JP2016210820A - Polymerizable composition, photosensitive composition, and cured product of said photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a polymerizable composition that produces a photosensitive composition capable of forming a pattern excellent in rectilinearity as well as excellent in adhesion to a substrate even at low exposure dose; a photosensitive composition containing said polymerizable composition; and a cured product of said photosensitive composition.SOLUTION: The polymerizable composition is obtained by modifying a so-called cardo structure-containing polymerizable compound having a predetermined structure containing a 9,9-diphenyl-fluorene skeleton using a polyfunctional (meth)acrylate having 1 or more hydroxyl groups. The polymerizable composition obtained by said method may contain a photopolymerization initiator and a coloring agent.SELECTED DRAWING: None

Description

  The present invention relates to a polymerizable composition and a photosensitive composition. Moreover, this invention relates to the hardened | cured material of the photosensitive composition containing the said polymeric composition.

  Compounds and resins having a structure containing a 9,9-diphenylfluorene skeleton called a cardo structure are widely known. Such a compound or resin having a cardo structure is blended in various photosensitive compositions because of its excellent optical properties and heat resistance.

  As such a photosensitive composition, for example, a photosensitive composition containing a photopolymerizable compound having a cardo structure, a photopolymerization initiator having a specific structure, and a colorant is known (patent) Reference 1).

JP 2007-072034 A

  However, with respect to the photosensitive compositions in general, it is desired that a good pattern can be formed at a low exposure amount by increasing the sensitivity. However, in a conventional photosensitive composition containing a compound or resin having a cardo structure, a low exposure amount is required. In the case of performing the exposure in step 1, it may be difficult to form a pattern having excellent straightness and adhesion to the substrate.

  The present invention provides a polymerizable composition that provides a photosensitive composition that can form a pattern that is excellent in straightness and excellent in adhesion to a substrate even at a low exposure amount, and a photosensitive composition comprising the polymerizable composition And a cured product of the photosensitive composition.

  The present inventors modify a polymerizable compound having a so-called cardo structure having a predetermined structure including a 9,9-diphenylfluorene skeleton with a polyfunctional (meth) acrylate having one or more hydroxyl groups. The present inventors have found that the above problems can be solved and have completed the present invention. Specifically, the present invention provides the following.

（式（１）中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。） In a first aspect of the present invention, a product obtained by reacting a compound represented by the following formula (1) with a polybasic acid anhydride is a polyfunctional (meth) acrylate having one or more hydroxyl groups: A polymerizable composition obtained by reacting,
It is a polymerizable composition containing a polyfunctional (meth) acrylate-modified compound, wherein the polyfunctional (meth) acrylate is a compound having two or more (meth) acryloyloxy groups.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.)

（式（１）中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。） The second aspect of the present invention is a polymerizable composition obtained by reacting a compound represented by the following formula (1) with a polybasic acid anhydride and a polyfunctional (meth) acrylate having one or more hydroxyl groups. Because
It is a polymerizable composition containing a polyfunctional (meth) acrylate-modified compound, wherein the polyfunctional (meth) acrylate is a compound having two or more (meth) acryloyloxy groups.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.)

（式（１）中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。）

（式（２）中、ａは２以上の整数であり、ｂは０以上の整数であり、Ａ^１は多塩基酸二無水物に由来する４価の有機基であり、Ａ^２は、ａ＋ｂ＋１価の有機基であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。） In the third aspect of the present invention, a compound represented by the following formula (1) and a polyfunctional (meth) acrylate modified product of a polybasic acid dianhydride represented by the following formula (2), or the following formula ( 2) Polymerizability containing a polyfunctional (meth) acrylate modified compound obtained by reacting a polyfunctional (meth) acrylate modified product of polybasic acid dianhydride represented by 2) with a mixture of polybasic acid anhydride It is a composition.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.)

(In the formula (2), a is an integer of 2 or more, b is an integer of 0 or more, A ¹ is a tetravalent organic group derived from polybasic acid dianhydride, and A ² is a + b + 1. And R ² is independently a hydrogen atom or a methyl group.)

  A fourth aspect of the present invention relates to a polymerizable composition according to any one of the first to third aspects, and a polymerizable composition containing a polyfunctional (meth) acrylate-modified compound having a hydroxyl group. A polymerizable composition containing a polyfunctional (meth) acrylate-modified compound obtained by reacting a polybasic acid monoanhydride with a hydroxyl group of a polyfunctional (meth) acrylate-modified compound having a hydroxyl group.

  A fifth aspect of the present invention is a photosensitive composition comprising the polymerizable composition according to any one of the first to fourth aspects.

  The sixth aspect of the present invention is a cured product of the photosensitive composition according to the fifth aspect.

  According to the present invention, a polymerizable composition that provides a photosensitive composition that can form a pattern that is excellent in straightness and excellent in adhesion to a substrate even at a low exposure amount, and a photosensitive property that includes the polymerizable composition. A composition and a cured product of the photosensitive composition can be provided.

（式（１）中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。） ≪First aspect≫
In a first aspect of the present invention, a product obtained by reacting a compound represented by the following formula (1) with a polybasic acid anhydride is a polyfunctional (meth) acrylate having one or more hydroxyl groups: A polymerizable composition obtained by reacting,
The present invention relates to a polymerizable composition containing a polyfunctional (meth) acrylate-modified compound, wherein the polyfunctional (meth) acrylate is a compound having two or more (meth) acryloyloxy groups.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.)

  In the present specification, “(meth) acrylate” means that the compound is either an acrylate compound or a methacrylate compound. Moreover, about polyfunctional (meth) acrylate, both the acryloyloxy group and the methacryloyloxy group may be contained in the same molecule | numerator.

The compound represented by the formula (1) can be obtained by reacting the epoxyfluorene compound represented by the following formula (1-1) with (meth) acrylic acid according to a conventional method. The compound represented by formula (1), R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, preferably a hydrogen atom.

（式（１−１）中、Ｒ^１は、式（１）と同様である。）

(In formula (1-1), R ¹ is the same as in formula (1).)

When R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and is preferably a saturated hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a structure combining these structures. When R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, a linear or branched saturated aliphatic hydrocarbon group, that is, an alkyl group is preferable.

Specific examples when R ¹ is an alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Examples include a butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, and neohexyl group.

  The compound represented by the formula (1) is subjected to a reaction with a polybasic acid anhydride to give a reaction product that is an intermediate of the polymerizable composition according to the first embodiment. A polybasic acid anhydride is a compound having a carboxylic acid anhydride group. The polybasic acid anhydride may be an acid anhydride of an aliphatic polycarboxylic acid or an acid anhydride of an aromatic polycarboxylic acid. The acid anhydride group possessed by the polybasic acid anhydride may be a five-membered ring acid anhydride group such as an acid anhydride group possessed by phthalic anhydride, for example, 1,8-naphthalene. It may be a 6-membered ring acid anhydride group as the acid anhydride has.

  The polybasic acid anhydride may be a monoanhydride or a compound having two or more acid anhydride groups. Hereinafter, a compound having two or more acid anhydride groups is also referred to as “polyhydric anhydride”. Moreover, you may use together monoanhydride and a polyhydric anhydride. When using together, the mixture of a polyhydric anhydride and monoanhydride may be sufficient, for example, and the use which adds both separately in steps may be sufficient. The polybasic acid anhydride has an acid anhydride group at the 2-position or higher because a product having a high molecular weight is easily obtained by the reaction of the compound represented by the formula (1) with the polybasic acid anhydride. Compounds are preferred and dianhydrides are preferred.

  Specific examples of polybasic acid monoanhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, nadic acid anhydride Products, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

  Specific examples of the polybasic acid dianhydride include pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane Anhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2,6,6-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-di Carboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) -1,1, , 3,3,3-hexafluoropropane dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2 , 3-Dicarboxyphenyl) ether dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 4,4- (p-phenylenedioxy) diphthalic dianhydride, 4,4 -(M-phenylenedioxy) diphthalic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6 , 7-Naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7 -Anthraces Tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-bis phthalic anhydride fluorene, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride Thing etc. are mentioned. Examples of the aliphatic tetracarboxylic dianhydride include, for example, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 1, 2, Examples include 4,5-cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclohexanetetracarboxylic dianhydride.

  When the polybasic acid anhydride is a monoanhydride, it is preferable to react 0.1 to 3 mol of the polybasic acid anhydride with respect to 1 mol of the compound represented by the formula (1). It is more preferable to carry out 2 mol reaction, and it is especially preferable to carry out 0.5-1.5 mol reaction.

When the polybasic acid anhydride is a polyhydric anhydride, 0.1 to 3 mol of the polybasic acid anhydride is preferably reacted with 1 mol of the compound represented by the formula (1). The reaction is more preferably 3 to 2 mol, and particularly preferably 0.5 to 1.5 mol.
When monoanhydride and polyhydric anhydride are used in combination, it is preferable to react 0.2 to 4 mol, and 0.6 to 2 mol with respect to 1 mol of the compound represented by the formula (1) in total. Is more preferable, and 0.8 to 1.5 mol is particularly preferable.

