soluble resin is preferably 1,000 to 100,000. In terms of good curability, the weight average molecular weight of the alkali-soluble resin is more preferably 2,000 to 50,000, even more preferably 3,000 to 20,000, even more preferably 3,500 to 15,000, and particularly preferably 4,000 to 10,000. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

[0091] The glass transition temperature (Tg) of the first alkali-soluble resin is preferably 40° C. or higher, more preferably 60° C. or higher, and even more preferably 80° C. or higher, in terms of improving film strength, and is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 200° C. or lower, in terms of good developability. The glass transition temperature (Tg) of the first alkali-soluble resin is preferably 40 to 300° C., more preferably 60 to 250° C., and even more preferably 80 to 200° C. The glass transition temperature can be determined by a method in accordance with JIS-K7121.

[0092] <Second Alkali-Soluble Resin> The second alkali-soluble resin of the present invention is characterized by having an aromatic ring-containing structure represented by the following formula (4) and a polymerizable unsaturated bond-containing structure represented by the following formula (2).

[0093]

[0094] (In formula (4), R ２３ represents an aromatic group which may have a substituent. ２４ is a hydrogen atom or a group represented by formula (3). 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. ７ and R ８ are the same or different and represent a direct bond or a divalent organic group. ９ is a hydrogen atom or a group represented by formula (3). ２４ and R ９At least one of the groups represented by formula (3) is a group represented by formula (3). １０ represents a divalent hydrocarbon group which may have a substituent.

[0095] The reason why the second alkali-soluble resin of the present invention has excellent photocurability and can give a cured product with a high refractive index is thought to be that the refractive index of the cured product can be increased by having the structure of formula (4) containing a sulfur atom and an aromatic group, and that the photocurability can be improved by having the structure of formula (2).

[0096] In the above formula (4), R ２３ represents an aromatic group which may have a substituent. ２３ The aromatic group which may have a substituent represented by the formula (1) is R ２ Examples of the aromatic group include the same groups as the aromatic group represented by the following formula (1) which may have a substituent.

[0097] In the above formula (4), R ２４ is a hydrogen atom or a group represented by formula (3). The group represented by formula (3) is the same as the group represented by formula (3) described in the above section <First alkali-soluble resin>.

[0098] The polymerizable unsaturated bond-containing structure represented by the formula (2) is the same as the polymerizable unsaturated bond-containing structure represented by the formula (2) described in the above section <First alkali-soluble resin>.

[0099] The second alkali-soluble resin preferably has a novolac structure as its main chain structure, similar to the first alkali-soluble resin.

[0100] Preferred examples of the alkali-soluble resin having the aromatic ring-containing structure represented by the above formula (4) and the polymerizable unsaturated bond-containing structure represented by the above formula (2) include alkali-soluble resins having a structural unit (E) represented by the following formula (e) and the structural unit (B) described in the above section <First alkali-soluble resin>:

[0101]

[0102] (In the formula, A represents a benzene ring or a naphthalene ring. R ２３and R ２４ are the same as those described above. ２５ represents a divalent hydrocarbon group having 1 to 20 carbon atoms. ２６ represents a substituent bonded to A. f represents R ２６ and is an integer from 0 to 5. ２６ When there are two or more R, they may be the same or different. ２７ represents a direct bond or a divalent organic group.

[0103] In the formula, A represents a benzene ring or a naphthalene ring, and preferably represents a benzene ring. ２５ The divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (a) is R １１ Examples include the same groups as the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the following formula:

[0104] R ２６ The substituent represented by the formula (a) is R １２ Examples of the substituent include the same groups as those represented by the following formula:

[0105] f is R ２６ and is an integer of 0 to 5. f is preferably 0 to 3, more preferably 1 to 3, and most preferably 1, in terms of good developability.

[0106] The second alkali-soluble resin may have one or more types of the structural unit (E). The content of the structural unit (E) in the second alkali-soluble resin is preferably 1 to 99 mol%, more preferably 20 to 95 mol%, even more preferably 40 to 93 mol%, still more preferably 50 to 90 mol%, particularly preferably 60 to 85 mol%, and most preferably 60 to 80 mol%, relative to 100 mol% of all structural units.

[0107] The content of the structural unit (B) in the second alkali-soluble resin is preferably 1 to 80 mol%, more preferably 2 to 70 mol%, even more preferably 3 to 50 mol%, still more preferably 5 to 40 mol%, particularly preferably 10 to 40 mol%, and most preferably 15 to 40 mol%, relative to 100 mol% of all structural units.

[0108] The second alkali-soluble resin may also contain other structural units in addition to the structural units (E) and (B). Examples of such other structural units include the structural unit (C) or the structural unit (D) described in the section <First alkali-soluble resin> above. When the second alkali-soluble resin contains the structural unit (C) and / or the structural unit (D), the content ratio thereof is preferably the same as the content ratio in the first alkali-soluble resin.

[0109] The polymerizable unsaturated bond equivalent of the second alkali-soluble resin is preferably 300 to 8000 g / equivalent, more preferably 500 to 6000 g / equivalent, even more preferably 700 to 5000 g / equivalent, still more preferably 800 to 4000 g / equivalent, and particularly preferably 800 to 2000 g / equivalent.

[0110] The acid value, epoxy group equivalent, weight average molecular weight, and glass transition temperature of the second alkali-soluble resin are preferably the same as the acid value, epoxy group equivalent, weight average molecular weight, and glass transition temperature of the first alkali-soluble resin.

[0111] 2. Method for Producing Alkali-Soluble Resin <Method for Producing First Alkali-Soluble Resin> The method for producing the first alkali-soluble resin of the present invention is not particularly limited as long as it can produce the first alkali-soluble resin described above. However, a production method including the following steps is preferred in terms of efficient production of the first alkali-soluble resin of the present invention: (1) a first step of reacting an epoxy resin (a) having two or more epoxy groups per molecule with an aromatic group-containing compound (b) and an unsaturated monocarboxylic acid (c), and (2) a second step of reacting the reaction product obtained in the first step with a polybasic acid anhydride (d). In addition, the first alkali-soluble resin of the present invention can be produced by adjusting the amounts of the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) used in the first step so that the resulting alkali-soluble resin has a polymerizable unsaturated bond equivalent of 700 to 8,000 g / equivalent.

[0112] This first method for producing an alkali-soluble resin, i.e., a method for producing an alkali-soluble resin, comprises a first step of reacting an epoxy resin (a) having two or more epoxy groups per molecule with an aromatic group-containing compound (b) and an unsaturated monocarboxylic acid (c), and a second step of reacting the reaction product obtained in the first step with a polybasic acid anhydride (d), wherein the amounts of the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) used in the first step are adjusted so that the resulting alkali-soluble resin has a polymerizable unsaturated bond equivalent of 700 to 8,000 g / equivalent. Each step is described below.

[0113] In the first method for producing an alkali-soluble resin of the present invention, the starting material epoxy resin (a) having two or more epoxy groups in one molecule is not particularly limited, and any known epoxy resin having two or more epoxy groups in one molecule can be used, including bisphenol-type epoxy resins; biphenyl-type epoxy resins; alicyclic epoxy resins; polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenylglycidyl ether ethane; phenol novolac-type epoxy resins and cresol novolac-type epoxy resins. Examples of epoxy resins include: polyphenol compounds obtained by the condensation reaction of phenolic compounds such as phenol, o-cresol, m-cresol, and naphthol with aromatic aldehydes having a phenolic hydroxyl group, and reaction products of epichlorohydrin with polyphenolic compounds obtained by the addition reaction of phenolic compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene; epoxidized ring-opening polymers of 4-vinylcyclohexene-1-oxide with peracids; and epoxy resins having heterocyclic rings such as triglycidyl isocyanurate. Furthermore, epoxy resins obtained by reacting two or more molecules of these epoxy resins with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol to bond and extend their chains can also be used. Alternatively, the epoxy resin may be a homopolymer or copolymer of a monomer having an epoxy group, such as glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, it is preferable to use a novolac type epoxy resin as the raw material in order to increase the number of ethylenically unsaturated bonds (polymerizable unsaturated double bonds) present in one molecule of the alkali-soluble resin and improve the photocurability.

[0114] The starting epoxy resin (a) having two or more epoxy groups per molecule preferably has an epoxy equivalent of 500 g / equivalent or less, more preferably 400 g / equivalent or less, and even more preferably 300 g / equivalent or less, in order to provide an alkali-soluble resin with excellent developability and photocurability.

[0115] The aromatic group-containing compound (b) is not particularly limited as long as it has an aromatic group and a group capable of reacting with an epoxy group, and examples thereof include the aromatic compounds described above. Examples of the aromatic group include the groups having the aromatic ring structure described above. Examples of the group capable of reacting with an epoxy group include an acidic group, an amino group, a hydroxyl group, etc. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, etc., and preferably a phenolic hydroxyl group or a mercapto group. The aromatic group-containing compound is preferably an aromatic group-containing acid compound having the aromatic group and an acidic group.

