JP2016142753A - Photosensitive resin composition, cured member comprising the same, and image display device having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can be patterned by photolithography and can form a cured member having excellent electrical reliability at a low temperature.SOLUTION: A photosensitive resin composition comprises (A) a vinyl polymer comprising a side chain α having an epoxy group, (B) a photocationic polymerization initiator, (C) an ethylenically unsaturated group-containing compound, and (D) a thermal radical polymerization initiator.SELECTED DRAWING: None

Description

  In the present invention, members such as a protective film, an insulating film, a planarizing film, a column spacer, a bank, a color filter, and a resin black matrix used for an image display device such as a liquid crystal display device or an organic EL display device are patterned with photolithography. It is related with the photosensitive resin composition which can be formed. More specifically, the present invention relates to a photosensitive resin composition that can be formed at a low temperature, a cured member composed thereof, and an image display device including the same.

  In recent years, flexible displays that satisfy required characteristics such as weight reduction, impact resistance, and bending characteristics have become widespread, and in these, flexible plastic substrates are used as substrates for forming members. In addition, flexible plastic substrates that can be used for roll-to-roll are also being studied from the viewpoint of printing electronics as a means of reducing costs and dealing with a small variety of products.

As such a flexible plastic substrate, polycarbonate, polyethylene terephthalate, and the like have been studied, but these are inferior in heat resistance as compared with a conventional glass substrate. Therefore, in order to reduce the thermal stress applied to the plastic substrate, the temperature of the flexible display manufacturing process is required to be lower than before. There is a baking process for forming a member such as a protective film and an insulating film as one of the processes requiring the highest temperature in manufacturing a flexible display, and the temperature of the baking process is required to be lowered.
In addition to this, for example, there is a movement to reduce the weight and cost by forming a polarizing film of a liquid crystal display by a coating type, but a protective film formed on a coating type polarizing film is also a polarizing film or a liquid crystal layer. It is necessary to form at a temperature that does not damage the material, and a low temperature (low temperature curability) is required.
Furthermore, for example, in color filters used in image display devices, as a method for achieving high contrast, various studies have been made on shifting a color material from a pigment system to a dye system. In view of this, the low temperature curability of the color filter forming material is also required. Further, even when a pigment is used as the color material, it is known that high-temperature curing can obtain higher contrast, and low-temperature curability is also required from this viewpoint.

As such a low temperature curable photosensitive resin composition, various reports using cationic polymerization of epoxy and oxetane, and further combining radically polymerizable materials with these are seen.
For example, Patent Document 1 includes a combination of an epoxy group-containing polymer and a cationic polymerization initiator, and Patent Document 2 includes a combination of an epoxy group and oxetanyl group-containing copolymer and a photosensitive acid generator such as an onium salt. Patent Document 3 describes a combination of an oxetanyl group-containing copolymer, a photo-sensitive acid generator such as an onium salt, and an epoxy compound.
Patent Documents 4 and 5 show a combination of a cationic polymerization system using an epoxy group-containing copolymer and a radical polymerization system, and Patent Documents 6 and 7 show a cationic polymerization system and a radical polymerization system using an oxetane compound. A combination of these is disclosed.

Japanese Patent Laid-Open No. 11-5816 JP 2005-84415 A International Publication No. 2006/006581 Pamphlet JP 2008-260909 A JP 2012-150180 A JP 2011-48064 A JP 2003-255531 A

In recent years, market demands for simplification of processes and panel structures are increasing, and materials having both photolithographic properties and sufficient strength are required even in low-temperature manufacturing processes.
When this inventor examined, the photosensitive resin composition described in patent documents 1-7 is not enough in electrical reliability, and when it is used for a liquid crystal display or an organic EL display, image burn-in and life reduction It has been found that there are problems such as an adverse effect such as an increase in driving voltage, and a decrease in mobility and the occurrence of hysteresis when close to the organic TFT semiconductor.

  The present invention has been made in view of such conventional techniques. That is, an object of the present invention is to provide a photosensitive resin composition that can be patterned by photolithography and can form a cured member having good electrical reliability at a low temperature.

  The inventor has made various studies to solve the above problems. As a result, a photosensitive resin composition containing a vinyl polymer containing a side chain α having an epoxy group, a cationic photopolymerization initiator, an ethylenically unsaturated group-containing compound, and a thermal radical polymerization initiator is patterned by photolithography. And the present inventors have found that it is possible to achieve both high electrical reliability during low-temperature curing and have completed the present invention. That is, the gist of the present invention is as follows.

[1] Contains (A) a vinyl polymer containing a side chain α having an epoxy group, (B) a photocationic polymerization initiator, (C) an ethylenically unsaturated group-containing compound, and (D) a thermal radical polymerization initiator. A photosensitive resin composition characterized by comprising:
[2] The photosensitive resin composition according to [1], wherein (D) the thermal radical polymerization initiator includes a thermal radical polymerization initiator having a 10-hour half-life temperature of 70 to 140 ° C.
[3] The photosensitive resin composition according to [1] or [2], wherein (D) the thermal radical polymerization initiator includes an azo compound represented by the following general formula (1).

(In the general formula (1), each independently of R ¹ and R ² represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, R ¹ attached to the same carbon atom And R ² may combine to form a ring, R ³ represents an optionally substituted alkyl group having 1 to 10 carbon atoms, and X represents O or NH.

[4] The method according to any one of [1] to [3], further comprising (E) a naphthalene compound or an anthracene compound having two or more substituents selected from the group consisting of an alkyl ether group and an acyloxyl group. Photosensitive resin composition.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein (A) the vinyl polymer includes a side chain β having a cyclic aliphatic group.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein (A) the vinyl polymer includes a side chain γ having a carboxyl group or an aromatic hydroxyl group.

[7] The photosensitive resin composition according to any one of [1] to [6], further comprising (F) a color material.
[8] The photosensitive resin composition according to any one of [1] to [7], further comprising (G) inorganic nanoparticles.
[9] The photosensitive resin composition according to any one of [1] to [8], further comprising (H) a liquid repellent.
[10] A cured member composed of the photosensitive resin composition according to any one of [1] to [9].
[11] The cured member according to [10], having one or more convex portions.
[12] An image display device comprising the curing member according to [10] or [11].