The method for reacting the compound represented by the formula (1) with the polybasic acid anhydride is not particularly limited, and a conventionally known method for the reaction of adding the polybasic acid anhydride to the hydroxyl group-containing compound is appropriately selected. Can be adopted.
The solvent used when the compound represented by the formula (1) is reacted with the polybasic acid anhydride is a functional group containing an active hydrogen atom such as a hydroxyl group or an amino group that can react with the acid anhydride group. The solvent is not particularly limited as long as it does not have a solvent. Suitable solvents include polar solvents such as ketone solvents, ester solvents, ether solvents, and amide solvents, and hydrocarbon solvents.

  The ketone solvent is an organic solvent containing C—C (═O) —C in the structure. The ester solvent is an organic solvent containing C—C (═O) —O—C in the structure. The ether solvent is an organic solvent containing C—O—C in the structure. Among organic solvents, there are organic solvents that contain multiple types of functional groups that characterize each of the above solvents in the structure, but in that case, those that fall under any solvent type that contains functional groups that the organic solvent has And A hydrocarbon solvent is a hydrocarbon solvent which consists of hydrocarbons and does not have a substituent (group or atom other than a hydrogen atom and a hydrocarbon group).

  Specific examples of each solvent include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone and diisobutyl. Ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, etc. It is done.

  Examples of ester solvents include chain ester solvents such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol. Monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol mono Butyl Ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl- 3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, -Methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropio And propyl-3-methoxypropionate. Examples of cyclic ester solvents include lactones such as γ-butyrolactone.

  Examples of ether solvents include glycol ether solvents such as ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether; diisopentyl ether, diisobutyl ether, dioxane, tetrahydrofuran , Anisole, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like. Of these, glycol ether solvents are preferred.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be mentioned.

  As the other polar solvent, dimethyl sulfoxide is also preferably used as the organic solvent (S).

  Examples of hydrocarbon solvents include fats such as pentane, hexane, octane, decane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, perfluoroheptane, limonene, and pinene. Aromatic hydrocarbon solvents: aromatics such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc. And hydrocarbon solvents. Among these, aromatic hydrocarbon solvents are preferable.

  The temperature at which the compound represented by formula (1) is reacted with the polybasic acid anhydride is not particularly limited. The temperature at which the compound represented by the formula (1) and the polybasic acid anhydride are reacted is preferably, for example, 30 to 200 ° C, more preferably 50 to 180 ° C, and particularly preferably 70 to 150 ° C. The reaction between the compound represented by the formula (1) and the polybasic acid anhydride is usually performed under atmospheric pressure. However, when the reaction temperature exceeds the boiling point of the solvent, the reaction may be performed in a pressure resistant container under a pressurized condition.

  The reaction between the compound represented by the formula (1) and the polybasic acid anhydride is preferably performed in an inert gas atmosphere. By performing the reaction in an inert gas atmosphere, hydrolysis of the acid anhydride group of the polybasic acid anhydride due to moisture in the air is suppressed.

  When reacting the compound represented by the formula (1) with the polybasic acid anhydride, a catalyst may be added as necessary. The type of the catalyst is not particularly limited, and examples thereof include phase transfer catalysts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, and tetrabutylammonium chloride.

  The reaction product of the compound represented by formula (1) and the polybasic acid anhydride may be used as it is in the next step without being isolated from the solvent. May be. Further, the reaction product may be purified according to a known method as necessary.

Next, by reacting the reaction product of the compound represented by the formula (1) and the polybasic acid anhydride with a polyfunctional (meth) acrylate having one or more hydroxyl groups, the polymerizability according to the first aspect is achieved. A composition is obtained.
Here, the polymerizable composition may contain unreacted raw materials, a plurality of types of products, a reaction solvent, a catalyst added during the reaction, and the like.

  The number of hydroxyl groups possessed by the polyfunctional (meth) acrylate is not particularly limited, but is preferably 1 or more, and more preferably 1.

  The polyfunctional (meth) acrylate may be derived from an aliphatic polyol, may be derived from an aromatic polyol, or is derived from a polyol having a phenolic hydroxyl group and an alcoholic hydroxyl group. There may be. In terms of the reactivity between the reaction product of the compound represented by formula (1) and the polybasic acid anhydride, the polyfunctional (meth) acrylate is preferably derived from an aliphatic polyol. Moreover, it is preferable that the hydroxyl group which polyfunctional (meth) acrylate has is a primary hydroxyl group at the reactive point with the reaction product of the compound represented by Formula (1) and a polybasic acid anhydride.

  Regarding the precursor of polyfunctional (meth) acrylate, aromatic polyols include novolak resins such as phenol novolak, cresol novolak, naphthol novolak; calixarene; benzene such as phloroglucinol, pyrogallol, 1,2,4-benzenetriol Triols; 1,4,5-naphthalenetriol, 1,2,4-naphthalenetriol, 1,3,8-naphthalenetriol, 1,2,7-naphthalenetriol and other naphthalenetriols; 3,3 ′, 4,4 And tetrahydroxybiphenyl such as '-tetrahydroxybiphenyl and 3,3', 5,5'-tetrahydroxybiphenyl.

  Examples of the aliphatic polyol include glycerin, trimethylolpropane, dipentaerythritol, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, sucrose, glucose, mannose, fructose, and methylglucoside.

  Moreover, the compound which added alkylene oxides, such as an ethylene polyol and a propylene oxide, to the aromatic polyol and aliphatic polyol demonstrated above is also useful as a precursor of polyfunctional (meth) acrylate.

  Specific examples of preferred polyfunctional (meth) acrylates include dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Di (meth) acrylate, ethylene oxide-added pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin-1,2-bis (meth) acrylate, glycerin-1,3-bis (meth) acrylate, Examples include sorbitol penta (meth) acrylate, sorbitol tetra (meth) acrylate, and sorbitol tri (meth) acrylate.

  Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol tetra (meth) acrylate are preferable because of having a large number of (meth) acryloyloxy groups in the molecule and reactivity at the time of modification. Dipentaerythritol penta (meth) acrylate is more preferred.

  The reaction that occurs between the reaction product of the compound represented by the formula (1) and the polybasic acid anhydride and the polyfunctional (meth) acrylate is a carboxyl group derived from the polybasic acid anhydride and a polyfunctional acid. This is an ester formation reaction with a hydroxyl group of (meth) acrylate. For this reason, the reaction of the reaction product of the compound represented by the formula (1) with the polybasic acid anhydride and the polyfunctional (meth) acrylate is carried out in the same manner as the well-known ester formation reaction.

As a specific method, for example, the carboxyl group of the reaction product of the compound represented by the formula (1) and the polybasic acid anhydride is converted to a carboxylic acid halide (carboxylic acid chloride) with phosphorus oxychloride or thionyl chloride. Examples of the method include a method of reacting the carboxylic acid halide with the hydroxyl group of the polyfunctional (meth) acrylate.
In addition, in the presence of an acid catalyst such as sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc., a carboxyl group possessed by the reaction product of the compound represented by formula (1) and the polybasic acid anhydride, and polyfunctional A method of dehydrating and condensing the hydroxyl group of (meth) acrylate is also preferred.
Even when no catalyst is added, dehydration condensation of the carboxyl group of the reaction product of the compound represented by formula (1) and the polybasic acid anhydride and the hydroxyl group of the polyfunctional (meth) acrylate proceeds The reaction product of the compound represented by formula (1) and the polybasic acid anhydride and the polyfunctional (meth) acrylate may be mixed and reacted in a solvent under heating.

  The reaction of the reaction product of the compound represented by the formula (1) with the polybasic acid anhydride and the polyfunctional (meth) acrylate is usually performed in an organic solvent. As such an organic solvent, a solvent similar to the solvent used for the reaction of the compound represented by the formula (1) and the polybasic acid anhydride can be used.

  The temperature at which the reaction product of the compound represented by formula (1) and the polybasic acid anhydride is reacted with the polyfunctional (meth) acrylate is not particularly limited. For example, the temperature at which the reaction is performed is preferably 30 to 200 ° C, more preferably 50 to 180 ° C, and particularly preferably 70 to 150 ° C.

  The amount of polyfunctional (meth) acrylate used when preparing the polymerizable composition according to the first aspect is not particularly limited. When the photolithographic property is not required for the photosensitive composition containing the polymerizable composition, the carboxyl group of the reaction product of the compound represented by the formula (1) and the polybasic acid anhydride is converted into a polyfunctional (meta ) It may be completely modified with acrylate. On the other hand, when photolithography characteristics are required for the photosensitive composition containing the polymerizable composition, a desired amount of polyfunctionality is maintained while leaving the carboxyl group within a range that can ensure the alkali developability of the photosensitive composition. Modification with (meth) acrylate may be performed.