[0116] The aromatic group-containing compound is not particularly limited as long as it can give the above-mentioned aromatic ring-containing structure to the obtained resin, but preferably includes phenol derivatives such as phenylphenol, thiophenol derivatives such as toluenethiol and benzenethiol, and alcohol derivatives such as hydroxyphenethyl alcohol.Among them, thiophenol derivatives are preferred, and benzenethiol is most preferred, because the thioether bond produced can achieve both high refractive index and high-speed developability.These compounds may be used alone or in combination of two or more.

[0117] Furthermore, when hydroxyphenethyl alcohol is used or used in combination with it, a chain-extended acid group can be introduced into the alkali-soluble resin by reacting it with a polybasic acid anhydride in step (2) described below. Such an acid group is located at a position away from the main chain, which improves developability and reactivity during curing.

[0118] The unsaturated monocarboxylic acid (c) is not particularly limited as long as it has an unsaturated bond and a carboxyl group, but preferably has 3 to 20 carbon atoms, more preferably has 3 to 10 carbon atoms, and even more preferably has 3 to 4 carbon atoms.

[0119] Examples of the unsaturated monocarboxylic acid (c) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, β-acryloxypropionic acid, a reaction product of a hydroxyalkyl (meth)acrylate having one hydroxyl group and one (meth)acryloyl group with a dibasic acid anhydride, and a reaction product of a polyfunctional (meth)acrylate having one hydroxyl group and two or more (meth)acryloyl groups with a dibasic acid anhydride. Among these, those having a (meth)acryloyl group, such as acrylic acid and methacrylic acid, are preferred. Methacrylic acid is particularly preferred because it allows the resulting alkali-soluble resin to give a cured product with particularly excellent solvent resistance. These may be used alone or in combination.

[0120] The aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) may be added all at once, or in portions or successively. However, addition in portions or successively is preferred in terms of suppressing side reactions.

[0121] In the method for producing an alkali-soluble resin of the present invention, in the first step of reacting an aromatic group-containing compound (b) and an unsaturated monocarboxylic acid (c) with an epoxy resin (a) having two or more epoxy groups per molecule, the epoxy resin (a) may be reacted with the unsaturated monocarboxylic acid (c) and then with the aromatic group-containing compound (b); the unsaturated monocarboxylic acid (c) and the aromatic group-containing compound (b) may be reacted with the epoxy resin (a) all at once; or the epoxy resin (a) may be reacted with the aromatic group-containing compound (b) and then with the unsaturated monocarboxylic acid (c).

[0122] In the first step, when the aromatic group-containing compound (b) is reacted with the epoxy resin (a), the amount of the aromatic group-containing compound (b) added is preferably such that the amount of acid groups in the aromatic group-containing compound (b) is 0.51 to 0.93 mol, more preferably 0.55 to 0.92 mol, even more preferably 0.6 to 0.91 mol, still more preferably 0.6 to 0.9 mol, particularly preferably 0.6 to 0.8 mol, and most preferably 0.6 to 0.75 mol, per chemical equivalent (molar equivalent) of the epoxy group in the epoxy resin (a).

[0123] The reaction rate of the epoxy resin (a) and the aromatic group-containing compound (b) can be increased by replacing the atmosphere in the reaction vessel with an inert gas such as nitrogen to reduce the oxygen concentration. The oxygen concentration in the reaction vessel is preferably 1% by volume or less, more preferably 0.5% by volume or less, and even more preferably 0.3% by volume or less. In order to reduce the oxygen concentration in the reaction solution, it is also preferable to bubble the solution with an inert gas such as nitrogen.

[0124] In the first step, the total amount of the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) used is preferably 0.8 to 1.2 moles per mole of epoxy group in the epoxy resin (a). Using them in such a ratio facilitates achieving good curability of the alkali-soluble resin and good physical properties of the cured product. The amount is preferably 0.85 to 1.15 moles, more preferably 0.9 to 1.1 moles.

[0125] By adjusting the amounts of the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c) used in the first step in this manner, an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 to 8,000 g / equivalent can be obtained.

[0126] In the first step of the first method for producing an alkali-soluble resin of the present invention, the reaction of the aromatic group-containing compound (b) with the epoxy resin (a) and the unsaturated monocarboxylic acid (c) may be carried out in either order, or simultaneously, as described above. These reactions can be carried out in the presence or absence of a diluent such as a polymerizable compound or solvent, as described below, in the presence of a polymerization inhibitor such as hydroquinone or oxygen, and a reaction catalyst such as a tertiary amine, a tertiary phosphine such as trimethylphosphine, tributylphosphine, or triphenylphosphine, lithium chloride, a quaternary ammonium salt, or a quaternary phosphonium salt, typically at 60 to 140°C. From the viewpoints of reaction efficiency, stability during the reaction, and storage stability of the alkali-soluble resin, tertiary phosphines are preferred, with triphenylphosphine being particularly preferred.

[0127] The amount of the reaction catalyst is not particularly limited, but is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass, per 100 parts by mass of the epoxy resin (a) having two or more epoxy groups per molecule.

[0128] Furthermore, in the first step, a polymerization inhibitor may be used. The polymerization inhibitor is not particularly limited, and known ones can be used, for example, benzoquinone, hydroquinones (e.g., hydroquinone, hydroquinone monomethyl ether, p-tert-butylhydroquinone, p-benzoquinone, etc.), phenols (e.g., 2,6-di-t-butyl-4-methylphenol, 6-t-butyl-2,4-dimethylphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol)), catechols (e.g., p-tert-butylcatechol, etc.), amines (e.g., N,N-diethylhydroxylamine, etc.), 1,1-diphenyl-2-picrylhydrazyl, tri-p-nitrophenylmethyl, phenothiazine, piperidine 1-oxyls (e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl, etc.), oxygen, etc. can be used.

[0129] When the polymerization inhibitor is used in the first step, the amount of the polymerization inhibitor used is preferably 0.001 to 1 mass %, more preferably 0.01 to 0.5 mass %, based on 100 mass % of the epoxy resin (a) having two or more epoxy groups per molecule.

[0130] The reaction may be carried out in a solvent, and examples of the reaction solvent include hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; esters such as cellosolve acetate, carbitol acetate, (di)propylene glycol monomethyl ether acetate, (di)methyl glutarate, (di)methyl succinate, and (di)methyl adipate; ketones such as methyl isobutyl ketone and methyl ethyl ketone; and ethers such as (di)ethylene glycol dimethyl ether.

[0131] The reaction temperature in the first step is not particularly limited as long as the reaction proceeds, but is preferably 40 to 140°C. By performing the reaction at such a temperature, the reaction can proceed efficiently. The reaction temperature is more preferably 50 to 135°C, and even more preferably 60 to 130°C.

[0132] In the first step, a carboxylic acid having no double bond may be reacted with the epoxy resin (a) together with the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c). By reacting the carboxylic acid having no double bond, the double bond equivalent, epoxy equivalent, glass transition temperature, etc. of the alkali-soluble resin can be adjusted. Examples of the carboxylic acid having no double bond include propionic acid, acetic acid, butyric acid, decanoic acid, and 2-ethylhexylcarboxylic acid.

[0133] In the first step, the epoxy resin (a) may be reacted with an acid compound having a functional group with radical scavenging ability or ultraviolet absorbing ability, together with the aromatic group-containing compound (b) and the unsaturated monocarboxylic acid (c). By reacting such an acid compound, weather resistance can be imparted to the resin.

[0134] Examples of the functional group having a radical scavenging ability or an ultraviolet absorbing ability include the functional groups having a radical scavenging ability or an ultraviolet absorbing ability described above. Examples of the acid group contained in the acid compound include the acid groups described above, with a carboxyl group being preferred.

[0135] Specific examples of the acid compound having a functional group with the radical scavenging ability or UV absorbing ability include, for example, 3,5-di-tert-butyl 4-hydroxybenzoic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3-methylsalicylic acid, trimethylhydroquinone, 3-phenylsalicylic acid, 4-hydroxy-3,5-dimethylbenzoic acid, 3,5-di-tert-butylsalicylic acid, mycophenolic acid, xanthohumol, and monoethyl 3,5-di-tert-butyl 4-hydroxybenzylphosphonate. Of these, 3,5-di-tert-butyl 4-hydroxybenzoic acid and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid are preferred.