[13] A protective layer formed on the anisotropic dye film, which is formed using the photosensitive resin composition according to any one of [1] to [6].
[14] The protective layer according to [13], wherein the anisotropic dye film is formed by coating.
[15] A polarizing element comprising the protective layer according to [13] or [14] on an anisotropic dye film.
[16] The photosensitive resin composition according to any one of [1] to [6] is wet-formed on the anisotropic dye film, and after exposure, the anisotropic dye film and the photosensitive resin are developed with a developer. A method for producing a polarizing element, wherein both of the composition films are developed.
[17] An image display device comprising the polarizing element according to [15].

  According to the photosensitive resin composition of the present invention, it is possible to form a cured member that can be patterned by photolithography and has good electrical reliability at a low temperature.

Hereinafter, embodiments of the present invention will be described in detail. However, the description described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist thereof.
In the present invention, “(meth) acrylic acid” includes both acrylic acid and methacrylic acid, and “(meth) acrylate”, “(meth) acryloyl” and the like have the same meaning. Moreover, what added "(poly)" before the monomer name means this monomer and this polymer.
In the present invention, the “total solid content” means all components except the solvent among the constituent components of the photosensitive resin composition of the present invention.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) a vinyl polymer containing a side chain α having an epoxy group, (B) a photocationic polymerization initiator, (C) an ethylenically unsaturated group-containing compound, and (D). Contains a thermal radical polymerization initiator. The photosensitive resin composition of the present invention may further contain (E) a naphthalene compound or an anthracene compound having two or more substituents selected from the group consisting of an alkyl ether group and an acyloxyl group. It may contain a coloring material, (G) inorganic nanoparticles, and (H) a liquid repellent. Further, silicon and / or fluorine-based surfactants may be contained, and other additives may be appropriately contained.

[(A) Vinyl polymer containing side chain α having epoxy group]
The photosensitive resin composition of the present invention contains (A) a vinyl polymer containing a side chain α having an epoxy group, so that photocurability during photolithography, development pattern formation, shrinkage during photo / thermosetting. It is possible to achieve excellent film quality with reduced reduction in flexibility and permeability.

  The chemical structure of the vinyl polymer containing the side chain α having an epoxy group is not particularly limited. For example, the vinyl polymer having a repeating unit structure represented by the following general formula (2) containing the side chain α having an epoxy group Can be mentioned.

In the general formula (2), R ⁴ represents a hydrogen atom or a methyl group.
α represents a direct bond or a divalent linking group. However, a carbon atom not bonded to α of the epoxy group in formula (2) may be bonded to α to form a ring.

Examples of the divalent linking group for α include an alkylene group which may have a substituent, and the methylene group in the alkylene group includes an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, and an amide. It may be substituted with at least one bond selected from the group consisting of a bond and a urethane bond. Examples thereof include a linking group containing an ester bond or an amide bond.
The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 or more from the viewpoint of ease of synthesis, and is preferably 9 or less from the viewpoint of film forming properties, and is 7 or less. Is more preferably 5 or less, and particularly preferably 3 or less.
Examples of the substituent that the alkylene group may have include, for example, a halogen atom, an alkenyl group having 2 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, and a cyano group. Group, acetyloxy group, C2-C9 alkylcarbonyloxy group, sulfamoyl group, C2-C9 alkylsulfamoyl group, C2-C9 alkylcarbonyl group, phenethyl group, hydroxyethyl group, acetyl An amide group, a dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, an alkylthio group having 1 to 8 carbon atoms, and the like. Preferably, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl having 2 to 8 carbon atoms , Sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, a halogen atom. From the viewpoint of ease of synthesis, the alkylene group is preferably unsubstituted.

Among α, from the viewpoint of ease of synthesis, an alkylene group interrupted by a direct bond, an ether bond, or an ester bond is preferable, and an alkylene group interrupted by an ester bond is more preferable, More preferably, it is a — (C═O) —O—CH ₂ — group. The alkylene group interrupted by an ether bond means an alkylene group having an ether bond (—O— bond) between C—C bonds constituting the alkylene group. Similarly, an alkylene group interrupted by an ester bond means an alkylene group having an ester bond (—CO—O— bond) between C—C bonds constituting the alkylene group.

  (A) In order to obtain a vinyl polymer containing a side chain α having an epoxy group, a method using an epoxy group-containing vinyl compound as a polymerization component can be mentioned. Examples of the epoxy group-containing vinyl compound include the following compounds.

  Examples of the epoxy group-containing vinyl compound include allyl glycidyl ether, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, α-n-propylglycidyl (meth) acrylate, α-n. -Butyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl ether glycidyl crotonate, glycidyl isocroto Crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate, o-vinyl Aliphatic epoxy group-containing compounds such as benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, epoxy group-containing vinyl compounds, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4 -Epoxycyclohexyl) ethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] oxymethyl (meth) acrylate And alicyclic epoxy group-containing vinyl compounds.

  One of these may be used alone, or two or more thereof may be used in any combination and ratio. Among these, from the viewpoint of adhesion to the substrate, it is preferable to use an aliphatic epoxy group-containing vinyl compound, more preferably a (meth) acrylate compound, glycidyl (meth) acrylate or 4-hydroxybutyl ( More preferably, (meth) acrylate glycidyl ether is used.

  (A) The content ratio of the repeating unit structure derived from the epoxy group-containing vinyl compound in the vinyl polymer (the repeating unit structure represented by the general formula (2)) is preferably 30 mol% or more, and 40 mol% or more. More preferably, it is more preferably 50 mol% or more. Moreover, it is 100 mol% or less normally, It is preferable that it is 99 mol% or less, It is more preferable that it is 90 mol% or less, It is further more preferable that it is 80 mol% or less, It is especially preferable that it is 70 mol% or less. There is a tendency that exposure sensitivity, electrical reliability, and chemical resistance can be ensured by setting it to the above lower limit value or more, and there is a tendency that excellent film quality and patterning property at the time of development can be ensured by setting the upper limit value or less. is there.

  (A) The vinyl polymer may further contain a side chain β having a cyclic aliphatic group. By including the side chain β, there is a tendency that uniform and excellent film quality is obtained.

  The chemical structure of the vinyl polymer containing the side chain β having a cycloaliphatic group is not particularly limited. For example, the repeating unit structure represented by the following general formula (3) containing the side chain β having a cycloaliphatic group Can be included.

In the general formula (3), R ⁵ represents a hydrogen atom or a methyl group.
β represents a direct bond or a divalent linking group.
R ⁶ represents a cyclic aliphatic group which may have a substituent.