  By the method described above, the polymerizable composition according to the first aspect is obtained. The polymerizable composition may be used in the form of a solution or suspension containing a reaction solvent, or may be used as a solid or paste obtained by partially or completely removing the reaction solution. By blending the polymerizable composition according to the first aspect into the photosensitive composition, a photosensitive composition capable of forming a pattern having excellent adhesion to the substrate and excellent straightness even at a low exposure amount is obtained. It is done.

（式（１）中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。） ≪Second aspect≫
The second aspect of the present invention is a polymerizable composition obtained by reacting a compound represented by the following formula (1) with a polybasic acid anhydride and a polyfunctional (meth) acrylate having one or more hydroxyl groups. Because
It is a polymerizable composition containing a polyfunctional (meth) acrylate-modified compound, wherein the polyfunctional (meth) acrylate is a compound having two or more (meth) acryloyloxy groups.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.)

  About a 2nd aspect, the compound represented by Formula (1), a polybasic acid anhydride, and a polyfunctional (meth) acrylate are the same as that of a 1st aspect.

The polymerizable composition according to the second aspect is obtained by reacting the compound represented by the formula (1), the polybasic acid anhydride, and the polyfunctional (meth) acrylate at the same time.
In the first aspect, polyfunctional (meth) acrylate is condensed to a carboxyl group derived from an acid anhydride group, which is generated by adding a polybasic acid anhydride to the compound represented by formula (1). To do. On the other hand, when producing the polymerizable composition according to the second embodiment, the polybasic acid anhydride includes a hydroxyl group possessed by the compound represented by the formula (1) and a hydroxyl group possessed by the polyfunctional (meth) acrylate. The composition of the polymerizable composition according to the second embodiment is somewhat different from that of the polymerizable composition according to the first embodiment.
For example, when preparing a polymerizable composition using a polybasic acid anhydride (polyhydric anhydride) having two or more acid anhydride groups and a polyfunctional (meth) acrylate having one hydroxyl group, the formula ( The polymerization reaction occurring between the compound represented by 1) and the polyhydric anhydride is stopped by the polyfunctional (meth) acrylate, and the average molecular weight of the compound contained in the polymerizable composition may be somewhat lowered. .

The conditions for reacting the compound represented by the formula (1), the polybasic acid anhydride, and the polyfunctional (meth) acrylate are represented by the formula (1) when the polymerizable composition of the first aspect is produced. The conditions for reacting the compound to be reacted with the polybasic acid anhydride are the same. An acid catalyst such as sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid or the like may be added to the reaction system in order to promote an ester production reaction involving a polyfunctional (meth) acrylate having a hydroxyl group.
Moreover, you may add a catalyst to a reaction system as needed. The type of the catalyst is not particularly limited, and examples thereof include phase transfer catalysts such as tetraethylammonium bromide and tetrabutylammonium bromide.

  The amount of polybasic acid anhydride used when producing the polymerizable composition according to the second aspect is the same as that when producing the polymerizable composition according to the first aspect. Moreover, the modification amount by polyfunctional (meth) acrylate when producing the second polymerizable composition is the same as that for producing the polymerizable composition according to the first embodiment.

  The polymerizable composition according to the second aspect is obtained by the method described above. The polymerizable composition may be used in the form of a solution or suspension containing a reaction solvent, or may be used as a solid or paste obtained by partially or completely removing the reaction solution. By blending the polymerizable composition according to the second aspect into the photosensitive composition, a photosensitive composition capable of forming a pattern having excellent adhesion to the substrate and excellent straightness even at a low exposure amount is obtained. It is done.

（式（１）中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。）

（式（２）中、ａは２以上の整数であり、ｂは０以上の整数であり、Ａ^１は多塩基酸二無水物に由来する４価の有機基であり、Ａ^２は、ａ＋ｂ＋１価の有機基であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。） ≪Third aspect≫
In the third aspect of the present invention, a compound represented by the following formula (1) and a polyfunctional (meth) acrylate modified product of a polybasic acid dianhydride represented by the following formula (2), or the following formula ( 2) Polymerizability containing a polyfunctional (meth) acrylate modified compound obtained by reacting a polyfunctional (meth) acrylate modified product of polybasic acid dianhydride represented by 2) with a mixture of polybasic acid anhydride It is a composition.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.)

(In the formula (2), a is an integer of 2 or more, b is an integer of 0 or more, A ¹ is a tetravalent organic group derived from polybasic acid dianhydride, and A ² is a + b + 1. And R ² is independently a hydrogen atom or a methyl group.)

  About a 3rd aspect, it is the same as that of a 1st aspect about the compound represented by Formula (1), and a polybasic acid anhydride. The polyfunctional (meth) acrylate modified product of the polybasic acid dianhydride represented by the formula (2) will be described later. The polyfunctional (meth) acrylate modified product of the polybasic acid dianhydride represented by the formula (2) is also referred to as “modified product represented by the formula (2)”.

  In the third embodiment, when the compound represented by the formula (1) and the modified product represented by the formula (2) are reacted, the compound represented by the formula (1) and the formula (2) The ratio of the amount of polybasic acid dianhydride used with the polyfunctional (meth) acrylate modified product is not particularly limited. For example, with respect to 1 mol of the compound represented by the formula (1), the modified product represented by the formula (2) is preferably used in an amount of 0.1 to 3 mol, and 0.3 to 2 mol is used. It is more preferable to use 0.5 to 1.5 mol.

  The method of reacting the compound represented by the formula (1) with the modified product represented by the formula (2) includes the compound represented by the formula (1) and the polybasic acid dianhydride in the first embodiment. This is the same as the method of reacting a product.

When the compound represented by the formula (1) is reacted with the mixture of the modified product represented by the formula (2) and the polybasic acid anhydride with respect to the third aspect, it is represented by the formula (1). The ratio of the usage-amount of a compound, the modified material represented by Formula (2), and a polybasic acid anhydride is not specifically limited.
When the polybasic acid anhydride is a monoanhydride, the total amount of the modified product represented by the formula (2) and the polybasic acid anhydride is 1 mol of the compound represented by the formula (1). The amount is preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, and particularly preferably 0.5 to 1.5 mol.
In this case, in the total amount of the modified product represented by the formula (2) and the polybasic acid anhydride, the amount of the modified product represented by the formula (2) is preferably 10 to 90 mol%.

  About a 3rd aspect, the compound represented by Formula (1), the modified material represented by Formula (2), the polybasic acid anhydride (polyhydric anhydride) which has two or more acid anhydride groups, In the case of reacting with a mixture of the above, the total amount of the modified product represented by the formula (2) and the polyhydric anhydride is 0.1 to 3 mol with respect to 1 mol of the compound represented by the formula (1). It is preferable that it is 0.3-2 mol, and it is especially preferable that it is 0.5-1.5 mol. In this case, in the total amount of the modified product represented by the formula (2) and the polyhydric anhydride, the amount of the modified product represented by the formula (2) is preferably 50 mol% or less, more preferably 30 mol% or less. preferable.

  A method of reacting a compound represented by the formula (1) with a mixture of a modified product represented by the formula (2) and a polyhydric anhydride is a compound represented by the formula (1) in the first embodiment. And the method of reacting polybasic acid dianhydride.

  The polymerizable composition according to the third aspect is obtained by the method described above. The polymerizable composition may be used in the form of a solution or suspension containing a reaction solvent, or may be used as a solid or paste obtained by partially or completely removing the reaction solution. By blending the polymerizable composition according to the third aspect into the photosensitive composition, a photosensitive composition capable of forming a pattern having excellent adhesion to the substrate and excellent straightness even at a low exposure amount is obtained. It is done.

≪Fourth aspect≫
A fourth aspect of the present invention relates to a polymerizable composition according to any one of the first to third aspects, and a polymerizable composition containing a polyfunctional (meth) acrylate-modified compound having a hydroxyl group. A polymerizable composition containing a polyfunctional (meth) acrylate-modified compound obtained by reacting a polybasic acid monoanhydride with a hydroxyl group of a polyfunctional (meth) acrylate-modified compound having a hydroxyl group.

  Here, the polyfunctional (meth) acrylate-modified compound contained in the polymerizable composition according to any one of the first to third aspects refers to the compound represented by the above formula (1). The compound produced | generated by giving the predetermined reaction in each aspect is meant. The compound produced by subjecting the compound represented by the above formula (1) to a predetermined reaction in each embodiment is usually a mixture of a plurality of compounds having various structures.

  4th aspect WHEREIN: A carboxyl group can be introduce | transduced into a polyfunctional (meth) acrylate modified compound by making a polybasic acid monoanhydride react with the hydroxyl group which a polyfunctional (meth) acrylate modified compound has. By doing so, the polymeric composition which concerns on a 4th aspect becomes what the alkali solubility was improved.

  Polybasic acid monoanhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, nadic acid anhydride, hexa Hydrophthalic anhydride and methylhexahydrophthalic anhydride one are preferably used.