[0136] In the second step of the method for producing the alkali-soluble resin, the reaction product (intermediate) obtained in the first step is reacted with a polybasic acid anhydride (d), whereby the polybasic acid anhydride (d) reacts with the hydroxyl groups present in the reaction product to obtain the alkali-soluble resin of the present invention having carboxyl groups introduced therein. The resulting alkali-soluble resin can be developed in an alkali, and therefore can be used as an alkali-developable curable resin for image formation, etc.

[0137] The polybasic acid anhydride (d) used in the second step is not particularly limited, but preferably has 3 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 4 to 10 carbon atoms.

[0138] Examples of the polybasic acid anhydride (d) include dibasic acid anhydrides such as phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic acid; and aliphatic or aromatic tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. These polybasic acid anhydrides can be used alone or in combination. Among these, it is preferable to use dibasic acid anhydrides. Furthermore, from the viewpoint of providing a cured product of the resulting alkali-soluble resin with particularly excellent solvent resistance, polybasic acid anhydrides such as phthalic anhydride, which give an alkali-soluble resin having a cyclic structure in its structure, are particularly preferred.

[0139] In the second step, the polybasic acid anhydride (d) is preferably reacted in a ratio of 0.1 mol to 1.1 mol per chemical equivalent of the hydroxyl groups in the reaction product obtained in the reaction of the first step. By reacting the polybasic acid anhydride (d) in this manner, the addition reaction of the polybasic acid anhydride (d) can be efficiently carried out, and carboxyl groups can be suitably introduced into the resulting alkali-soluble resin.

[0140] The reaction of the reaction product obtained in the reaction of the first step with the polybasic acid anhydride (d) in the second step can be carried out in the presence or absence of a polymerizable compound or a diluent such as a solvent, as described below, and, if necessary, in the coexistence of the polymerization inhibitor and reaction catalyst described above, as in the reaction of the first step. In the second step, a reaction catalyst may be used, and a tertiary phosphine is preferred, with triphenylphosphine being more preferred.

[0141] The reaction temperature in the second step is not particularly limited as long as the reaction proceeds, but is preferably 45 to 130°C. By performing the reaction at such a temperature, the reaction can proceed efficiently. The reaction temperature is more preferably 50 to 120°C, and even more preferably 55 to 110°C.

[0142] Furthermore, when the alkali-soluble resin has the structural unit (D), for example, prior to the first step, the epoxy resin (a) is reacted with a compound capable of introducing the structural unit (D) to thereby chain-extend the epoxy resin (a), and the chain-extended epoxy resin (a) is then subjected to the first step, thereby producing an alkali-soluble resin having the structural unit (D).

[0143] Examples of compounds into which the structural unit (D) can be introduced include the bisphenol compounds from which the structural unit (D) is derived.

[0144] In the above reaction, a reaction catalyst may be used. Examples of the reaction catalyst used in this reaction include the same catalysts as those used in the first and second steps described above.

[0145] The method for producing the first alkali-soluble resin may include other steps as long as it includes the first and second steps.

[0146] <Method for producing second alkali-soluble resin> The method for producing the second alkali-soluble resin may include a method including the same first and second steps as the method for producing the first alkali-soluble resin described above, except that the aromatic group-containing compound used contains a sulfur atom and the polymerizable unsaturated bond equivalent of the alkali-soluble resin is not limited to 700 to 8000 g / equivalent.

[0147] The aromatic group-containing compound (b') used in the second method for producing an alkali-soluble resin preferably contains a sulfur atom. The aromatic group-containing compound (b') is preferably one of the aromatic group-containing compounds (b) used in the first method for producing an alkali-soluble resin, in which the group reactive with an epoxy group contains a sulfur atom. The aromatic group-containing compound (b') is preferably a compound containing the aromatic group and a mercapto group described above.

[0148] In the first step of the second method for producing an alkali-soluble resin, the aromatic group-containing compound (b') is preferably added and reacted in an amount such that the amount of acid groups in the aromatic group-containing compound (b') is 0.01 to 0.99 mol, more preferably 0.2 to 0.95 mol, even more preferably 0.4 to 0.93 mol, still more preferably 0.6 to 0.9 mol, particularly preferably 0.6 to 0.85 mol, and most preferably 0.6 to 0.80 mol, per chemical equivalent (molar equivalent) of epoxy groups in the epoxy resin (a).

[0149] In the second alkali-soluble resin, the polymerizable unsaturated bond equivalent is not limited, but by adjusting the amounts of the aromatic group-containing compound (b') and the unsaturated monocarboxylic acid (c) used in the first step, an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 300 to 8000 g / equivalent can be obtained.

[0150] The method for producing an alkali-soluble resin of the present invention described above includes the first and second steps described above. The reaction product (intermediate) obtained in the first step is preferably a resin having an aromatic ring-containing structure represented by the following formula (1') and a polymerizable unsaturated bond-containing structure represented by the following formula (2'), and having a polymerizable unsaturated double bond equivalent of 600 to 7000 g / equivalent.

[0151]

[0152] (In formula (1'), R １ represents an oxygen atom or a sulfur atom. ２ represents an aromatic group which may have a substituent. ４ , R ５ and R ６are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. ７ and R ８ and are the same or different and represent a direct bond or a divalent organic group.) Such a resin also constitutes one aspect of the present invention, and is capable of providing a cured product with excellent photocurability and a high refractive index.

[0153] R in the above formula (1′) １ and R ２ is the same as the above formula (1), and R in the above formula (2′) ４ ~R ８ is the same as the above-mentioned equation (2).

[0154] The polymerizable unsaturated bond equivalent of the resin is not particularly limited, but is preferably 650 to 6,000 g / equivalent, more preferably 700 to 5,000 g / equivalent, and even more preferably 750 to 4,000 g / equivalent.

[0155] The resin having an aromatic ring-containing structure represented by the formula (1′) is a resin having a structure represented by the formula (a) above, which is “—CH—O—R ３ A preferred example is a resin having a structural unit (A') in which "-CH-OH" is substituted for "-CH-OH". The content of the structural unit (A') in the above resin is preferably in the same range as the content of the structural unit (A) described above.

[0156] The resin having a polymerizable unsaturated bond-containing structure represented by the formula (2′) is a resin having a structure represented by the formula (b) above, which is “—CH—O—R ９ A preferred example is a resin having a structural unit (B') in which "-CH-OH" is substituted for "-CH-OH". The content of the structural unit (B') in the above resin is preferably within the same range as the content of the structural unit (B) described above.

[0157] The above resin may further include the structural unit (C) and the structural unit (D) described above.

[0158] 3. Photosensitive Resin Composition A photosensitive resin composition containing the first and / or second alkali-soluble resin of the present invention, a polymerizable compound, and a photopolymerization initiator also constitutes one aspect of the present invention. Because the photosensitive resin composition of the present invention contains the alkali-soluble resin described above, it has excellent photocurability and can provide a cured product with a high refractive index. Hereinafter, the first alkali-soluble resin of the present invention and the second alkali-soluble resin described above will also be collectively referred to as the alkali-soluble resin of the present invention.

[0159] The content of the first and / or second alkali-soluble resin is not particularly limited and may be set appropriately depending on the application, the blending of other components, etc. For example, it is preferably 5 to 90 mass %, more preferably 10 to 80 mass %, even more preferably 15 to 75 mass %, and particularly preferably 15 to 70 mass %, relative to 100 mass % of the total solid content of the photosensitive resin composition. In this specification, the "total solid content" means the total amount of components that form a cured product (components excluding solvents and the like that volatilize during the formation of a cured product and curing catalysts).

[0160] (Polymerizable Compound) The polymerizable compound is a low molecular weight compound having a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), and electron beams, and examples thereof include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.

[0161] Examples of the monofunctional compound include N-substituted maleimide monomers, (meth)acrylic acid esters, (meth)acrylamides, unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended, unsaturated acid anhydrides, aromatic vinyls, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, unsaturated isocyanates, etc. Furthermore, monomers having an active methylene group or an active methine group can also be used.

[0162] Examples of the polyfunctional compound include the following compounds: bifunctional (meth)acrylate compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F alkylene oxide di(meth)acrylate;

[0163] Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid-modified product, pentaerythritol triacrylate succinic acid-modified product, dipentaerythritol pentaacrylate phthalic acid-modified product, pentaerythritol triacrylate phthalic acid-modified product,

[0164]

[0165] a tri- or higher functional (meth)acrylate compound such as a modified product of dipentaerythritol hexaacrylate represented by the formula:

[0166] polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether;

[0167] vinyl ether group-containing (meth)acrylic acid esters such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate;

[0168] polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether;

[0169] Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; polyfunctional aromatic vinyls such as divinylbenzene; etc. These polymerizable compounds may be used alone or in combination of two or more.