Examples of the divalent linking group in β include an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, a urethane bond, and an alkylene group that may have a substituent. A part of the methylene group of the alkylene group may be substituted with at least one bond selected from the group consisting of an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond and a urethane bond. Examples thereof include a linking group containing an ester bond or an amide bond.
The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 or more from the viewpoint of ease of synthesis, and is preferably 9 or less from the viewpoint of film forming properties, and is 7 or less. Is more preferable.
Examples of the substituent that the alkylene group may have include, for example, a halogen atom, an alkenyl group having 2 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, and a cyano group. Group, acetyloxy group, C2-C9 alkylcarbonyloxy group, sulfamoyl group, C2-C9 alkylsulfamoyl group, C2-C9 alkylcarbonyl group, phenethyl group, hydroxyethyl group, acetyl An amide group, a dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, an alkylthio group having 1 to 8 carbon atoms, and the like. Preferably, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl having 2 to 8 carbon atoms , Sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, a halogen atom. From the viewpoint of ease of synthesis, the alkylene group is preferably unsubstituted.

  Among β, from the viewpoint of ease of synthesis, a direct bond, an ether bond, an ester bond, an alkylene group interrupted by an ether bond, or an alkylene group interrupted by an ester bond is preferable, and an ester bond is more preferable. The alkylene group interrupted by an ether bond means an alkylene group having an ether bond (—O— bond) between C—C bonds constituting the alkylene group. Similarly, an alkylene group interrupted by an ester bond means an alkylene group having an ester bond (—CO—O— bond) between C—C bonds constituting the alkylene group.

The number of carbon atoms of the cycloaliphatic group in R ⁶ is not particularly limited, but is preferably 5 or more from the viewpoint of film strength, more preferably 6 or more, further preferably 8 or more, From the viewpoint of the reactivity of the vinyl polymer, it is preferably 20 or less, more preferably 15 or less, and even more preferably 12 or less.
The cyclic aliphatic group may be monocyclic or polycyclic, but is preferably polycyclic from the viewpoint of film strength.
Specific examples of the cycloaliphatic group include a cyclohexyl group, a dicyclopentanyl group, an adamantyl group, a norbornyl group, a tetracyclodecanyl group, etc. Among these, from the viewpoint of the strength of the film, a dicyclopentanyl group Or an adamantyl group is preferable.

In order to obtain a vinyl polymer containing a side chain β having a cycloaliphatic group, it is preferable to use a cycloaliphatic group-containing vinyl compound as a polymerization component. Examples of the cyclic aliphatic group-containing vinyl compound include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxy. Examples include ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate. .
One of these may be used alone, or two or more thereof may be used in any combination and ratio. Among these, it is preferable to use a polycyclic cycloaliphatic group-containing vinyl compound from the viewpoint of the strength of the film formed, and dicyclopentanyl (meth) acrylate or 2-methyl-2-adamantyl (meth). More preferably, acrylate is used.

  (A) The content ratio of the repeating unit structure derived from these cyclic aliphatic group-containing vinyl compounds in the vinyl polymer (repeating unit structure represented by the general formula (3)) is preferably 1 mol% or more, and 10 mol. % Or more is more preferable, and it is further more preferable that it is 15 mol% or more. Moreover, it is preferable that it is 40 mol% or less, It is more preferable that it is 35 mol% or less, It is further more preferable that it is 20 mol% or less. There exists a tendency which can ensure the intensity | strength and electric reliability of the film | membrane which apply | coated and formed by setting it as the said lower limit or more, and there exists a tendency which can ensure exposure sensitivity by setting it as the said upper limit or less.

  (A) The vinyl polymer may contain a side chain γ having a carboxyl group or an aromatic hydroxyl group for the purpose of imparting alkali developability.

  The chemical structure of the vinyl polymer containing a side chain γ having a carboxyl group or an aromatic hydroxyl group is not particularly limited. For example, in the following general formula (4) containing a side chain γ having a carboxyl group or an aromatic hydroxyl group The thing containing the repeating unit structure represented can be mentioned.

In the general formula (4), R ⁷ represents a hydrogen atom or a methyl group.
γ represents a direct bond or a divalent linking group.
R ⁸ represents a carboxyl group or a group having an aromatic hydroxyl group.

Examples of the divalent linking group for γ include an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, a urethane bond, and an alkylene group that may have a substituent. A part of the methylene group of the alkylene group may be substituted with at least one bond selected from the group consisting of an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond and a urethane bond. Examples thereof include a linking group containing an ester bond or an amide bond.
The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 or more from the viewpoint of ease of synthesis, and is preferably 9 or less from the viewpoint of film forming properties, and is 7 or less. Is more preferable.
Examples of the substituent that the alkylene group may have include, for example, a halogen atom, an alkenyl group having 2 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, and a cyano group. Group, acetyloxy group, C2-C9 alkylcarbonyloxy group, sulfamoyl group, C2-C9 alkylsulfamoyl group, C2-C9 alkylcarbonyl group, phenethyl group, hydroxyethyl group, acetyl An amide group, a dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, an alkylthio group having 1 to 8 carbon atoms, and the like. Preferably, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl having 2 to 8 carbon atoms , Sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, a halogen atom. From the viewpoint of ease of synthesis, the alkylene group is preferably unsubstituted.

  Among γ, from the viewpoint of ease of synthesis, a direct bond, an ether bond, an ester bond, an alkylene group interrupted by an ether bond, or an alkylene group interrupted by an ester bond is preferable, and the direct bond or the ester bond is More preferred is a direct bond. The alkylene group interrupted by an ether bond means an alkylene group having an ether bond (—O— bond) between C—C bonds constituting the alkylene group. Similarly, an alkylene group interrupted by an ester bond means an alkylene group having an ester bond (—CO—O— bond) between C—C bonds constituting the alkylene group.

Examples of the group containing an aromatic hydroxyl group in R ⁸ include a hydroxyphenyl group, a hydroxycarboxylphenyl group, a dihydroxyphenyl group, a trihydroxyphenyl group, a bromophenyl group, a dibromophenyl group, a hydroxynaphthyl group, a hydroxynitrophenyl group, a hydroxy group. A benzyl group etc. are mentioned. Among R ^8, a hydroxyphenyl group is preferable and a p-hydroxyphenyl group is more preferable from the viewpoints of cost and film formability.