  In the fourth aspect, the method of reacting the polybasic acid monoanhydride with the hydroxyl group of the polyfunctional (meth) acrylate-modified compound is the same as the compound represented by the formula (1) and the polybasic acid in the first aspect. This is the same as the method of reacting with an anhydride.

  The polymerizable composition according to the fourth aspect is obtained by the method described above. The polymerizable composition may be used in the form of a solution or suspension containing a reaction solvent, or may be used as a solid or paste obtained by partially or completely removing the reaction solution. By blending the polymerizable composition according to the fourth aspect into the photosensitive composition, a photosensitive composition capable of forming a pattern having excellent adhesion to the substrate and excellent straightness even at a low exposure amount is obtained. It is done. Moreover, since the carboxyl group is introduce | transduced into the terminal in the polymeric composition which concerns on a 4th aspect, the photosensitive composition containing the polymeric composition which concerns on a 4th aspect is excellent in alkali developability.

（式（２）中、ａは２以上の整数であり、ｂは０以上の整数であり、Ａ^１は多塩基酸二無水物に由来する４価の有機基であり、Ａ^２は、ａ＋ｂ＋１価の有機基であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基である。） <Modified product represented by formula (2)>
Hereinafter, the polyfunctional (meth) acrylate modified product of polybasic acid dianhydride represented by the following formula (2) used in the third embodiment will be described.

(In the formula (2), a is an integer of 2 or more, b is an integer of 0 or more, A ¹ is a tetravalent organic group derived from polybasic acid dianhydride, and A ² is a + b + 1. And R ² is independently a hydrogen atom or a methyl group.)

（式（２−１）中、Ａ^１は４価の有機基である。式（２−２）中、ａは２以上の整数であり、ｃは１以上の整数であり、Ａ^２はａ＋ｃ価の有機基である。） The modified product represented by the formula (2) comprises a polybasic acid dianhydride represented by the following formula (2-1) and a polyfunctional (meth) acrylate represented by the following formula (2-2). It is obtained by reacting.

(In Formula (2-1), A ¹ is a tetravalent organic group. In Formula (2-2), a is an integer of 2 or more, c is an integer of 1 or more, and A ² is a + c. Valent organic group.)

A ¹ is a tetravalent organic group, is not limited to a hydrocarbon group, and may contain a hetero atom such as O, S, N, P, or a halogen atom as long as the object of the present invention is not impaired. Good.
Specific examples of the polybasic acid dianhydride represented by the formula (2-1) include pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis ( 2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3, 3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2,6,6-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis (2,3-dicarboxyphene Nyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) Ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 4,4- (p-phenylenedioxy) diphthal Acid dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid di Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride , 2, 3, 6, 7- Anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-bisphthalic anhydride fluorene, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid An anhydride etc. are mentioned. Examples of the aliphatic tetracarboxylic dianhydride include, for example, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 1, 2, Examples include 4,5-cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclohexanetetracarboxylic dianhydride.

A ² is an a + c-valent polyvalent organic group, which may be an aliphatic group, an aromatic group, or a group containing a combination of an aliphatic group and an aromatic group. Good. A ² is not limited to a hydrocarbon group, and may contain a heteroatom such as O, S, N, P, and a halogen atom as long as the object of the present invention is not impaired. In formula (2-2), c is preferably 1. In this case, b is 0 in the formula (2).

  Specific examples of the polyfunctional (meth) acrylate represented by the formula (2-2) include dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene oxide-added pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin-1,2-bis (meth) acrylate, glycerin Examples include -1,3-bis (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol tetra (meth) acrylate, and sorbitol tri (meth) acrylate.

  The method of reacting the polybasic acid dianhydride represented by the formula (2-1) and the polyfunctional (meth) acrylate represented by the formula (2-2) is not particularly limited. The embodiment is carried out by the same method as the method of reacting the compound represented by the formula (1) and the polybasic acid anhydride described above.

  The polyfunctional (meth) acrylate modified product of the polybasic acid dianhydride represented by the formula (2) is a polymerizable composition containing a polyfunctional (meth) acrylate modified compound or a polyfunctional (meth) acrylate modified compound described later. It is used suitably for manufacture of a thing.

（式（３）中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基であり、ｍは０以上の整数であり、Ｘは、それぞれ独立にＯＨ基、又は下式（４）で表される基であり、Ａ^３は多塩基酸二無水物に由来する４価の有機基であり、Ｙは、水素原子、又は下式（５）で表される基である。ｍが０である場合、Ａ^４は下式（６）で表される基である。ｍが１以上の整数である場合、Ａ^４は、Ｘ又は下式（６）で表される基である。式（３）で表される化合物中、式（４）で表される基、又は式（５）で表される基が少なくとも一つ存在する。）

（式（４）中、ｐは２以上の整数であり、ｑは０以上の整数であり、Ａ^５は、ｐ＋ｑ＋１価の有機基である。）

（式（５）中、Ｚは、ＯＨ基又は前記式（４）で表される基であり、Ａ^６は多塩基酸二無水物に由来する４価の有機基である。）

（式（６）中、Ｒ^１及びＲ^２は、式（３）におけるＲ^１及びＲ^２と同様である。） << Polyfunctional (meth) acrylate modified compound represented by Formula (3) >>
As a polymeric compound contained in the polymeric composition demonstrated above, the polyfunctional (meth) acrylate modified compound represented by the following Formula (3) is mentioned, for example.

(In Formula (3), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom; R ² is each independently a hydrogen atom or a methyl group; Is an integer of 0 or more, X is independently an OH group or a group represented by the following formula (4), and A ³ is a tetravalent organic group derived from polybasic acid dianhydride. Y is a hydrogen atom or a group represented by the following formula (5): When m is 0, A ⁴ is a group represented by the following formula (6): m is an integer of 1 or more A ⁴ is X or a group represented by the following formula (6): In the compound represented by the formula (3), the group represented by the formula (4) or the formula (5) There is at least one group represented.)

(In formula (4), p is an integer of 2 or more, q is an integer of 0 or more, and A ⁵ is a p + q + 1 valent organic group.)

(In Formula (5), Z is an OH group or a group represented by Formula (4), and A ⁶ is a tetravalent organic group derived from polybasic acid dianhydride.)

(In the formula (6), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (3).)

The manufacturing method of the compound represented by Formula (3) is not specifically limited. When m in Formula (3) is an integer greater than or equal to 1, the compound represented by Formula (3) is manufactured by the following method, for example.
First, the compound represented by the above formula (1) and the tetracarboxylic dianhydride represented by the following formula (3-1) are reacted to form the following formula (3-2) or the following formula (3- The intermediate represented by 3) is obtained.
Next, at least part of the plurality of carboxyl groups bonded to A ³ in the intermediate represented by the following formula (3-2) or the following formula (3-3) is represented by the following formula (3-4). Polyfunctional (meth) acrylate is condensed.
The terminal hydroxyl group of the product after the polyfunctional (meth) acrylate represented by the formula (3-4) is condensed is optionally a polybasic represented by the following formula (3-5) An acid dianhydride or a polyfunctional (meth) acrylate modified product of a polybasic acid dianhydride represented by the following formula (3-6) may be reacted.

  When m is 0 in the compound represented by the formula (3), it is represented by the following formula (3-6) on at least one of the two hydroxyl groups of the compound represented by the formula (1). The polyfunctional (meth) acrylate modified compound represented by the formula (3) is obtained by reacting the polybasic acid dianhydride modified polyfunctional (meth) acrylate.

（式（３−１）中、Ａ^３は４価の有機基である。）

(In formula (3-1), A ³ is a tetravalent organic group.)

A ³ is a tetravalent organic group, and is not limited to a hydrocarbon group, and may contain heteroatoms such as O, S, N, P, and halogen atoms as long as the object of the present invention is not impaired. Good.
Specific examples of the polybasic acid dianhydride represented by the formula (3-1) include pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis ( 2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3, 3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2,6,6-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis (2,3-dicarboxyphene Nyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) Ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 4,4- (p-phenylenedioxy) diphthal Acid dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid di Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride , 2, 3, 6, 7- Anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 9,9-bisphthalic anhydride fluorene, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid An anhydride etc. are mentioned. Examples of the aliphatic tetracarboxylic dianhydride include, for example, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 1, 2, Examples include 4,5-cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclohexanetetracarboxylic dianhydride.
By reacting the polybasic acid dianhydride represented by the formula (3-1) with the compound represented by the above formula (1), the following formula (3-2) or the following formula (3-3) ) Is obtained.

（式（３−２）中、Ｒ^１、Ｒ^２、及びＡ^３は式（３）と同様であり、ｍは１以上の整数である。）

(In formula (3-2), R ¹ , R ² and A ³ are the same as in formula (3), and m is an integer of 1 or more.)