[0170] Among the above polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further enhancing the curability of the photosensitive resin composition. The number of functions of the above polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more. The number of functions is preferably 10 or less, more preferably 8 or less. The number of functional groups is preferably 3 to 10, more preferably 4 to 8. The molecular weight of the above polymerizable compound is not particularly limited, but from the viewpoint of handling, it is preferably, for example, 2000 or less.

[0171] As the polyfunctional polymerizable compound, from the viewpoints of reactivity, economy, availability, etc., preferred are compounds having a (meth)acryloyl group, such as polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and (meth)acryloyl group-containing isocyanurate compounds, and more preferred are polyfunctional (meth)acrylate compounds. By including a compound having a (meth)acryloyl group, the photosensitive resin composition has better photosensitivity and curability, and a cured product with even higher hardness and transparency can be obtained. It is more preferred to use a trifunctional or higher polyfunctional (meth)acrylate compound as the polyfunctional polymerizable compound.

[0172] The content of the polymerizable compound is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 40% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0173] (Photopolymerization Initiator) Specific examples of the photopolymerization initiator include aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE (registered trademark) 907", manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1-one ("IRGACURE 369", manufactured by BASF), and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one ("IRGACURE 379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE 651", manufactured by BASF), and phenylglyoxylic acid methyl ester ("DAROCURE benzyl ketal compounds such as 1-hydroxycyclohexylphenyl ketone ("IRGACURE184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR1173", manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE2959", manufactured by BASF), 2-hydroxy Hydroketone compounds such as 1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one ("IRGACURE 127", manufactured by BASF Corporation) and 1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone ("IRGACURE 500", manufactured by BASF Corporation); and other alkylphenone compounds exemplified in paragraphs

[0084] to

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

[0174] The content of the photopolymerization initiator is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 8% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0175] The photosensitive resin composition of the present invention contains at least the alkali-soluble resin, polymerizable compound, and photopolymerization initiator described above, and may further contain one or more other components as needed. Furthermore, one or more of each component may be used. The other components are described below.

[0176] (Polyfunctional thiol compound) The photosensitive resin composition may further contain a polyfunctional thiol compound. When the photosensitive resin composition contains the alkali-soluble resin containing a polymerizable unsaturated bond in a side chain and a polyfunctional thiol compound, an enethiol reaction occurs simultaneously upon exposure or heating, and the crosslink density can be improved. In particular, when an acrylate-type polymerizable unsaturated bond is present in the resin, the enethiol reaction proceeds well.

[0177] The polyfunctional thiol compound is preferably a compound having two or more mercapto groups in one molecule and a molecular weight of 200 to 1000, and particularly preferably a tri- to penta-functional secondary thiol. By adding such a polyfunctional thiol compound to the photosensitive resin composition, the curability and storage stability can be further improved.

[0178] Examples of the polyfunctional thiol compound include mercaptopropionic acid derivatives such as butanediol bisthiopropionate, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate) (Karenz (registered trademark) PE-1), 1,4-bis(3-mercaptobutyryloxy)butane (Karenz BD-1), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Karenz NR-1). Note that the polyfunctional thiol compound is preferably a compound that does not have a hydroxyl group and / or an aromatic ring in the molecule.

[0179] Commercially available products of the polyfunctional thiol compounds can also be used, and examples thereof include "Chiokalchol 20" manufactured by Kao Corporation, "Karenz MT (registered trademark) PE1," "Karenz MT BD1," "Karenz MT NR1," "TPMB," and "TEMB" manufactured by Showa Denko K.K., and "TMMP," "TEMPIC," "PEMP," "EGMP-4," "DPMP," "TMMP II-20P," and "PEMP II-20P" manufactured by SC Organic Chemical Co., Ltd.

[0180] The content of the polyfunctional thiol compound is preferably 0.3 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 8% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0181] (Metal oxide particles) The photosensitive resin composition preferably also contains metal oxide particles. When the photosensitive resin composition contains metal oxide particles, a cured product with a high refractive index can be obtained. In addition, the photosensitivity and dielectric properties are improved. Although the reason for this is unclear, it is presumed that a small refractive index difference between the resin and the metal oxide particles can reduce light loss due to Rayleigh scattering during exposure. Even when the photosensitive resin composition is highly loaded with metal oxide particles, the resolution is not impaired, and therefore the dielectric properties can be improved.

[0182] Examples of the metal oxide particles include oxide particles of light-transmitting metals with high refractive indexes 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, and Te. Among these, the metal oxide particles preferably contain at least one metal element selected from the group consisting of Ti, Al, Zr, Zn, Sn, Ce, and Si, in order to provide a cured product with a higher refractive index. Furthermore, it is more preferable that the metal oxide particles contain Zr from the viewpoint of being able to provide a cured film with a high dielectric constant, and it is more preferable that the metal oxide particles contain Si from the viewpoint of being able to provide a cured film with high hardness.

[0183] The metal oxide may be an oxide of a single metal, a solid solution of two or more oxides, or a composite oxide. Examples of single metal oxides include aluminum oxide (Al ２ O ３ ), titanium oxide (TiO ２ ), zirconium oxide (ZrO ２ ), indium oxide (In ２ O ３ ), zinc oxide (ZnO), tin oxide (SnO ２ ), lanthanum oxide (La ２ O ３ ), yttrium oxide (Y ２ O ３ ), cerium oxide (CeO ２ ), magnesium oxide (MgO), silicon oxide (SiO ２Examples of solid solutions of two or more oxides include ITO and ATO. Examples of composite oxides include barium titanate (BaTiO ３ ), perovskite (CaTiO ３ ), spinel (MgAl ２ O ４ Among these, zirconium dioxide particles (ZrO ２ particles) and / or silicon dioxide particles (SiO ２ particles) are preferred.

[0184] The metal oxide particles are preferably surface-modified, since this can enhance dispersibility in the photosensitive resin composition. The surface modification of the metal oxide particles can be achieved by a known method, such as mixing the metal oxide particles with a surface modifier in a solvent or performing a hydrothermal reaction in the presence of water.

[0185] The surface modifier is not particularly limited, and examples thereof include known coupling agents, surfactants, carboxylic acid compounds, etc. Only one type of surface modifier may be used, or two or more types may be used.

[0186] Among these, carboxylic acid compounds are preferred as the surface modifier in terms of further improving the dispersibility of the metal oxide particles. Examples of the carboxylic acid compound include carboxylic acids and (meth)acrylic acid, which may have a substituent. Examples of the substituent include an ester group, an ether group, an amide group, a thioester group, a thioether group, a carbonate group, a urethane group, and a urea group. Examples of the carboxylic acid compound include aliphatic carboxylic acids and cyclic carboxylic acids, such as acetic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, salicylic acid, naphthenic acid, decanoic acid, and lauric acid.

[0187] As the metal oxide particles, the metal oxide particles described in JP-A-2013-216858 are preferred.

[0188] The crystallite diameter of the metal oxide particles is preferably 1 to 20 nm, more preferably 1 to 15 nm, and even more preferably 1 to 10 nm. The crystallite diameter can be determined by X-ray diffraction analysis.

[0189] The number average primary particle diameter of the metal oxide particles is preferably less than 30 nm, more preferably 1 to 25 nm, even more preferably 3 to 20 nm, still more preferably 5 to 20 nm, and particularly preferably 5 to 15 nm. The number average primary particle diameter can be determined by magnifying and observing the metal oxide particles with a transmission electron microscope (TEM), field emission transmission electron microscope (FE-TEM), field emission scanning electron microscope (FE-SEM), or the like, randomly selecting 100 particles, measuring their lengths in the major axis direction, and calculating the arithmetic average.

[0190] The refractive index of the metal oxide particles is preferably 1.70 to 2.70, and more preferably 1.90 to 2.70.

[0191] The specific surface area of ​​the metal oxide particles is preferably 10 to 400 m ２ / g, more preferably 20 to 200m ２ / g, and more preferably 30 to 150m ２ / g.

[0192] The content of the metal oxide particles is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, relative to 100% by mass of the total solid content of the alkali-soluble resin composition.

[0193] The photosensitive resin composition may also contain other components in addition to the above-mentioned components, as necessary. Examples of the other components include solvents; colorants (pigments, dyes); dispersants; heat resistance improvers; leveling agents; development aids; silane-based, aluminum-based, titanium-based, and other coupling agents; fillers; thermosetting resins such as phenolic resins, polyvinylphenols, epoxy compounds, and epoxy resins; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants; matting agents; defoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinone diazide compounds; polyhydric phenol compounds; cationically polymerizable compounds; and thermal acid generators. These may be used alone or in combination of two or more. These other components can be appropriately selected from known compounds and their amounts can be appropriately determined.

[0194] Furthermore, a photosensitive resin composition (also referred to as photosensitive resin composition (x)) containing the resin that is the reaction product (intermediate) of the first step, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator also constitutes one aspect of the present invention.