In order to obtain a vinyl polymer containing a side chain γ having a carboxyl group or an aromatic hydroxyl group, it is preferable to use a carboxyl group-containing vinyl compound or an aromatic hydroxyl group-containing vinyl compound as a polymerization component. Examples of the carboxyl group-containing vinyl compound include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other unsaturated carboxylic acids. Examples of the aromatic hydroxyl group-containing vinyl compound include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxyphenyl ( And (meth) acrylate, N- (4-hydroxyphenyl) (meth) acrylamide and the like.
One of these may be used alone, or two or more thereof may be used in any combination and ratio. Among these, from the viewpoint of sufficient alkali developability, it is preferable to use a carboxyl group-containing vinyl compound, while in order to achieve higher electrical reliability, it is preferable to use an aromatic hydroxyl group-containing vinyl compound, More preferably, (meth) acrylic acid is used as the carboxyl group-containing vinyl compound, and p-hydroxystyrene or p-hydroxyphenyl (meth) acrylate is used as the aromatic hydroxyl group-containing vinyl compound.

  (A) When a carboxyl group or an aromatic hydroxyl group is introduced into a vinyl polymer to impart alkali developability, a repeating unit structure derived from these carboxyl group-containing vinyl compound or aromatic hydroxyl group-containing vinyl compound (the above general formula ( The content of the repeating unit structure represented by 4) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. Moreover, it is preferable that it is 40 mol% or less, It is more preferable that it is 35 mol% or less, It is further more preferable that it is 30 mol% or less. There exists a tendency which becomes easy to ensure alkali developability by setting it as the said lower limit or more, and there exists a tendency for the manufacturing stability of (A) polymer to become easy to be ensured by setting it as the said upper limit or less.

  (A) When obtaining a vinyl polymer, other vinyl compounds may be used as other copolymerization components in addition to the three kinds of polymerization components. Examples of other vinyl compounds include styryl compounds such as styrene and α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl. (Meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, benzyl (meta ) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-meth Roll (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, (meth) acrylate compound, vinyl compound such as vinyl acetate, and the like. These may be used in any combination and ratio as long as the amount of the repeating unit structure derived from (A) the vinyl polymer is less than 50 mol%. Among these, it is preferable to use a (meth) acrylate compound from the viewpoint of reactivity.

  The method for polymerizing the epoxy group-containing vinyl compound, the cycloaliphatic group-containing vinyl compound, the carboxyl group-containing vinyl compound, the aromatic hydroxyl group-containing vinyl compound, and other vinyl compounds is not limited at all. The polymerization initiator can be synthesized by a known method such as adding a chain transfer agent as necessary and heating at the activation temperature of the radical polymerization initiator.

  The weight average molecular weight of the (A) vinyl polymer of the present invention is preferably 3000 or more, and more preferably 5000 or more. Moreover, it is preferable that it is 100,000 or less, It is more preferable that it is 70000 or less, It is further more preferable that it is 50000 or less, It is especially preferable that it is 20000 or less. There exists a tendency which can ensure film | membrane strength, such as chemical resistance, by setting it as the said lower limit or more, and there exists a tendency which can ensure the outstanding patterning characteristic by setting it as the said upper limit or less.

  In addition, let the weight average molecular weight in this invention be the value of polystyrene conversion measured using "Column GPC-804" by Shimadzu Corporation with "Gel permeation chromatograph system LS Solution" by Shimadzu Corporation.

  The content ratio of the (A) vinyl polymer in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content of the photosensitive resin composition. Is more preferably 40% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and 60% by mass. It is particularly preferred that When the amount is not less than the above lower limit value, the patterning property by photolithography tends to be easily secured, while when the amount is not more than the above upper limit value, sufficient curability tends to be easily secured.

[(B) Photocationic polymerization initiator]
The (B) cationic photopolymerization initiator contained in the photosensitive resin composition of the present invention is one that generates an acid by irradiation with visible light, ultraviolet light or the like to initiate an epoxy group polymerization reaction. Examples of the photocationic polymerization initiator include onium salts such as aromatic iodonium salts and aromatic sulfonium salts, halogen-containing compounds such as s-triazine derivatives, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Although not particularly limited, aromatic iodonium salts and aromatic sulfonium salts are preferred from the viewpoint of curability.

An aromatic iodonium salt is a compound having a diaryl iodonium cation, and an aromatic sulfonium salt is a compound having a triarylsulfonium cation. These cations are paired with anions (anions) to form a photocationic polymerization initiator.
Examples of the diaryl iodonium cation include a diphenyl iodonium cation having an alkyl group, an ether group, or the like as a substituent. Specifically, a (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium cation, (4-methylphenyl) (4-isopropylphenyl) iodonium cation, (4-methylphenyl) (4-isobutyl) iodonium cation, bis (4-tert-butyl) iodonium cation, bis (4-dodecylphenyl) iodonium cation, (2,4,6-trimethylphenyl) [4- (1-methylacetic acid ethyl ether) phenyl] iodonium cation and the like.
Examples of the triarylsulfonium cation include a triphenylsulfonium cation having an alkyl group, a thioether group, an ether group, or the like as a substituent. For example, a diphenyl [4- (phenylthio) phenyl] sulfonium cation, a triphenylsulfonium cation, an alkyltrication And phenylsulfonium cation.

Examples of anions constituting the photocationic polymerization initiator include hexafluorophosphate anion PF ⁶⁻ , hexafluoroantimonate anion SbF ⁶⁻ , pentafluorohydroxyantimonate anion SbF ₅ (OH) ⁻ , hexafluoroarsenate anion. Examples include AsF ⁶⁻ , tetrafluoroborate anion BF ⁴⁻ , tetrakis (pentafluorophenyl) borate anion B (C ₆ F ₅ ) ⁴⁻ , and preferably hexafluorophosphate anion PF ⁶⁻ . These anions become sources of acid, and the higher the acidity of the acid generated, the higher the efficiency of the polymerization reaction. On the other hand, problems such as deterioration of electrical reliability and corrosion of the electrodes are likely to occur. You can use them according to your purpose.

Specific examples of the aromatic sulfonium salt include CPI-100P, CPI-101A, CPI-200K, CPI-210S, Adeka optomer SP-150, SP-170, SP-171, etc., manufactured by San Apro. Can be mentioned.
In addition, as aromatic iodonium salts, PHOTOINITITOR 2074 of Solvay Japan, IRGACURE 250 (IRGACURE is a registered trademark) of BASF Japan, CI-5102 of Nippon Soda Co., WPI-113, WPI-116 of Wako Pure Chemical Industries, etc. A specific example is given.