（式（３−３）中、Ｒ^１、Ｒ^２、及びＡ^３は式（３）と同様であり、ｍは１以上の整数である。）

(In Formula (3-3), R ¹ , R ² , and A ³ are the same as in Formula (3), and m is an integer of 1 or more.)

The method of reacting the compound represented by the above formula (1) with the polybasic acid dianhydride represented by the formula (3-1) is the same as the method described for the first embodiment. A polyfunctional group represented by the following formula (3-4) is present in at least a part of a plurality of carboxyl groups bonded to A ³ in the intermediate represented by the above formula (3-2) or formula (3-3) ( By condensing (meth) acrylate, a polyfunctional (meth) acrylate-modified compound represented by formula (3), wherein Y is a hydrogen atom, is obtained.

（式（３−４）中、ｐは２以上の整数であり、ｒは１以上の整数であり、Ａ^５はｐ＋ｒ価の有機基である。）

(In Formula (3-4), p is an integer of 2 or more, r is an integer of 1 or more, and A ⁵ is a p + r-valent organic group.)

A ⁵ is a p + r-valent polyvalent organic group, which may be an aliphatic group, an aromatic group, or a group containing a combination of an aliphatic group and an aromatic group. Good. A ⁵ is not limited to a hydrocarbon group, and may contain a hetero atom such as O, S, N, P, or a halogen atom as long as the object of the present invention is not impaired.

  Preferred specific examples of the polyfunctional (meth) acrylate represented by the formula (3-3) include dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene oxide-added pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin-1,2-bis (meth) acrylate, glycerin Examples include -1,3-bis (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol tetra (meth) acrylate, and sorbitol tri (meth) acrylate.

  The terminal hydroxyl group of the product after the polyfunctional (meth) acrylate represented by the formula (3-4) is condensed is optionally a polybasic represented by the following formula (3-5) An acid dianhydride or a polyfunctional (meth) acrylate modified product of a polybasic acid dianhydride represented by the following formula (3-6) may be reacted. By this reaction, the functional group represented by the formula (5) is introduced as Y in the compound represented by the formula (3).

（式（３−４）及び式（３−５）中、Ａ^６は４価の有機基であり、ｐ、ｑ、及びＡ^５は式（４）と同様である。）

(In Formula (3-4) and Formula (3-5), A ⁶ is a tetravalent organic group, and p, q, and A ⁵ are the same as in Formula (4).)

  About the manufacturing method of the compound represented by Formula (3) demonstrated above, the method of condensing the polyfunctional (meth) acrylate which has a hydroxyl group in a carboxyl group, and the method of making a polybasic acid anhydride react with a hydroxyl group are the following. This is the same as the method described for the first to third aspects.

  By the method demonstrated above, the polyfunctional (meth) acrylate modified compound represented by Formula (3) is obtained. When the photosensitive composition contains the polyfunctional (meth) acrylate-modified compound represented by the formula (3), it is easy to form a pattern having excellent adhesion to the substrate and excellent straightness even at a low exposure amount.

（式（７）中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子であり、Ｒ^２は、それぞれ独立に水素原子又はメチル基であり、ｎは１以上の整数であり、Ｘは、それぞれ独立に−ＯＨ基、又は下式（４）で表される基である。Ａ^８は、Ｘ又は下式（８）で表される基である。式（７）中の複数のＸのうち少なくとも一つは式（４）で表される基であり、Ａ^３は多塩基酸二無水物に由来する４価の有機基であり、Ａ^７は多塩基酸一無水物に由来する２価の有機基である。）

（式（４）中、ｐは２以上の整数であり、ｑは０以上の整数であり、Ａ^５はｐ＋ｑ＋１価の有機基である。） << Polyfunctional (meth) acrylate-modified compound represented by formula (7) >>
As the polymerizable compound contained in the polymerizable composition described above, in addition to the polyfunctional (meth) acrylate-modified compound represented by the above formula (3), for example, represented by the following formula (7): A polyfunctional (meth) acrylate modified compound is mentioned.

(In Formula (7), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ² is each independently a hydrogen atom or a methyl group, and n Is an integer of 1 or more, and X is independently an —OH group or a group represented by the following formula (4), and A ⁸ is a group represented by X or the following formula (8). At least one of the plurality of Xs in the formula (7) is a group represented by the formula (4), A ³ is a tetravalent organic group derived from polybasic acid dianhydride, and A ⁷ Is a divalent organic group derived from polybasic acid monoanhydride.)

(In formula (4), p is an integer of 2 or more, q is an integer of 0 or more, and A ⁵ is a p + q + 1 valent organic group.)

（式（８）中、Ｒ^１、Ｒ^２及びＡ^７は、式（７）におけるＲ^１、Ｒ^２、及びＡ^７と同様である。）

(In the formula ^(8), R 1, ^{R 2} and ^{A 7} are the same as ^R 1, ^{R 2,} and ^{A 7} in the formula (7).)

  Although the manufacturing method of the polyfunctional (meth) acrylate modified compound represented by Formula (7) is not particularly limited, the polyfunctional (meth) acrylate modified compound represented by Formula (7) is, for example, the following method Manufactured by. First, the compound represented by the following formula (7-1) or the following formula (7-2) is obtained by the same method as that described for the polyfunctional (meth) acrylate-modified compound represented by the formula (3). . Subsequently, the carboxyl group which the compound represented by Formula (7-1) or Formula (7-2) has by the method similar to the method demonstrated about the polyfunctional (meth) acrylate modified compound represented by Formula (3). A compound represented by the formula (7-3) or the formula (7-4) is obtained by condensing the polyfunctional (meth) acrylate represented by the above formula (3-4) to at least a part of the above. Then, the terminal hydroxyl group of the compound represented by formula (7-3) or formula (7-4) is reacted with a polybasic acid monoanhydride represented by the following formula (7-5) to obtain a formula The polyfunctional (meth) acrylate modified compound represented by (7) is obtained.

（式（７−１）中、Ｒ^１、Ｒ^２、ｎ、及びＡ^３は式（７）と同様である。）

(In Formula (7-1), R ¹ , R ² , n, and A ³ are the same as in Formula (7).)

（式（７−２）中、Ｒ^１、Ｒ^２、ｎ、及びＡ^３は式（７）と同様である。）

(In formula (7-2), R ¹ , R ² , n, and A ³ are the same as in formula (7).)

（式（７−３）中、Ｒ^１、Ｒ^２、ｎ、Ｘ、及びＡ^３は式（７）と同様である。）

(In formula (7-3), R ¹ , R ² , n, X, and A ³ are the same as in formula (7).)

（式（７−４）中、Ｒ^１、Ｒ^２、ｎ、Ｘ、及びＡ^３は式（７）と同様である。）

(In formula (7-4), R ¹ , R ² , n, X, and A ³ are the same as in formula (7).)

（式（７−５）中、Ａ^７は２価の有機基である。）

(In formula (7-5), A ⁷ is a divalent organic group.)

A ⁷ is a divalent organic group, and may be an aliphatic group, an aromatic group, or a group containing a combination of an aliphatic group and an aromatic group. A ⁷ is not limited to a hydrocarbon group and may contain heteroatoms such as O, S, N, P, and halogen atoms as long as the object of the present invention is not impaired.

  Preferable examples of the compound represented by the formula (7-5) which is a polybasic acid monoanhydride include phthalic anhydride, trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Phthalic anhydride, methyl nadic acid anhydride, nadic acid anhydride, hexahydrophthalic anhydride, and methyl hexahydrophthalic anhydride are preferably used.

  The method of reacting the polybasic acid monoanhydride represented by the formula (7-5) with the hydroxyl group of the compound represented by the formula (7-3) or the formula (7-4) in the first aspect This is the same as the method of reacting the compound represented by the formula (1) with the polybasic acid anhydride.

  By the method demonstrated above, the polyfunctional (meth) acrylate modified compound represented by Formula (7) is obtained. When the photosensitive composition contains the polyfunctional (meth) acrylate-modified compound represented by the formula (7), it is easy to form a pattern having excellent adhesion to the substrate and excellent straightness even at a low exposure amount. In addition, since the polyfunctional (meth) acrylate-modified compound represented by the formula (7) has a carboxyl group introduced at the terminal, the photosensitivity includes the polyfunctional (meth) acrylate-modified compound represented by the formula (7). The composition is excellent in alkali developability.

≪Fifth aspect≫
A fifth aspect is a photosensitive composition comprising the polymerizable composition according to any one of the first to fourth aspects.
The photosensitive composition according to the fifth aspect is not particularly limited as long as it contains a predetermined polymerizable composition and can be cured by exposure. For this reason, the photosensitive composition usually contains a photopolymerization initiator.

Typical examples of the photosensitive composition include the following 1) to 4):
1) Photosensitive composition containing a predetermined polymerizable composition and a photopolymerization initiator 2) A predetermined polymerizable composition, a photopolymerization initiator, and a photopolymerizable compound other than the predetermined polymerizable composition Photosensitive composition 3) containing a predetermined polymerizable composition, a photopolymerization initiator, and an alkali-soluble resin other than the predetermined polymerizable composition 4) a predetermined polymerizable composition; The composition of the photosensitive composition containing a photoinitiator, photopolymerizable compounds other than a predetermined polymerizable composition, and alkali-soluble resin other than a predetermined polymerizable composition is mentioned.