[0195] The alkali-soluble resin contained in the photosensitive resin composition (x) is not particularly limited, and any known alkali-soluble resin can be used, and the alkali-soluble resin of the present invention described above may also be used.

[0196] The polymerizable compound and the photopolymerization initiator contained in the photosensitive resin composition (x) may be the same as those described above. The content of each of these components may be the same as those described above.

[0197] The photosensitive resin composition (x) may also contain other components, including the same components as those in the photosensitive resin composition described above. The content of each of these components can be appropriately set.

[0198] 4. Method for Producing Photosensitive Resin Composition The method for producing the photosensitive resin composition of the present invention is not particularly limited and may be a known method, for example, a method in which the above-mentioned components are mixed and dispersed using various mixers or dispersers. The mixing and dispersion steps are not particularly limited and may be carried out by a known method. In addition, the method may further include other steps that are usually carried out.

[0199] Among these, the photosensitive resin composition can be produced by the above-mentioned method for producing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 700 to 8000 g / equivalent or R １ is a sulfur atom, a method including the steps of: preparing an alkali-soluble resin having a polymerizable unsaturated bond equivalent of 300 to 8,000 g / equivalent; and mixing the obtained alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. Such a method for preparing a photosensitive resin composition also constitutes one aspect of the present invention.

[0200] By using the alkali-soluble resin or photosensitive resin composition of the present invention, a cured product having a high refractive index and excellent curability can be obtained. A cured product obtained by curing such an alkali-soluble resin or photosensitive resin composition of the present invention also constitutes one aspect of the present invention. Furthermore, the above-mentioned photosensitive resin composition (x) can also provide a cured product having a high refractive index and excellent curability. A cured product of such photosensitive resin composition (x) also constitutes one aspect of the present invention.

[0201] When the cured product is a cured film, the film thickness is preferably 0.1 to 50 μm, more preferably 0.5 to 40 μm, and even more preferably 1 to 30 μm.

[0202] The method for obtaining the cured product is not particularly limited, and any known method may be used, such as a method in which the above-mentioned alkali-soluble resin or photosensitive resin composition is applied to or molded on a substrate, and then cured by heating, irradiating with active energy rays such as ultraviolet rays, or a combination of these to obtain a cured product. Among these, the method for producing a cured product is preferably a method including the steps of applying the photosensitive resin composition to a substrate to form a coating film, irradiating the formed coating film with light, and heating the irradiated coating film.

[0203] The substrate is not particularly limited and may be appropriately selected depending on the purpose and application. Examples include substrates made of various materials such as glass plates and plastic plates.

[0204] The method for applying the photosensitive resin composition to a substrate to form a coating film is not particularly limited, and can be performed by a known method such as spin coating, slit coating, roll coating, or cast coating.

[0205] After applying the photosensitive resin composition to a substrate, it is preferable to dry the applied product to form a coating film. The drying can be carried out by a known method, for example, using a hot plate, an IR oven, a convection oven, etc. The drying conditions are appropriately selected depending on the boiling point of the solvent components contained, the type of curable component, the film thickness, the performance of the dryer, etc., but it is usually preferable to perform the drying at a temperature of 50 to 160°C for 10 to 300 seconds.

[0206] The method for irradiating the formed coating film with light is not particularly limited, and can be any known method. Examples of light sources for actinic rays used for light irradiation include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers.

[0207] When the coating film is irradiated with light, the irradiation may be carried out through a photomask. A mask having a light-shielding portion formed according to the desired pattern may be used as the photomask. After the irradiation with light through the photomask, a development process using a developer to remove the unirradiated portions may be carried out. The irradiated portions are cured by the light irradiation, and the cured product becomes insoluble or poorly soluble in the developer. Meanwhile, the unirradiated portions dissolve in the developer and are removed by the development process, thereby obtaining a patterned cured film. The development process can usually be carried out at a development temperature of 10 to 50°C by a method such as immersion development, spray development, brush development, or ultrasonic development.

[0208] The developer is not particularly limited as long as it dissolves the photosensitive resin composition, but typically an organic solvent or an alkaline aqueous solution is used, or a mixture thereof may be used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. Examples of organic solvents and alkaline aqueous solutions include those described in JP 2015-157909 A.

[0209] After the light irradiation, the coating film is preferably heated to 160°C or lower. The heating temperature of the coating film is more preferably 150°C or lower. The lower limit of the heating temperature is preferably 70°C or higher, more preferably 80°C or higher, in terms of maintaining curability. The heating temperature is preferably 70 to 160°C, more preferably 80 to 150°C.

[0210] The heating time is not particularly limited, and is preferably 5 to 60 minutes, for example. The heating method is also not particularly limited, and can be performed using known heating equipment such as a hot plate, a convection oven, or a high-frequency heater.

[0211] The alkali-soluble resin and photosensitive resin composition of the present invention have excellent curability and can give cured products with a high refractive index. Therefore, the alkali-soluble resin and photosensitive resin composition can be suitably used in applications requiring curability and a high refractive index.

[0212] The alkali-soluble resin and photosensitive resin composition of the present invention can also be suitably used in applications requiring high development speed and developability. Therefore, they are suitably used for optical materials, particularly for resists. The photosensitive resin composition of the present invention can be suitably used for both negative-working and positive-working applications.

[0213] The alkali-soluble resin and photosensitive resin composition of the present invention, which have a high refractive index, can be used in a wide variety of applications, including magnetic recording materials, catalyst materials, ultraviolet absorbing materials, dental materials, contact lenses, intraocular lenses, high refractive index lenses for spectacles, optical computing, optical storage media, anti-reflection films, conformal coatings, microlens arrays, automotive top coats, paints, coating agents, hair cosmetics, gradient refractive index optical components and dynamic gradient refractive index components, nanoimprint materials, photocurable plastics, polymerizable compounds for hologram recording, glass surface coating materials, transparent coating materials for solar cells, plastic lenses, printing plates, semiconductor light-emitting elements (light-emitting diodes, organic light-emitting diodes, laser diodes), and the like. The alkali-soluble resin and photosensitive resin composition of the present invention can be widely used in a variety of applications, such as optical fibers, light guides (both planar and "fiber" geometric shapes), semiconductor elements, light diffusing members, prism sheets, hard coating materials, optical wiring members, diffraction gratings, sealing materials for LEDs and the like, pressure-sensitive adhesives, protective films used on the surfaces of glass, films, and sheets used in sensor elements such as CCD / CMOS and display elements such as displays, photocurable resins (OCR) used to bond image display members such as liquid crystals to plastic cover panels, reflective protective films used in transparent electrodes, index matching to prevent bones from appearing in ITO electrodes of touch panels, antiblocking layers, antireflective films for displays, and interlayer insulating films for semiconductors. In particular, 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.

[0214] In the present invention, the term "optical material" refers to a material used in components of devices in the optical field or the electrical / electronic field, such as color filters, light extraction layers, black matrices, photospacers, black column spacers, photoresists, overcoats, TFT planarization layers, TFT insulating films, and surface coatings for optical lenses used in liquid crystal, organic electroluminescence (EL), quantum dot, mini / micro LED display devices, solid-state imaging devices, and touch panel display devices. The alkali-soluble resin of the present invention is suitable for use in applications involving photolithography due to its alkali solubility, and can form cured films with high refractive index, 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 electroluminescence (EL) display devices. The alkali-soluble resin of the present invention can be suitably used as a highly refractive component that is photolithographically applicable and highly transparent.

[0215] In particular, the alkali-soluble resin and photosensitive resin composition are preferably used for display devices, and a member for a display device and a display device containing a cured product of the photosensitive resin composition also constitute one aspect of the present invention.

[0216] The alkali-soluble resin and photosensitive resin composition can also be suitably used for various optical components such as inks, printed wiring boards, insulating films, films, and organic protective films, as well as components for electrical and electronic devices.

[0217] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0218] The various evaluation methods used in the present examples are as follows.

[0219] <Weight-average molecular weight> The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions were as follows: Apparatus: Gel permeation chromatography apparatus HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSKgel Super HZM-M (manufactured by Tosoh Corporation) Detector: RI detector for liquid chromatography Measurement temperature: 40°C Solvent: THF (tetrahydrofuran) Sample concentration: 0.05 g / 10 cc Sample flow rate: 0.6 ml / min

[0220] <Acid Value> 3 g of resin solution was precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1 N KOH aqueous solution as the titrant. The titration was performed using an automatic titrator (product name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of solids (mg KOH / g) was determined from the acid value of the resin solution and the solids content of the resin solution. The solids content of the resin solution was determined as follows. That is, approximately 1 g of the resin solution was weighed into an aluminum cup, dissolved by adding approximately 3 g of acetone, and then allowed to dry naturally at room temperature. Then, using a vacuum dryer (manufactured by EYELA, product name: VOS-301SD), the resin solution was dried under vacuum at 140°C for 1.5 hours, allowed to cool in a desiccator, and the mass was measured. The solids content (mass%) of the resin solution was calculated from the mass loss.