  In the aromatic sulfonium salt and the aromatic iodonium salt, the aromatic sulfonium salt has higher sensitivity and can be photocured more efficiently, but the electrical reliability tends to be low, so the blending amount is kept small. It is desirable. In that respect, aromatic iodonium salts are used for applications requiring electrical reliability, such as column spacers formed inside liquid crystal cells, protective layers for in-cell type polarizing films, organic EL banks and gate insulating films adjacent to semiconductors, etc. It is preferable to do. The photosensitive resin composition of the present invention uses an aromatic iodonium salt having low sensitivity by using (C) an ethylenically unsaturated group-containing compound (E) and a specific naphthalene compound or anthracene compound, which will be described later. However, sufficient photocurability can be ensured.

  Examples of the s-triazine derivative include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloro Methyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and the like.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.

  Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy). ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

  The content ratio of the (B) photocationic polymerization initiator in the photosensitive resin composition of the present invention is 0.05% by mass when an aromatic sulfonium salt is used with respect to the total solid content of the photosensitive resin composition. It is preferable that the amount is 0.1% by mass or more, more preferably 3% by mass or less, and more preferably 1% by mass or less. On the other hand, when using an aromatic iodonium salt, 0.5 mass% or more is preferable, 1 mass% or more is more preferable, 10 mass% or less is preferable, 7 mass% or less is more preferable, and 5 mass% or less is further more preferable. . By setting it to the above lower limit or more, it tends to ensure sufficient photocurability, and by setting it to the above upper limit or less, there is a tendency that deterioration of film performance such as deterioration of electrical reliability and coloring can be suppressed. is there.

[(C) ethylenically unsaturated group-containing compound]
The photosensitive resin composition of the present invention contains (C) an ethylenically unsaturated group-containing compound. (C) The ethylenically unsaturated group-containing compound is a compound having at least one ethylenically unsaturated group in the molecule. The photosensitive resin composition of the present invention includes (C) an ethylenically unsaturated group-containing compound, so that the patterning property of the photosensitive resin composition is improved and the effect of improving chemical resistance tends to be obtained. is there.

As the number of ethylenically unsaturated groups increases in the molecule, the network at the time of crosslinking (curing) becomes denser, and it tends to ensure chemical resistance and electrical reliability. Moreover, even if the crosslinking ratio in all ethylenically unsaturated groups is reduced due to low-temperature baking, it is advantageous from the viewpoint of securing a suitable network.
From this, it is preferable that the (C) ethylenically unsaturated group-containing compound has a large number of ethylenically unsaturated groups, specifically two or more, preferably three or more. More preferably, it is more preferably 5 or more. Moreover, although there is no upper limit in the number of ethylenically unsaturated bonds, it is 12 or less normally, Preferably it is 6 or less. In addition, you may use what has many ethylenically unsaturated bonds like a dendrimer.

(C) The ethylenically unsaturated group contained in the ethylenically unsaturated group-containing compound is preferably an allyl group and / or a (meth) acryloyl group from the viewpoint of reactivity.
(C) The ethylenically unsaturated group-containing compound may be used alone or in combination of two or more in any ratio. In the case of using a plurality of types of ethylenically unsaturated group-containing compounds, the number of ethylenically unsaturated groups is the molar average of the number of ethylenically unsaturated groups possessed by the plurality of types of ethylenically unsaturated group-containing compounds. It is good to make a value into the above-mentioned preferable range.

  Hereinafter, a particularly preferable compound among the (C) ethylenically unsaturated group-containing compounds will be described. Specifically, for example, (C1) esters of unsaturated carboxylic acid and polyhydroxy compound, (C2) urethane (meth) acrylates of hydroxy (meth) acrylate compound and polyisocyanate compound, and (C3) ( Examples include meth) acrylic acid or epoxy (meth) acrylates of a hydroxy (meth) acrylate compound and a polyepoxy compound.

(C1) Esters of unsaturated carboxylic acid and polyhydroxy compound include, for example, a reaction product of unsaturated carboxylic acid and sugar alcohol, a reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol, Examples include a reaction product of a saturated carboxylic acid and an alcohol amine.
Here, specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, and itaconic acid.

  Specific examples of the sugar alcohol include ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and trimethylol. Examples thereof include polyhydric alcohols such as propane, glycerol, pentaerythritol and dipentaerythritol.

Specific examples of the alkylene oxide adduct of sugar alcohol include compounds obtained by adding ethylene oxide or propylene oxide to the above-mentioned sugar alcohol.
Specific examples of the alcohol amine include polyhydric alcohol amines such as diethanolamine and triethanolamine.

  Specific examples of esters of unsaturated carboxylic acids and polyhydroxy compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, penta Erythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Rupenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and their crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like. The esters of unsaturated carboxylic acid and polyhydroxy compound include derivatives of these compounds. Among the derivatives, a derivative having an acid group is preferable from the viewpoint of patterning properties. For example, a derivative obtained by replacing part of the polyhydroxy compound in the ester with a compound having an acid group, specifically a carboxyl group-containing compound. The one replaced with is preferable.

  Moreover, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts And the like. Specific examples include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], and the like.

In addition, a reaction product of the unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, A tri (meth) acrylate etc. are also mentioned.
Also, a reaction product of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyhydroxy compound, for example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, or (meth) acrylic acid, maleic acid and diethylene glycol. Examples include condensates, condensates of (meth) acrylic acid, terephthalic acid, and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  (C2) As urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, for example, a hydroxy (meth) acrylate compound, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate or Examples thereof include a reaction product with a polyisocyanate compound such as a heterocyclic polyisocyanate.

  Specifically, examples of the hydroxy (meth) acrylate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylolethane tri (meth) acrylate, and the like. Polyisocyanate compounds include aliphatic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyloctane; cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicyclo Examples include alicyclic polyisocyanates such as heptane triisocyanate; aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanatephenyl) thiophosphate, and heterocyclic polyisocyanates such as isocyanurate.