  Hereinafter, components that the photosensitive composition may contain will be described. In addition, content of the following components in a photosensitive composition is suitably set according to the intended purpose of the photosensitive composition.

(Photopolymerization initiator)
As a photoinitiator, what is conventionally mix | blended with the photosensitive composition containing the photopolymerizable compound which has an unsaturated bond can be used without a restriction | limiting in particular.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2. -Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy- 2-methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4 -Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Til, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- ( o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisiso Butyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4 ' -Bisdimethylaminobenzophenone (ie Michler's ketone), , 4′-bisdiethylaminobenzophenone (ie, ethyl Michler's ketone), 4,4′-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetate Phenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9 -Acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s- Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3 -Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bi S-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, “IRGACURE OXE02”, “IRGACURE OXE01”, “IRGACURE 369”, “IRGACURE 651”, “IRGACURE 907” (trade name: manufactured by BASF), “NCI-831” (trade name: manufactured by ADEKA), and the like. These photopolymerization initiators can be used alone or in combination of two or more.

[Photopolymerizable compound]
The photosensitive composition may contain a photopolymerizable compound in addition to the polymerizable composition according to any one of the first to fourth aspects. As the photopolymerizable compound, a monomer having an ethylenically unsaturated group is usually used. Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers may be used alone or in combination of two or more.

  Polyfunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate Rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meta Acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, Examples thereof include polyfunctional monomers such as a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers may be used alone or in combination of two or more.

[Alkali-soluble resin]
The photosensitive composition may contain an alkali-soluble resin. In this specification, the alkali-soluble resin means that a resin film having a film thickness of 1 μm is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and 0.04% by mass of hydroxide. When immersed in a potassium (KOH) aqueous solution for 1 minute, it means a film that dissolves in a thickness of 0.01 μm or more. The alkali-soluble resins can be used alone or in combination of two or more.

  The alkali-soluble resin is not particularly limited, and examples thereof include novolak resins, polyhydroxystyrene resins, acrylic resins, and resins having a cardo structure not modified with polyfunctional (meth) acrylate.

  As the alkali-soluble resin, a polymer of a monomer having an ethylenically unsaturated double bond is preferable because it is excellent in film-forming properties and the characteristics of the resin can be easily adjusted by selecting a monomer. As monomers having an ethylenically unsaturated double bond, (meth) acrylic acid; (meth) acrylic acid ester; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Itaconic acid, anhydrides of these dicarboxylic acids; such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol Allyl compounds; hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Tilbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4 -Vinyl ethers such as dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, Vinyl methoxyacetate, Vinyls such as nylbutoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate Esters: styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, Acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene Styrene or styrene derivatives such as: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene 1-octadecene, and olefins such as 1-eicosene.

  From the viewpoint of alkali solubility and transparency, the alkali soluble resin is preferably a polymer of a monomer having an ethylenically unsaturated double bond and containing a unit derived from an unsaturated carboxylic acid.

  Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the desired alkali solubility. . 5-25 mass% is preferable with respect to the whole alkali-soluble resin, and, as for the quantity of the unit derived from unsaturated carboxylic acid in alkali-soluble resin, 8-16 mass% is more preferable.

  Among polymers of monomers having an ethylenically unsaturated double bond, which are polymers of one or more monomers selected from the monomers exemplified above, transparency, film-forming property, hardness Because of such a good balance of mechanical properties, a polymer of at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester is preferable. Hereinafter, a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester will be described.

  The (meth) acrylic acid ester used for the preparation of a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester is particularly within the range not hindering the object of the present invention. It is not limited, It selects suitably from well-known (meth) acrylic acid ester.

  Suitable examples of (meth) acrylic acid esters include linear or methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, and the like. Branched alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) Examples include acrylate, furfuryl (meth) acrylate; (meth) acrylic acid ester having a group having an epoxy group; and (meth) acrylic acid ester having a group having an alicyclic skeleton. Details of the (meth) acrylic acid ester having a group having an epoxy group and the (meth) acrylic acid ester having a group having an alicyclic skeleton will be described later.

  Among polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, adhesion of a film formed by using a photosensitive composition to a substrate or a machine From the viewpoint of excellent mechanical strength, a resin containing a unit derived from a (meth) acrylic acid ester having a group having an epoxy group is preferred.

  Even if the (meth) acrylic ester having a group having an epoxy group is a (meth) acrylic ester having a group having a chain aliphatic epoxy group, a group having an alicyclic epoxy group as described later (Meth) acrylic acid ester having

  The (meth) acrylic acid ester having a group having an epoxy group may contain an aromatic group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of (meth) acrylic acid ester having an aromatic group and a group having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyl. Examples thereof include oxyphenyl (meth) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, and 2-glycidyloxyphenylmethyl (meth) acrylate.

  Examples of (meth) acrylic acid ester having a group having a chain aliphatic epoxy group include an ester group (—O—CO, such as epoxyalkyl (meth) acrylate, epoxyalkyloxyalkyl (meth) acrylate, and the like. (Meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to the oxy group (—O—) in —). Such a chain aliphatic epoxy group possessed by the (meth) acrylate ester may contain one or a plurality of oxy groups (—O—) in the chain. Although carbon number of a chain | strand-shaped aliphatic epoxy group is not specifically limited, 3-20 are preferable, 3-15 are more preferable, and 3-10 are especially preferable.

  Specific examples of the (meth) acrylic acid ester having a group having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6 , 7-epoxyheptyl (meth) acrylate and other epoxy alkyl (meth) acrylates; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl ( Examples thereof include epoxyalkyloxyalkyl (meth) acrylates such as (meth) acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate.

  Epoxy group in a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, including a unit derived from (meth) acrylic acid ester having a group having an epoxy group 1-95 mass% is preferable with respect to the weight of resin, and, as for content of the unit derived from the (meth) acrylic acid ester which has group which has a more preferable 30-70 mass%.

  Moreover, in the polymer of 1 or more types of monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, it is easy to form the film | membrane excellent in transparency using a photosensitive composition. A resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton is also preferable.

  In the (meth) acrylic acid ester having a group having an alicyclic skeleton, the group having an alicyclic skeleton is a group having an alicyclic epoxy group, even if the group has an alicyclic hydrocarbon group. May be. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Among the (meth) acrylic acid ester having a group having an alicyclic skeleton, examples of the (meth) acrylic acid ester having a group having an alicyclic hydrocarbon group include the following formulas (a1-1) to (a1- The compound represented by 8) is mentioned. In these, the compound represented by the following formula (a1-3)-(a1-8) is preferable, and the compound represented by the following formula (a1-3) or (a1-4) is more preferable.

In the above formula, R ^a1 represents a hydrogen atom or a methyl group, R ^a2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a3 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 5. R ^a2 is preferably a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. R ^a3 is preferably a methyl group or an ethyl group.

  Among the (meth) acrylic acid ester having a group having an alicyclic skeleton, specific examples of the (meth) acrylic acid ester having a group having an alicyclic epoxy group include, for example, the following formulas (a2-1) to ( and a compound represented by a2-16). Among these, the compounds represented by the following formulas (a2-1) to (a2-6) are preferable in order to make the developability of the film-forming resin composition appropriate, and the following formula (a2-1) ) To (a2-4) are more preferred.

In the above formula, R ^a4 represents a hydrogen atom or a methyl group, R ^a5 represents a divalent aliphatic saturated hydrocarbon group having 1 to ⁶ carbon atoms, and R ^a6 represents a divalent divalent hydrocarbon having 1 to 10 carbon atoms. A hydrocarbon group is shown, t shows the integer of 0-10. R ^a5 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. Examples of R ^a6 include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph Represents a phenylene group).

  Resin containing a unit derived from (meth) acrylic acid ester, in which a polymer of at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester has a group having an alicyclic skeleton The amount of the unit derived from the (meth) acrylic acid ester having a group having an alicyclic skeleton in the resin is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and 30 to 70%. Even more preferred is mass%.

  Moreover, the polymer of the 1 or more types of monomer selected from the (meth) acrylic acid and the (meth) acrylic acid ester containing the unit derived from the (meth) acrylic acid ester which has group which has alicyclic skeleton Among these, a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group is preferable. Such a resin is excellent in adhesion to a substrate on which a transparent insulating film is formed. When such a resin is used, it is possible to cause a self-reaction between a carboxyl group contained in the resin and an alicyclic epoxy group. Therefore, when a photosensitive composition containing such a resin is used, a film formed by causing a self-reaction between a carboxyl group and an alicyclic epoxy group using a method of heating the film or the like. It is possible to improve mechanical properties such as hardness.