[0221] <Polymerizable Unsaturated Bond Equivalent> The polymerizable unsaturated bond equivalent was determined by dividing the mass (g) of the resin solid content by the amount (mol) of polymerizable unsaturated bonds in the resin.

[0222] <Epoxy Equivalent> The epoxy equivalent was determined in terms of solid content by a method in accordance with JIS K7236:2001.

[0223] <Refractive Index (Resin)> The resin solution in Table 1 was uniformly applied onto a 5 cm square glass substrate (soda lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.) using a spin coater (1H-D7, manufactured by Mikasa Co., Ltd.). The coated plate was dried at 90°C for 3 minutes to obtain a laminate. After removing the resin composition adhering to the edge of the glass substrate, the obtained laminate was heat-treated at 95°C for 60 minutes using a Perfect Oven incubator (manufactured by Espec Corporation) and cooled to room temperature to obtain a laminate with a coating film thickness of 0.5 μm. The obtained laminate was used as a measurement sample, and the refractive index of the coating film at a light wavelength of 589 nm was calculated by performing a coating film reflectance simulation based on the Fresnel equation using the measured reflectance due to coating film interference using the following device. Device: Film Thickness Measurement System F-20, manufactured by Filmetrics. Standard fiber stage SS-1 (spot diameter 1.5 mm).

[0224] <Refractive Index (Photosensitive Resin Composition)> The photosensitive resin compositions according to the formulations shown in Tables 2 and 4 were uniformly coated onto a 5 cm square glass substrate (soda-lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.) using a spin coater (1H-D7, manufactured by Mikasa Co., Ltd.). The coated plate was dried at 90°C for 3 minutes and then exposed to 100 mJ using a high-pressure mercury lamp to obtain a laminate in which a coating film was formed on the glass substrate. After removing the resin composition adhering to the edge of the glass substrate, the obtained laminate was subjected to a heat treatment at 95°C for 60 minutes using a Perfect Oven incubator (manufactured by Espec Corporation) and cooled to room temperature to obtain a laminate with a coating film thickness of 0.5 μm. The obtained laminate was used as a measurement sample, and the refractive index value was determined in the same manner as for the refractive index of the resin described above.

[0225] <Solvent Resistance> A photosensitive resin composition having the formulation shown in Table 3 was spin-coated onto a 5 cm square glass substrate, dried at 100°C for 3 minutes, exposed to 200 mJ using a high-pressure mercury lamp, and heat-treated (post-cured) at 150°C for 40 minutes, yielding a cured film with a thickness of 2 μm. The cured film was then immersed in 20 g of propylene glycol monomethyl ether (PGME) at 40°C for 10 minutes and then removed. The absorbance of the immersion liquid (PGME) after removing the cured film was measured using a UV3100 spectrophotometer (manufactured by Shimadzu Corporation). A higher absorbance value indicated that more colorant had eluted into the immersion liquid, and the photosensitive resin composition was evaluated as having poor solvent resistance.

[0226] <Development Rate> The photosensitive resin composition was applied to a 10 cm square glass substrate by spin coating, followed by heat treatment (90°C, 3 minutes). The substrate was then exposed to light at an exposure dose of 60 mJ / cm2 (equivalent to 365 nm illuminance) using a UV aligner (manufactured by Dai Nippon Kaken Co., Ltd., trade name "MA-1100") equipped with a 2.0 kW ultra-high pressure mercury lamp through a photomask having 30 μm line-and-space openings at a distance of 50 μm from the coating film. A 0.05% potassium hydroxide aqueous solution was sprayed using a spin developer to dissolve and remove the unexposed areas, and the remaining exposed areas were developed by rinsing with pure water for 10 seconds, thereby evaluating developability. Specifically, the coating film developed as described above through the photomask was observed with a surface roughness meter (manufactured by Ryoka Systems Co., Ltd., trade name "VertScan 2.0"), and the spraying time of the 0.05% potassium hydroxide aqueous solution required for the unexposed areas to flow was defined as the development time. ◎: Development time less than 20 seconds ○: Development time 20 seconds or more but less than 30 seconds △: Development time 30 seconds or more but less than 40 seconds ×: Development time 40 seconds or more

[0227] <Weather Resistance> The photosensitive resin composition solutions in Table 4 were uniformly coated onto a 5 cm square glass substrate (soda lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.) using a spin coater (1H-D7, manufactured by Mikasa Co., Ltd.). The coated plate was dried at 100°C for 3 minutes to obtain a laminate. After removing the resin composition adhering to the edge of the glass substrate, the obtained laminate was exposed to 100 mJ using a high-pressure mercury lamp. Using a Perfect Oven incubator (manufactured by Espec Corporation), the laminate was subjected to a heat treatment 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. Apparatus: Xenon Weather Meter X25 (manufactured by Suga Test Instruments) Conditions: Chamber temperature 50°C, chamber humidity 17%, irradiance 0.45 kW / m ２ , 200 hours Evaluation method: The film thickness reduction rate (%) before and after the test was measured using a film thickness measurement system F-20 manufactured by Filmetrics Inc. The smaller the value, the better the weather resistance was evaluated to be.

[0228] <Measurement of Mass Loss Rate> The zirconia particles were heated in an air atmosphere from room temperature to 800°C at a rate of 10°C / min using a TG-DTA (thermogravimetric-differential thermal analysis) device, and the mass loss rate of the particles was measured. From the mass loss rate, the proportion of the compound surface-modifying the zirconia particles and the proportion of the zirconia particles were determined.

[0229] (Synthesis Example 1) Production of Alkali-Soluble Resin (A-1) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 132.1 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of cresol novolac epoxy resin (trade name "YDCN-704A", manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 206 g / equivalent), and the mixture was heated to 120°C. After the temperature of the reaction vessel reached 120°C, the system was purged with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 102.1 g (0.6 moles) of o-phenylphenol and 1 g of triphenylphosphine were added to carry out an addition reaction. The reaction was allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 28.8 g (0.4 mol) 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 to carry out an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 41.9 g (0.42 mol) of succinic anhydride and 108.2 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out for 7 hours at 100 ° C. to complete the reaction, and 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.

[0230] (Synthesis Example 2) Production of Alkali-Soluble Resin (A-2) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping tank inlet, 138.7 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1 were charged and heated to 120 ° C. After the temperature of the reaction vessel reached 120 ° C., the system was purged with nitrogen gas bubbling while maintaining the same temperature 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 to carry out an addition reaction, which was then allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in 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 to carry out an addition reaction, and 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 for 7 hours at 100 ° C. to complete the reaction, and 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.

[0231] (Synthesis Example 3) Preparation of Alkali-Soluble Resin (A-3) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping tank inlet, 142.9 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1 were charged and heated to 120 ° C. After the temperature of the reaction vessel reached 120 ° C., the system was purged with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume 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 to carry out an addition reaction, which was then allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in 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 to carry out an addition reaction, and 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 for 7 hours at 100 ° C. to complete the reaction, and then 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.

[0232] (Synthesis Example 4) Production of Alkali-Soluble Resin (A-4) In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping tank inlet, 134.3 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1 were charged and heated to 120 ° C. After the temperature of the reaction vessel reached 120 ° C., the system was purged with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5 vol% or less, and 93.6 g (0.55 mol) of o-phenylphenol, 13.8 g (0.1 mol) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in 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 to carry out an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 29.6 g (0.3 mol) of succinic anhydride and 100.3 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out for 7 hours at 100 ° C to complete the reaction, and 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.

[0233] (Synthesis Example 5) Production of Alkali-Soluble Resin (A-5) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 116.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1, and the temperature was raised to 120°C. After the temperature of the reaction vessel reached 120°C, the system was purged with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 66.1 g (0.6 mole) of thiophenol and 0.9 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 28.8 g (0.4 mol) 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 to carry out an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 37.4 g (0.37 mol) of succinic anhydride and 96.6 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out for 7 hours at 100 ° C to complete the reaction, and 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.

[0234] (Synthesis Example 6) Production of Alkali-Soluble Resin (A-6) 203.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1 were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping tank inlet, and the temperature was raised to 100°C. After the temperature of the reaction vessel reached 100°C, the temperature was maintained for 30 minutes to dissolve the resin. The system was purged with nitrogen while the temperature was cooled to 70°C. 99.2 g (0.9 mole) of thiophenol and 0.2 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 5 hours to complete the reaction. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 7.2 g (0.1 mol) of acrylic acid, 1.3 g of triphenylphosphine, and 0.3 g of Antage W-400 were added to carry out an addition reaction, and the reaction was carried out for 16 hours at 120 ° C. to complete the reaction. After cooling to room temperature, 27.5 g (0.275 mol) of succinic anhydride and 23.5 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out for 7 hours at 110 ° C. to complete the reaction. 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.