As a commercial item of urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, for example, “U-4HA”, “UA-306A”, “UA-MC340H” manufactured by Shin-Nakamura Chemical Co., Ltd., “ UA-MC340H "and" U6LPA ".
As urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, four or more urethane bonds [—NH—CO—O— are used to ensure sufficient chemical resistance of the cured product. And a compound having 4 or more (meth) acryloyloxy groups. Such a compound is, for example, a compound having 4 or more hydroxyl groups and a diisocyanate compound, a compound having 2 or more hydroxyl groups, and a compound having 3 or more isocyanate groups. It can be obtained by a method of reacting a compound having an isocyanate group with one or more hydroxyl groups and a compound having two or more (meth) acryloyloxy groups.

  Specific examples include the following compounds. That is, compounds obtained by reacting a compound having four or more hydroxyl groups with a diisocyanate compound include compounds having four or more hydroxyl groups such as pentaerythritol and polyglycerol, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. And compounds obtained by reacting with diisocyanate compounds such as isophorone diisocyanate and tolylene diisocyanate.

  As a compound obtained by reacting a compound having two or more hydroxyl groups with a compound having three or more isocyanate groups, a compound having two or more hydroxyl groups such as ethylene glycol and “Duranate” manufactured by Asahi Kasei Chemicals Corporation (Registered trademark) 24A-100 "," Duranate (registered trademark) 22A-75PX "," Duranate (registered trademark) 21S-75E "," Duranate (registered trademark) 18H-70B "and other biuret types Three or more adduct types such as “DURANATE (registered trademark) P-301-75E”, “DURANATE (registered trademark) E-402-90T”, and “DURANATE (registered trademark) E-405-80T” Examples thereof include compounds obtained by reacting with a compound having an isocyanate group.

  As a compound obtained by reacting a compound having four or more isocyanate groups, one or more hydroxyl groups and a compound having two or more (meth) acryloyloxy groups, isocyanate ethyl (meth) acrylate or the like is polymerized. Alternatively, a compound having four or more, preferably six or more isocyanate groups obtained by copolymerization, “Duranate (registered trademark) ME20-100” manufactured by Asahi Kasei Chemicals Corporation, and pentaerythritol di (meth) 1 or more hydroxyl groups and 2 or more, preferably 3 or more (meth) acryloyl such as acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. A compound having an oxy group and And compounds obtained by reacting the like.

  Examples of epoxy (meth) acrylates of (C3) (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound include (meth) acrylic acid or the above hydroxy (meth) acrylate compound and aliphatic Examples thereof include compounds obtained by reaction with polyepoxy compounds such as polyepoxy compounds, aromatic polyepoxy compounds, and heterocyclic polyepoxy compounds.

  Specifically, for example, (meth) acrylic acid or the above hydroxy (meth) acrylate compound, (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether (Poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, ( Poly) aliphatic polyepoxy compounds such as sorbitol polyglycidyl ether; phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds , (O-, m-, p-) cresol novolak polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds and other aromatic polyepoxy compounds; sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris ( And compounds obtained by reaction with a polyepoxy compound such as a heterocyclic polyepoxy compound such as 2-hydroxyethyl) isocyanurate.

Examples of the ethylenically unsaturated group-containing compound other than (C1) to (C3) include (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, and vinyl groups such as divinyl phthalate. And compounds having a thioether bond obtained by sulfidizing an ether bond of an ethylenically unsaturated compound having an ether bond with phosphorus pentasulfide to form a thioether bond.
In addition to this, a special ethylenically unsaturated group-containing compound such as a macromonomer or a dendrimer acrylate may be used according to required characteristics. For example, examples of dendrimers include STAR-501 and SIRIUS-501 from Osaka Organic Chemical Company. Examples of the macromonomer include AA-6, AS-6, AB-6, and AN-6S manufactured by Toa Gosei Co., Ltd.

  These ethylenically unsaturated group-containing compounds may be used alone or in combination of two or more, but (C1) unsaturated in terms of ensuring high electrical reliability and chemical resistance. It is preferable to use esters of a carboxylic acid and a polyhydroxy compound, and compounds having 5 or more ethylenically unsaturated groups such as dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

  The photosensitive resin composition of the present invention is preferably used after being developed with a developer after exposure. However, when an alkali developer is used, for the purpose of optimizing developability, a carboxyl group, a hydroxyl group, polyethylene glycol, Alternatively, an ethylenically unsaturated group-containing compound into which a polypropylene glycol group has been introduced may be used.

  The content ratio of the (C) ethylenically unsaturated group-containing compound in the photosensitive resin composition of the present invention is preferably 3% by mass or more based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably 10% by mass or more, further preferably 20% by mass or more, particularly preferably 35% by mass or more, preferably 60% by mass or less, and 50% by mass or less. Is more preferable. By making it the above lower limit or more, the effect of using the ethylenically unsaturated group-containing compound tends to be sufficiently expressed, and by making it the above upper limit or less, it tends to ensure sufficient low-temperature curability. There is.

[(D) Thermal radical polymerization initiator]
The photosensitive resin composition of the present invention contains (D) a thermal radical polymerization initiator. (D) The thermal radical polymerization initiator is a compound that can be decomposed by thermal energy to generate radicals, and conventionally known organic peroxides, azo compounds, and the like can be used.
Among these, the 10-hour half-life temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and particularly preferably 90 ° C. or higher. Moreover, it is preferable that it is 140 degrees C or less, It is more preferable that it is 130 degrees C or less, It is especially preferable that it is 120 degrees C or less. When it is at least the lower limit, storage stability tends to be ensured, and when it is at most the upper limit, sufficient low temperature curability tends to be ensured.
Further, as (D), one having a 10-hour half-life temperature outside the above range may be used.

  From the viewpoint of 10-hour half-life temperature and safety, the (D) thermal radical polymerization initiator preferably contains an azo compound, and among them, an azo compound represented by the following general formula (1) is preferable.

In the general formula (1), R ¹ and R ² each independently represents an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ and R ¹ bonded to the same carbon atom R ² may be bonded to form a ring. R ³ represents a C 1-10 alkyl group which may have a substituent. X represents O or NH.

The carbon number of the alkyl group in R ¹ and R ² is usually 1 to 6, but is preferably 3 or less, more preferably 2 or less, from the viewpoint of reaction efficiency.
As the substituent that the alkyl group may have, any substituent may be used as long as it is inert to the reaction. Examples thereof include a phenyl group, a tolyl group, and a xylyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
Specific examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group. From the viewpoint of reaction efficiency, a methyl group and an ethyl group are preferable. More preferably a methyl group.