  In a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group, a unit derived from (meth) acrylic acid in the resin Is preferably 1 to 95% by mass, more preferably 10 to 50% by mass. In a resin including a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group, a group having an alicyclic epoxy group in the resin 1-95 mass% is preferable and, as for the quantity of the unit derived from the (meth) acrylic acid ester which has, 30-70 mass% is more preferable.

  It is selected from (meth) acrylic acid and (meth) acrylic acid ester, including a unit derived from (meth) acrylic acid and a unit derived from (meth) acrylic acid ester having a group having an alicyclic epoxy group. Among the polymers of one or more monomers, a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, A resin containing a unit derived from a (meth) acrylic acid ester having a group having a cyclic epoxy group and a unit derived from styrene or a styrene derivative is preferable.

  (Meth) acrylic acid ester having a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a group having an alicyclic epoxy group In the resin containing the unit derived from styrene and the unit derived from styrene or a styrene derivative, the amount of the unit derived from (meth) acrylic acid in the resin is preferably 1 to 95% by mass, and 10 to 50% by mass. Is more preferable.

  (Meth) acrylic acid ester having a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a group having an alicyclic epoxy group In the resin containing the unit derived from styrene and the unit derived from styrene or a styrene derivative, the amount of the unit derived from the (meth) acrylate ester having a group having a chain aliphatic epoxy group in the resin is 1 -95 mass% is preferable, and 10-70 mass% is more preferable.

  (Meth) acrylic acid ester having a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a group having an alicyclic epoxy group In the resin containing the unit derived from styrene and the unit derived from styrene or a styrene derivative, the amount of the unit derived from the (meth) acrylic acid ester having a group having an alicyclic epoxy group in the resin is 1 to 95 mass% is preferable and 30-70 mass% is more preferable.

  (Meth) acrylic acid ester having a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a group having an alicyclic epoxy group In the resin containing a unit derived from styrene and a unit derived from styrene or a styrene derivative, the amount of the unit derived from styrene or a styrene derivative in the resin is preferably 1 to 95% by mass, and 10 to 70% by mass. More preferred.

  The mass average molecular weight of the alkali-soluble resin is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability. In addition, in this specification, a mass average molecular weight means the value by polystyrene conversion measured by gel permeation chromatography (GPC).

[Colorant]
The photosensitive composition may contain a colorant. The photosensitive composition containing a colorant is preferably used, for example, as a color filter forming application for a liquid crystal display. Moreover, the photosensitive composition containing a light-shielding agent as a colorant is preferably used, for example, as a black matrix forming application in a color filter of a display device.

  Although it does not specifically limit as a coloring agent, For example, the compound classified into the pigment (Pigment) in the color index (CI; issue | issued by The Society of Dyers and Colorists), specifically, as follows It is preferable to use a color index (CI) number.

C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 185;
C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 : 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 : 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 166, 168, 170, 171, 172, 174, 175, 176, 177, 78, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  When the colorant is a light-shielding agent, it is preferable to use a black pigment as the light-shielding agent. Examples of black pigments include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and other metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, etc. Various pigments can be mentioned regardless of organic matter and inorganic matter. Among these, it is preferable to use carbon black having high light shielding properties.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

  Resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so there is little leakage of current when used as a black matrix for liquid crystal display elements such as liquid crystal display, and high reliability and low A display with power consumption can be manufactured.

  Moreover, in order to adjust the color tone of carbon black, you may add said organic pigment suitably as an auxiliary pigment.

  In order to uniformly disperse the colorant in the photosensitive composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

  In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when used in combination, the organic pigment is used in an amount of 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. Preferably, it is used in the range of 20 to 40 parts by mass.

Although the usage-amount of the coloring agent in a photosensitive composition should just be determined suitably according to the use of a photosensitive composition, as an example, it is 5-70 with respect to a total of 100 mass parts of solid content of a photosensitive composition. A mass part is preferable and 25-60 mass parts is more preferable. By setting it as said range, a black matrix and each colored layer can be formed with the target pattern, and it is preferable.
In particular, when forming a black matrix using the photosensitive composition, it is preferable to adjust the amount of the light-shielding agent in the photosensitive composition so that the OD value per 1 μm of the coating film of the black matrix is 4 or more. . If the OD value per 1 μm film in the black matrix is 4 or more, sufficient display contrast can be obtained when used in the black matrix of a liquid crystal display.

  The colorant is preferably added to the photosensitive composition after making it into a dispersion liquid dispersed at an appropriate concentration using a dispersant.

[Other ingredients]
Various additives may be added to the photosensitive composition as necessary. Specifically, solvents, sensitizers, curing accelerators, photocrosslinkers, photosensitizers, dispersion aids, fillers, adhesion promoters, antioxidants, UV absorbers, anti-aggregation agents, and thermal polymerization are prohibited Examples include agents, antifoaming agents, surfactants and the like.

  Examples of the solvent used in the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Mono-n-butyl ether, dipropylene glycol mono (Poly) alkylene glycol monoalkyl ethers such as chill ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate ; Other ethers such as glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, pyruvine Other esters such as methyl acid, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N , N-dimethylformamide, amides such as N, N-dimethylacetamide, and the like. These solvents may be used alone or in combination of two or more.

  Although the usage-amount of a solvent should just be determined suitably according to the use of a photosensitive composition, about 50-900 mass parts is used with respect to the total of 100 mass parts of solid content of a photosensitive composition as an example.

  Examples of the thermal polymerization inhibitor used in the photosensitive composition include hydroquinone and hydroquinone monoethyl ether. Examples of the antifoaming agent include silicone-based and fluorine-based compounds, and examples of the surfactant include anionic, cationic, and nonionic compounds.

[Method for preparing photosensitive composition]
The photosensitive composition is prepared by mixing all the above components with a stirrer. In addition, you may filter using a filter so that the prepared photosensitive composition may become uniform.

≪Sixth aspect≫
The sixth aspect is a cured product of the photosensitive composition according to the fifth aspect. The cured product according to the sixth aspect is not particularly limited as long as the photosensitive composition according to the fifth aspect is cured by exposure. Usually, after apply | coating the photosensitive composition which concerns on a 5th aspect to a board | substrate, exposure is performed with respect to a coating film, and hardened | cured material is formed as a cured film. When forming the cured product, a patterned cured product may be formed by applying a photolithography method.

  Hereinafter, a suitable method for forming the cured product as a patterned cured film will be described.

  First, the photosensitive composition is applied onto the substrate using a contact transfer type coating apparatus such as a roll coater, reverse coater, or bar coater, or a non-contact type coating apparatus such as a spinner (rotary coating apparatus) or a curtain flow coater.

  Next, the coated photosensitive composition is dried to form a coating film. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds, (2) several hours at room temperature Examples include a method of leaving for several days, and (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours.

Next, the coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The energy dose to be irradiated varies depending on the composition of the photosensitive composition, but is preferably about 10 to 2000 mJ / cm ² , for example.

  Next, the exposed film is developed into a desired shape by developing with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. As already explained, by using the photosensitive composition according to the present invention, it is possible to form a pattern having excellent straightness and excellent adhesion to a substrate even when exposure is performed at a low exposure amount. .

  Next, it is preferable to perform post-baking on the developed pattern at about 200 ° C. to 250 ° C.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

[Example 1]
In a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid are charged. The solution was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate which is colorless and transparent, and was represented with the following solid formula.

After dissolving 600 g of 3-methoxybutyl acetate in 307.0 g of the above bisphenolfluorene type epoxy acrylate, 80.5 g of benzophenonetetracarboxylic dianhydride, 4.5 g of dipentaerythritol pentaacrylate (DPPA), dipentaerythritol Hexaacrylate (DPHA) (4.6 g) and tetraethylammonium bromide (1 g) were mixed, gradually heated to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Resin A. The disappearance of the acid anhydride group was confirmed by IR spectrum.
Dipentaerythritol hexaacrylate (DPHA) does not participate in the modification reaction because it does not have a hydroxyl group.

  A solution of the resin A having a solid content of 20 parts by mass, 20 parts by mass of dipentaerythritol hexaacrylate, 10 parts by mass of an oxime ester photopolymerization initiator having the following formula, and 3-methoxybutyl acetate 50 parts by mass of carbon black dispersion (CF black (manufactured by Mikuni Dye Co., Ltd.), solid concentration 25% by mass) in which carbon black is dispersed is added to an organic solvent so that the solids concentration becomes 17.5% by mass. Diluted. As the organic solvent, a mixed solvent in which diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate were mixed at a mass ratio of 1: 1 was used. The diluted mixture was uniformly mixed with a stirrer for 1 hour, and then filtered through a membrane filter having a pore size of 1 μm to obtain a black photosensitive composition.

  About the pattern formed using the obtained photosensitive composition, according to the following method, the linearity of a pattern, the adhesiveness to the board | substrate of a pattern, and surface resistance were evaluated. These evaluation results are shown in Table 1.