[0235] (Synthesis Example 7) Production of Alkali-Soluble Resin (A-7) 215.9 g of propylene glycol monomethyl ether acetate and 231 g (1 mole of epoxy group) of NC-7000-L (naphthalene-containing novolac epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 231.0 g / equivalent) were charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping vessel inlet, and the temperature was raised to 100°C by heating. After the temperature of the reaction vessel reached 100°C, the temperature was maintained for 30 minutes to dissolve the resin. The system was purged with nitrogen while the temperature was cooled to 70°C. 92.5 g (0.84 mol) of thiophenol and 0.2 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 5 hours to complete the reaction. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 11.5 g (0.16 mol) of acrylic acid, 1.3 g of triphenylphosphine, and 0.3 g of Antage W-400 were added to carry out an addition reaction, and the reaction was carried out for 16 hours at 120 ° C. to complete the reaction. After cooling to room temperature, 27.5 g (0.275 mol) of succinic anhydride and 27.2 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out for 7 hours at 110 ° C. to complete the reaction, and 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.

[0236] (Synthesis Example 8) Production of Alkali-Soluble Resin (A-8) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping vessel inlet was charged with 135.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1, and the temperature was raised to 120°C. After the temperature of the reaction vessel reached 120°C, the system was purged with nitrogen while maintaining the same temperature, and 108.9 g (0.64 moles) of p-phenylphenol, 1.4 g (0.01 moles) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in 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 to carry out 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 for 10 hours at 100 ° C to complete the reaction, and 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.

[0237] (Synthesis Example 9) Production of Alkali-Soluble Resin (A-9) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping vessel inlet was charged with 135 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1, and the temperature was raised to 120°C. After the temperature of the reaction vessel reached 120°C, the system was purged with nitrogen while maintaining the same temperature, and 102.1 g (0.6 moles) of o-phenylphenol, 6.9 g (0.05 moles) of p-hydroxyphenyl-2-ethanol, and 1 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in 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 to carry out 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 for 8 hours at 100 ° C. to complete the reaction, and then 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.

[0238] (Synthesis Example 10) Production of Alkali-Soluble Resin (A-10) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 310.5 g of propylene glycol monomethyl ether acetate, and after nitrogen substitution, the vessel was heated to 90 ° C. On the other hand, as the dropping vessel (A), a beaker containing 70.0 g of methyl methacrylate (MMA), 142.2 g of glycidyl methacrylate (GMA) (1 mol of epoxy group), and 4.2 g of t-butylperoxy-2-ethylhexanoate (NOF Corporation's "Perbutyl (registered trademark) O") was prepared by stirring and mixing, and as the dropping vessel (B), 2.1 g of n-dodecyl mercaptan (nDM) and 7.8 g of propylene glycol monomethyl ether acetate were prepared by stirring and mixing. After the temperature of the reaction vessel reached 90 ° C, while maintaining the same temperature, dropwise addition from the dropping vessel was initiated over 3 hours, and polymerization was carried out. After the completion of the dropwise addition, the reaction vessel was kept at 90 ° C for 1 hour, then the temperature was raised to 115 ° C, and aging was carried out for 90 minutes. Thereafter, it was cooled to room temperature, and under nitrogen gas bubbling, 74.9 g (0.68 mol) of thiophenol and 0.9 g of triphenylphosphine were added to carry out an addition reaction, and the reaction was carried out for 8 hours to complete the reaction. Thereafter, while blowing in 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 Antege W-400 were added to carry out 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 added, and the reaction was carried out for 7 hours at 100 ° C to complete the reaction, and an alkali-soluble resin solution (A-10) was obtained. The physical properties of the resulting alkali-soluble resin (A-10) are shown in Table 1.

[0239] (Synthesis Example 11) Production of Resin Intermediate (A-11) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping tank inlet was charged with 116.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1, and the temperature was raised to 120°C. After the temperature of the reaction vessel reached 120°C, the system was purged with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 66.1 g (0.6 mole) of thiophenol and 0.9 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 28.8 g (0.4 mol) 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 to carry out an addition reaction, which was carried out for 16 hours to complete the reaction, thereby obtaining a resin intermediate (A-11). Various physical properties of the obtained resin intermediate (A-11) are shown in Table 1.

[0240] (Synthesis Example 12) Production of Alkali-Soluble Resin (A-12) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping tank inlet was charged with 181.5 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1, and the temperature was raised to 120°C. After the temperature of the reaction vessel reached 120°C, the system was purged with nitrogen gas bubbling while maintaining the same temperature until the oxygen concentration was 0.5% by volume or less, and 66.1 g (0.6 mole) of thiophenol and 0.9 g of triphenylphosphine were added to carry out an addition reaction, which was then allowed to proceed for 8 hours to complete the reaction. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 28.1 g (0.39 mol) of acrylic acid, 2.8 g (0.01 mol) of 3-(3,5-di-t-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 to carry out an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 37.4 g (0.37 mol) of succinic anhydride and 24.3 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out for 7 hours at 100 ° C. to complete the reaction, and 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.

[0241] Comparative Synthesis Example 1: Production of Comparative Alkali-Soluble Resin (B-1) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping tank inlet was charged with 117.5 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1, and the mixture was heated to 120°C. After the temperature of the reaction vessel reached 120°C, the system was purged with nitrogen while maintaining the same temperature, and 68.1 g (0.4 mole) of o-phenylphenol and 1 g of triphenylphosphine were added to carry out an addition reaction, which was then carried out for 8 hours to complete the reaction. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 43.2 g (0.6 mol) of acrylic acid, 0.6 g of triphenylphosphine, 0.3 g of Antage W-400, and 18.5 g of propylene glycol monomethyl ether acetate were added to carry out an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 39.5 g (0.39 mol) of succinic anhydride and 101.9 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out for 7 hours at 100 ° C to complete the reaction. 726.8 g of propylene glycol monomethyl ether was then added to obtain a comparative alkali-soluble resin solution (B-1). The various physical properties of the obtained alkali-soluble resin (B-1) are shown in Table 1.

[0242] Comparative Synthesis Example 2: Production of Comparative Alkali-Soluble Resin (B-2) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping tank inlet was charged with 157.6 g of propylene glycol monomethyl ether acetate and 206 g (1 mole of epoxy group) of the same cresol novolac epoxy resin "YDCN-704A" used in Example 1, and the mixture was heated to 120°C. After the temperature of the reaction vessel reached 120°C, the system was purged with nitrogen while maintaining the same temperature, and 161.7 g (0.95 mole) of o-phenylphenol and 1.1 g of triphenylphosphine were added to carry out an addition reaction, which was then carried out for 8 hours to complete the reaction. Thereafter, while blowing in a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, 3.6 g (0.05 mol) of acrylic acid, 0.7 g of triphenylphosphine, 0.4 g of Antage W-400, and 1.5 g of propylene glycol monomethyl ether acetate were added to carry out an addition reaction, and the reaction was carried out for 16 hours to complete the reaction. After cooling to room temperature, 46.2 g (0.46 mol) of succinic anhydride and 119.2 g of propylene glycol monomethyl ether acetate were added, and the reaction was carried out for 10 hours at 100 ° C to complete the reaction. 850.4 g of propylene glycol monomethyl ether was then added to obtain a comparative alkali-soluble resin solution (B-2). The various physical properties of the obtained alkali-soluble resin (B-2) are shown in Table 1.

[0243] Using the resins of Example Synthesis Examples 1 to 12 and Comparative Synthesis Examples 1 and 2, photosensitive resin compositions were prepared according to the formulations shown in Table 2, and the refractive indexes of the resins were measured by the method described above. The results are shown in Table 2.

[0244] (Examples 13 to 39, Comparative Examples 3 to 6) Photosensitive resin compositions 1 to 31 were obtained by mixing the resin solutions obtained in the Example Synthesis Examples and Comparative Synthesis Examples, dipentaerythritol hexaacrylate, a photopolymerization initiator (Irgacure (registered trademark) OXE-02, manufactured by BASF), pigment dispersion 1 or zirconia particle dispersion, and propylene glycol monomethyl ether acetate in the formulations (solid content amounts) shown in Table 3 or Table 4. The pigment dispersion 1 and zirconia particle dispersion were prepared by the following methods.

[0245] (Preparation of Pigment Dispersion 1) 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a dispersant, 2.25 parts of C.I. Pigment Green 58 and 1.5 parts of C.I. Pigment Yellow 138 as colorants were mixed and dispersed for 3 hours using a paint shaker to obtain Pigment Dispersion 1.