R ¹ and R ² bonded to the same carbon atom may form a ring. For example, R ¹ and R ² may be bonded to form a cycloalkyl group.
Examples of the ring formed include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. Among them, a cyclopentyl group and a cyclohexyl group are more preferable from the viewpoint of reaction efficiency and production as an initiator. Is a cyclohexyl group.

Among R ¹ and R ² , from the viewpoint of the ease of movement of the generated radicals, each independently is preferably an alkyl group which may have a substituent, more preferably an alkyl group, and a methyl group. More preferably it is.

The carbon number of the alkyl group in R ³ is usually 1 to 10, preferably 2 or more, more preferably 3 or more, preferably 8 or less, more preferably 7 or less. By setting it to the lower limit value or more, there is a tendency that affinity with other components of the solvent and the photosensitive composition tends to be improved, and by setting the upper limit value or less, radicals easily move and reaction efficiency is improved. Tend.
Examples of the substituent that the alkyl group may have include a hydroxyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
Specific examples of the alkyl group which may have a substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, s-butyl, and tert-butyl groups. , Isopentyl group, neopentyl group, Tert-pentyl group, isohexyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, bis (hydroxymethyl) -2-hydroxyethyl group, vinyl group, 2-propenyl group, isopropenyl group , 2-butenyl group, 3-butenyl group, isobutenyl group, cyclopentyl group, cyclohexyl group, etc., preferably methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, isopropyl group, isobutyl group, 2-propiphenyl group, more preferably propyl , Butyl group, hexyl group, a cyclohexyl group, an isopropyl group, an isobutyl group.

  X is O or NH, and NH is more preferable from the viewpoint that the 10-hour half-life temperature can be easily designed from 70 ° C to 140 ° C.

  Specific examples of the compound represented by the general formula (1) include 2,2′-azobis (N-butyl-2-methylpropionamide) (110 ° C.), 2,2′-azobis (N-cyclohexyl-2). -Methylpropionamide) (111 ° C.), 2,2′-azobis [N- (2-methylpropyl) -2-methylpropionamide] (112 ° C.), 2,2′-azobis [N- (2-methyl) Ethyl) -2-methylpropionamide] (111 ° C.), 2,2′-azobis (N-hexyl-2-methylpropionamide) (112 ° C.), 2,2′-azobis (N-propyl-2-methyl) Propionamide) (111 ° C.), 2,2′-azobis (N-ethyl-2-methylpropionamide) (110 ° C.), 2,2′-azobis [2-methyl-N- (2-hydroxy ester) L) propionamide] (86 ° C.), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide] (86 ° C.), 2,2′-azobis {2-methyl-N- [ 1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} (80 ° C.), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide] (96 ° C.), dimethyl -1,1′-azobis (1-cyclohexanecarboxylate) (73 ° C.) and the like. In addition, () represents a 10-hour half-life temperature.

  Of the above examples, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N—) are particularly preferable in terms of half-life temperature, solubility, safety and the like. Hexyl-2-methylpropionamide), 2,2′-azobis (N-propyl-2-methylpropionamide).

(D) A thermal radical polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
The content ratio of the thermal radical polymerization initiator (D) in the photosensitive resin composition of the present invention is preferably 0.5% by mass or more based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. It is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less. When the amount is not less than the above lower limit value, sufficient chemical resistance tends to be obtained. On the other hand, when the amount is not more than the above upper limit value, there is a tendency that deterioration of developability can be suppressed.
In addition, the content ratio of the thermal radical polymerization initiator in which the 10-hour half-life temperature satisfies the above range in (D) the thermal radical polymerization initiator is usually 100% by mass or less, and is sufficiently cured at a low temperature. Further, from the viewpoint of developing the portion to be removed during development without leaving a residual, it is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and most preferably 100% by mass. %.

[(E) Naphthalene compound or anthracene compound having two or more substituents selected from the group consisting of alkyl ether groups and acyloxyl groups]
The photosensitive resin composition of the present invention includes (B) a naphthalene compound having two or more substituents selected from the group consisting of an alkyl ether group and an acyloxyl group for the purpose of increasing the sensitivity of the photocationic polymerization initiator (B). Alternatively, an anthracene compound may be contained. By using the component (E), sufficient sensitivity is likely to be secured even when a photocationic polymerization initiator that is not high in sensitivity but advantageous in electrical reliability, for example, an aromatic iodonium hexafluorophosphate salt is used.

The number of carbon atoms of the alkyl ether group is not particularly limited, but is preferably 1 or more from the viewpoint of solubility, and is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less from the viewpoint of sensitivity. Specific examples of the alkyl ether group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, and an octoxy group. From the viewpoint of a balance between solubility and sensitivity, an ethoxy group, A propoxy group or a butoxy group is more preferable.
The number of carbon atoms of the acyloxyl group is not particularly limited, but is preferably 5 or more, more preferably 7 or more from the viewpoint of solubility, and is preferably 12 or less, more preferably 10 or less, from the viewpoint of sensitivity. Specific examples of the acyloxyl group include pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, ethylpentanoyloxy group, decanoyloxy group, dodecanoyloxy group, etc. From the viewpoint of the balance between properties and sensitivity, an octanoyloxy group and an ethylpentanoyloxy group are preferable, and an octanoyloxy group is more preferable.

The naphthalene ring or anthracene ring in the naphthalene compound or anthracene compound may be substituted with any substituent other than two or more substituents selected from the group consisting of an alkyl ether group and an acyloxyl group. Examples of the optional substituent include an alkyl group, a halogen atom, and an amino group. From the viewpoint of ease of synthesis, it is preferable not to have any substituent.
Examples of the combination of an alkyl ether group and / or an acyloxyl group possessed by a naphthalene compound or an anthracene compound include, for example, a combination of one alkyl ether group and one acyloxyl group, and two alkyl ether groups which may be the same or different. A combination of two acyloxyl groups which may be the same or different, and from the viewpoint of transparency and sensitivity, a combination of two identical alkyl ether groups or a combination of two identical acyloxyl groups It is preferable that

  (E) As a naphthalene compound or anthracene compound having two or more substituents selected from the group consisting of an alkyl ether group and an acyloxyl group, for example, naphthalene-1,4-diether, anthracene-9,10-diether, 9, Examples thereof include 10-bisacyloxylanthracene.