<Pattern straightness evaluation>
The photosensitive composition was applied onto a glass substrate (100 mm × 100 mm) using a spin coater, and pre-baked at 80 ° C. for 120 seconds to form a coating film. Next, a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Corporation) is used, the exposure gap is set to 100 μm, and the coating film is irradiated with ultraviolet rays through a negative mask on which a line pattern with a width of 6 μm is formed. did. The exposure amount was set in four stages of 10, 20, 30, and 40 mJ / cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 25 ° C. for 70 seconds and then post-baked at 230 ° C. for 20 minutes to form a line pattern with a thickness of 1.3 μm.
The formed line pattern was observed with an optical microscope, and pattern straightness was evaluated. The straightness of the pattern was evaluated as “◎” when the edge of the line was not rattled, “◯” when it was slightly shaky, and “x” if it was shaky.

<Pattern adhesion evaluation>
The line pattern formed in the pattern straightness evaluation was checked for the presence or absence of pattern peeling with an optical microscope.

<Surface resistance>
A coating film having a thickness of 1.0 μm was formed on a glass substrate (100 mm × 100 mm) in the same manner as in the pattern straightness evaluation. Next, a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Corporation) was used, the exposure gap was set to 100 μm, and the coating film was irradiated with ultraviolet rays without using a photomask. The exposure amount was 40 mJ / cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 25 ° C. for 50 seconds and then post-baked at 230 ° C. for 30 minutes to prepare a cured film. The surface resistance value of this cured film was measured as the initial surface resistance. Further, the cured film was further post-baked at 230 ° C. for 3 hours, and the surface resistance value of the cured film subjected to further heat treatment was measured as the surface resistance after the heat treatment.

[Example 2]
A bisphenolfluorene type epoxy acrylate was obtained in the same manner as in Example 1. After adding and dissolving 600 g of 3-methoxybutyl acetate in 307.0 g of bisphenolfluorene type epoxy acrylate, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually heated to 110 The reaction was carried out at ˜115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride, 2.3 g of dipentaerythritol pentaacrylate (DPPA), and dipentaerythritol hexaacrylate (DPHA) 2 And 4 g were mixed and reacted at 90 ° C. for 6 hours to obtain Resin B. The disappearance of the acid anhydride group was confirmed by IR spectrum.
Dipentaerythritol hexaacrylate (DPHA) does not participate in the modification reaction because it does not have a hydroxyl group.

  A photosensitive composition was prepared in the same manner as in Example 1 except that the resin B solution obtained by changing to the resin A solution was used. About the pattern formed using the obtained photosensitive composition, like Example 1, the straight advanceability of the pattern, the adhesiveness to the board | substrate of a pattern, and surface resistance were evaluated. These evaluation results are shown in Table 1.

Example 3
A bisphenolfluorene type epoxy acrylate was obtained in the same manner as in Example 1. After adding and dissolving 600 g of 3-methoxybutyl acetate in 307.0 g of bisphenolfluorene type epoxy acrylate, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually heated to 110 The reaction was carried out at ˜115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride, 4.5 g of dipentaerythritol pentaacrylate (DPPA), and dipentaerythritol hexaacrylate (DPHA) 4 And 6 g were mixed and reacted at 90 ° C. for 6 hours to obtain Resin C. The disappearance of the acid anhydride group was confirmed by IR spectrum.
Dipentaerythritol hexaacrylate (DPHA) does not participate in the modification reaction because it does not have a hydroxyl group.

  A photosensitive composition was prepared in the same manner as in Example 1 except that the resin C solution obtained by changing to the resin A solution was used. About the pattern formed using the obtained photosensitive composition, like Example 1, the straight advanceability of the pattern, the adhesiveness to the board | substrate of a pattern, and surface resistance were evaluated. These evaluation results are shown in Table 1.

Example 4
A bisphenolfluorene type epoxy acrylate was obtained in the same manner as in Example 1. After adding 85.4 g of 3-methoxybutyl acetate solution to 48.5 g of bisphenol fluorene type epoxy acrylate, 11.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was mixed and gradually added. The mixture was heated to 100 to 105 ° C. for 14 hours.
After confirming disappearance of the acid anhydride group, 16.7 g of methoxybutyl acetate was added to dilute the reaction solution. In the reaction solution, 4.5 g of dipentaerythritol pentaacrylate (DPPA) and 4.6 g of dipentaerythritol hexaacrylate (DPHA) were mixed and reacted at 90 to 95 ° C. for 4 hours to obtain Resin D. The disappearance of the acid anhydride group was confirmed by IR spectrum. Moreover, the solid content concentration of the solution containing the obtained resin D was 56.9% by mass. The acid value of the resin D was 48.4 mgKOH / g, and the mass average molecular weight was 3,800.
Dipentaerythritol hexaacrylate (DPHA) does not participate in the modification reaction because it does not have a hydroxyl group.
In addition, Example 4 was carried out for the purpose of demonstrating the synthesis of Resin D. For this reason, about the photosensitive composition containing resin D, the linearity of a pattern, the adhesiveness to the board | substrate of a pattern, and surface resistance were not evaluated.

[Comparative Example 1]
A bisphenolfluorene type epoxy acrylate was obtained in the same manner as in Example 1. After adding and dissolving 600 g of 3-methoxybutyl acetate in 307.0 g of bisphenolfluorene type epoxy acrylate, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually heated to 110 The reaction was carried out at ˜115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Resin E. The disappearance of the acid anhydride group was confirmed by IR spectrum.

  A photosensitive composition was prepared in the same manner as in Example 1 except that the resin E solution obtained by changing to the resin A solution was used. About the pattern formed using the obtained photosensitive composition, like Example 1, the straight advanceability of the pattern, the adhesiveness to the board | substrate of a pattern, and surface resistance were evaluated. These evaluation results are shown in Table 1.

According to Table 1, when the photosensitive compositions of Examples 1 to 3 including a resin having a cardo structure modified with polyfunctional acrylate (DPPA: dipentaerythritol pentaacrylate) are used, 10 mJ / cm ² It can be seen that a pattern having excellent straightness and excellent adhesion to the substrate can be formed even with a low exposure amount. On the other hand, when the photosensitive composition of Comparative Example 1 containing a resin having a cardo structure not modified with a polyfunctional acrylate is used, at a low exposure amount of about 10 mJ / cm ² , the linearity is excellent, and to the substrate. A pattern with excellent adhesion could not be formed.

  Moreover, although the modification timing by polyfunctional acrylate differs in Example 1 and Examples 2 and 3, from Table 1, the modification timing greatly affects the performance of the photosensitive composition containing the modified resin. It can be seen that

  From Table 1, it can be seen that the presence or absence of modification by the polyfunctional acrylate regarding the resin having a cardo structure does not affect the surface resistance of the cured product (cured film).

Claims (8)

A polymerizable composition obtained by reacting a product represented by the following formula (1) and a polybasic acid anhydride with a polyfunctional (meth) acrylate having one or more hydroxyl groups. Because
A polymerizable composition comprising a polyfunctional (meth) acrylate-modified compound, wherein the polyfunctional (meth) acrylate is a compound having two or more (meth) acryloyloxy groups.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.) A polymerizable composition obtained by reacting a compound represented by the following formula (1) with a polybasic acid anhydride and a polyfunctional (meth) acrylate having one or more hydroxyl groups,
A polymerizable composition comprising a polyfunctional (meth) acrylate-modified compound, wherein the polyfunctional (meth) acrylate is a compound having two or more (meth) acryloyloxy groups.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.) A compound represented by the following formula (1) and a polyfunctional (meth) acrylate modified product of the polybasic acid dianhydride represented by the following formula (2), or a polybasic acid represented by the following formula (2) A polymerizable composition comprising a polyfunctional (meth) acrylate-modified compound obtained by reacting a mixture of a polyfunctional (meth) acrylate modified dianhydride and a polybasic acid anhydride.

(In Formula (1), R ¹ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ² is each independently a hydrogen atom or a methyl group.)

(In the formula (2), a is an integer of 2 or more, b is an integer of 0 or more, A ¹ is a tetravalent organic group derived from polybasic acid dianhydride, and A ² is a + b + 1. And R ² is independently a hydrogen atom or a methyl group.)   About the polymeric composition containing the polyfunctional (meth) acrylate modified compound which has a hydroxyl group as described in any one of Claims 1-3, the hydroxyl group which the polyfunctional (meth) acrylate modified compound which has the said hydroxyl group has A polymerizable composition containing a polyfunctional (meth) acrylate-modified compound obtained by reacting polybasic acid monoanhydride.   A photosensitive composition comprising the polymerizable composition according to claim 1.   Furthermore, the photosensitive composition of Claim 5 containing a photoinitiator.   Furthermore, the photosensitive composition of Claim 5 or 6 containing a coloring agent.   Hardened | cured material of the photosensitive composition of any one of Claims 5-7.