[0246] (Preparation of Zirconia Particle Dispersion) Production Example 1 (Coated Zirconium Oxide Nanoparticles Coated with 2-ethylhexanoic Acid and / or a Carboxylate Derived from 2-ethylhexanoic Acid (Coated ZrO ２ Preparation of Particles 1) A zirconium 2-ethylhexanoate mineral spirit solution (782 g, zirconium 2-ethylhexanoate content: 44% by mass, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) was mixed with pure water (268 g). The resulting mixture was placed in an autoclave equipped with a stirrer, and the atmosphere inside the autoclave was replaced with nitrogen gas. The mixture was then heated to 180°C and maintained at that temperature for 16 hours (autoclave internal pressure: 0.94 MPa) to react and produce zirconium oxide particles. The reacted mixture was then removed, and the precipitate that had accumulated at the bottom was filtered off, washed with acetone, and then dried. The dried precipitate (100 g) was dispersed in toluene (800 mL), resulting in a cloudy solution. Next, as a purification step, the mixture was again filtered using quantitative filter paper (Advantec Toyo Co., Ltd., No. 5C) to remove coarse particles and other particles from the precipitate. Furthermore, the filtrate was concentrated under reduced pressure to remove toluene, yielding white zirconium oxide nanoparticles 1 (coated ZrO ２ The particles 1) were collected. ２ When the crystalline structure of particle 1 was confirmed by XRD diffraction pattern, diffraction lines attributed to tetragonal and monoclinic crystals were detected. From the intensity of the diffraction lines, the ratio of tetragonal and monoclinic crystals was 54 / 46, and the particle diameter (crystallite diameter) was 5 nm. The coated ZrO obtained by measurement with an electron microscope (FE-TEM JEM-2100F TEM manufactured by JEOL Ltd., 600,000 times magnification) ２ The average particle size (number average primary particle size) of the particles 1 was 12 nm. ２When particle 1 was analyzed by infrared absorption spectroscopy, absorption due to C—H and absorption due to COOH were confirmed. ２ This is thought to be due to the 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid that coats the surface of Particle 1. Furthermore, the coated ZrO measured according to the above <Measurement of Mass Reduction Rate> ２ The mass reduction rate of particle 1 was 12 mass%. ２ The 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid coating the surface of the particle 1 is a coated ZrO ２ It was found that the amount was 12 mass % of the total amount of particles 1.

[0247] Production Example 2 (Zirconium oxide nanoparticles coated with 2-ethylhexanoic acid and / or a carboxylate derived from 2-ethylhexanoic acid and 2-acryloyloxyethyl succinate (coated ZrO ２ Preparation of particles 2)) The coated ZrO particles obtained in Preparation Example 1 ２ Particles 1 (10 g) and 2-acryloyloxyethyl succinate (1.5 g) were mixed and stirred in propylene glycol monomethyl ether acetate (12 g, hereinafter referred to as "PGMEA") until uniformly dispersed. Next, n-hexane (36 g) was added to aggregate the dispersed particles, making the solution cloudy, and the aggregated particles were separated from the cloudy solution using filter paper. Thereafter, the separated aggregated particles were added to n-hexane (36 g), and after stirring for 10 minutes, the aggregated particles were separated using filter paper. The obtained particles were dried in vacuum at room temperature to obtain zirconium oxide nanoparticles (coated ZrO) surface-treated with 2-ethylhexanoic acid and / or a carboxylate derived from 2-ethylhexanoic acid and 2-acryloyloxyethyl succinate. ２ Particles 2) were prepared. ２ Particle 2 is dispersed in deuterated chloroform to prepare a measurement sample. １Analysis by H-NMR was carried out. As a result, it was found that the molar ratio of 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid to 2-acryloyloxyethyl succinate was 24:76. The coated ZrO measured according to the above <Measurement of mass reduction rate> ２ The mass loss rate of Particle 2 was 18% by mass. Therefore, it was found that the amount of 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid, and 2-acryloyloxyethyl succinate coating the coated zirconium oxide particles was 18% by mass of the entire coated zirconium oxide particles. ２ Particles 2 (7 g), methyl ethyl ketone (3 g), and DISPER BYK-111 (manufactured by BYK Japan, 0.14 g) were mixed and stirred to obtain a zirconia particle dispersion. ２ The number average primary particle diameter of particles 2 was 12 nm.

[0248] The resulting photosensitive resin compositions 1 to 15 were evaluated for development speed and solvent resistance by the methods described above. The results are shown in Table 3. The resulting photosensitive resin compositions 16 to 31 were evaluated for development speed, refractive index, and weather resistance by the methods described above. The results are shown in Table 4.

[0249]

[0250] The descriptions in Table 1 represent the following: YDCN-704A: cresol novolac epoxy resin (epoxy equivalent weight 206 g / equivalent) NC-7000-L: naphthalene-containing novolac epoxy resin (epoxy equivalent weight 231.0 g / equivalent)

[0251]

[0252]

[0253]

[0254] As can be seen from Tables 1 to 4, the alkali-soluble resins of the examples, which have a predetermined aromatic ring-containing structure and a polymerizable unsaturated bond-containing structure and have a polymerizable unsaturated bond equivalent of 700 to 8,000 g / equivalent, and the cured products of the photosensitive resin compositions containing them all had a high refractive index of approximately 1.6. In particular, resins having a structure containing sulfur atoms and benzene rings exhibited a high refractive index. Although the incorporation of metal oxide particles slightly decreased the development speed, the refractive index was further improved. Furthermore, the alkali-soluble resins of the examples also exhibited good solvent resistance and developability. Photosensitive resin compositions using resins having a structure containing sulfur atoms and benzene rings exhibited good weather resistance, and when resins having functional groups with radical scavenging ability were used, very good results were obtained. Furthermore, Resin Intermediate (A-11) of Synthesis Example 11 is a synthetic intermediate of Resin (A-5) of Synthesis Example 5, and is not alkali-soluble. Therefore, when used alone, this resin does not have the developability when a photosensitive resin composition is prepared, but it can impart a high refractive index and high solvent resistance to the photosensitive resin composition. When used in combination with another alkali-soluble resin, a photosensitive resin composition with excellent developability can be prepared.

Claims

1. An alkali-soluble resin having an aromatic ring-containing structure represented by the following formula (4) and a polymerizable unsaturated bond-containing structure represented by the following formula (2). 【Chemical 1】 (In formula (4), R ２３ represents an aromatic group which may have a substituent. 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 each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ７ and R ８ are the same or different and each represents 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 which may have a substituent.)

2. The alkali-soluble resin according to Claim 1, wherein the acid value is 30 to 150 mgKOH / g.

3. The alkali-soluble resin according to Claim 1, wherein the epoxy equivalent is more than 10,000 g / equivalent.

4. The alkali-soluble resin according to Claim 1, wherein the main chain structure has a novolak structure.

5. The alkali-soluble resin according to Claim 1, wherein the polymerizable unsaturated bond equivalent is 300 to 8000 g / equivalent.

6. A photosensitive resin composition comprising the alkali-soluble resin according to Claim 1, a polymerizable compound, and a photopolymerization initiator.

7. A cured product obtained by curing the alkali-soluble resin according to Claim 1 or the photosensitive resin composition according to Claim 6.

8. A member for a display device, comprising the cured product according to Claim 7.

9. A display device, comprising the member for a display device according to Claim 8.

10. A method for producing an alkali-soluble resin, the production method including a first step of reacting an epoxy resin (a) having two or more epoxy groups in one molecule with an aromatic group-containing compound (b') and an unsaturated monocarboxylic acid (c), and a second step of reacting the reaction product obtained in the first step with a polybasic acid anhydride (d), wherein the aromatic group-containing compound (b') is a compound containing an aromatic group and a mercapto group A method for producing an alkali-soluble resin, characterized in that.

11. A method for producing a photosensitive resin composition, the production method including a step of producing an alkali-soluble resin by the method for producing an alkali-soluble resin according to Claim 10, and a step of mixing the obtained alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

12. Having an aromatic ring-containing structure represented by the following formula (1') and a polymerizable unsaturated bond-containing structure represented by the following formula (2'), wherein the polymerizable unsaturated double bond equivalent is 600 to 7000 g / equivalent A resin, characterized in that. 【Chemical 2】 (In formula (1'), R １ represents a sulfur atom. R ２ represents an aromatic group which may have a substituent. In formula (2'), R ４ , R ５ and R ６ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ７ and R ８ are the same or different and each represents a direct bond or a divalent organic group.)

13. A photosensitive resin composition comprising the resin according to Claim 12, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

14. A cured product obtained by curing the photosensitive resin composition according to claim 13.

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