Specific examples of naphthalene-1,4-diether include 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-di (n-propoxy) naphthalene, 1,4-di (i-propoxy). ) Naphthalene, 1,4-di (n-butoxy) naphthalene, 1,4-di (i-butoxy) naphthalene, 1,4-di (n-pentyloxy) naphthalene, 1,4-di (n-hexyloxy) ) Naphthalene, 1,4-bis (2-ethylhexyloxy) naphthalene, 1,4-di (n-dodecyloxy) naphthalene and the like.
Specific examples of anthracene-9,10-diether include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di (n-propoxy) anthracene, and 9,10-di (i-propoxy). Anthracene, 9,10-di (n-butoxy) anthracene and the like can be mentioned.

Specific examples of 9,10-bisacyloxyanthracene include 9,10-bis (n-pentanoyloxy) anthracene, 9,10-bis (n-hexanoyloxy) anthracene, and 9,10-bis (n -Heptanoyloxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2-ethylhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) anthracene, 9, Examples thereof include 10-bis (n-decanoyloxy) anthracene and 9,10-bis (n-dodecanoyloxy) anthracene.
Among these (E) naphthalene compounds or anthracene compounds having two or more substituents selected from the group consisting of alkyl ether groups and acyloxyl groups, 1,4-dimethoxynaphthalene and 1,4-diethoxy are preferred from the viewpoint of sensitivity. Naphthalene, 9,10-di (n-butoxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene and the like are preferable.

  In the photosensitive resin composition of the present invention, (E) a naphthalene compound or anthracene compound having two or more substituents selected from the group consisting of an alkyl ether group and an acyloxyl group may be used alone. Two or more kinds may be used in combination. The content ratio of the total amount of (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the photosensitive resin composition, and 1% by mass. % Or more, more preferably 5% by mass or less, and further preferably 4% by mass or less. When it is at least the lower limit, sufficient photocurability tends to be secured, and when it is at most the upper limit, adverse effects such as coloring tend to be suppressed.

[(F) Color material]
When the photosensitive resin composition of the present invention is used for a purpose such as a color filter or a resin black matrix for light leakage and antireflection purposes, it is preferable to use (F) a coloring material. As the coloring material, known materials such as dyes, organic pigments, and inorganic pigments can be appropriately used depending on the use. However, since the photosensitive resin composition of the present invention can be cured at a low temperature, it is easily decomposed or deteriorated at a high temperature condition. A dye can be suitably used.

  Examples of the dye include xanthene dyes, triarylmethane dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, cyanine dyes, methine dyes, and phthalocyanine dyes. In particular, when forming a blue pixel, xanthene dyes, triarylmethane dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, cyanine dyes, phthalocyanine dyes, and the like can be given. Since dyes can achieve high brightness, they are preferably used for color filter applications such as liquid crystal displays and organic EL displays.

  Since organic pigments tend to have higher heat resistance than dyes, they are usually suitable for use in color filters, but they tend to have lower luminance than dyes. However, if the composition containing the pigment can be cured at a low temperature to form a color filter, the reduction in the brightness of the pigment due to heat can be suppressed. There is a tendency that a color filter having higher brightness than that of a normal high-temperature cured product can be obtained. In addition, since the photosensitive resin composition of the present invention is excellent in electrical reliability, it is a color filter on array that requires high electrical reliability, black column spacers and black ribs in liquid crystal cells, and black for organic EL. It can also be suitably used for applications such as banks.

  As the organic pigment, pigments of various colors such as red, orange, yellow, blue, green, purple, brown, and black can be used. Examples of the chemical structure include phthalocyanine, quinacridone, and benzimidazolone. And organic pigments such as those based on dioxazine, indanthrene, perylene, azo, quinophthalone, anthraquinone, aniline and cyanine. For example, known organic pigments listed in Color Index can be used. These organic pigments are usually dispersed in a liquid together with a solvent, a dispersant, and other components as required, and used as a pigment dispersion mixed with the photosensitive resin composition.

  Examples of inorganic pigments include carbon black, titanium black, ultramarine blue, prussian blue, yellow lead, zinc yellow, red lead, iron oxide red, zinc white, lead white, lithopone, and titanium dioxide. Among these, carbon black is particularly excellent in terms of light shielding rate and image formation, and can be suitably used for resin black matrix applications. However, since carbon black is conductive, if it causes a problem, it may be insulated and used, for example, by coating with resin. These inorganic pigments are also preferably used as a pigment dispersion in the same manner as organic pigments and then mixed with the photosensitive resin composition.

In the present invention, as the color material (F), for example, dyes and organic pigments, organic pigments of a plurality of colors, organic pigments and inorganic pigments, etc., which are appropriately combined may be used.
The content ratio of the color material (F) that may be contained in the photosensitive resin composition of the present invention is not particularly limited, but in the case of a dye, preferably 1 mass from the viewpoint of securing sufficient luminance and light shielding properties. % Or more, more preferably 5% by mass or more, more preferably 8% by mass or more, and from the viewpoint that it is difficult to reduce photocurability and can maintain sufficient film strength, preferably 40% by mass or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less. In the case of a pigment, it is preferably 3% by mass or more, more preferably 6% by mass or more, and still more preferably 10% by mass or more from the viewpoint of securing sufficient luminance and light-shielding property. Further, from the viewpoint of ensuring the developer solubility, it is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.

[(G) Inorganic nanoparticles]
Examples of inorganic nanoparticles that may be used in the photosensitive resin composition of the present invention include fillers and metal oxide nanoparticles. Examples of the filler include kaolinite and calcium carbonate. Since the filler has an effect of improving the physical strength of the cured member, it is preferably used when it is desired to impart hard coat properties. Examples of the metal oxide particles include metal oxide nanoparticles such as aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium. Among these, oxide particles of zirconium, titanium, or zinc are included. It is preferably used for applications requiring high refractive index and high dielectric constant. Examples of applications requiring a high dielectric constant include a gate insulating film. As with the pigment, the inorganic nanoparticles of the present invention are preferably used as a dispersion and then mixed with the photosensitive resin composition. Further, in the case where leakage due to conductivity becomes a problem, it can be used by covering with a resin and insulating the surface.
The content ratio of (G) inorganic nanoparticles that may be contained in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.5% by mass or more from the viewpoint that the effect of addition can be sufficiently expressed. , More preferably 1% by mass or more, further preferably 3% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, from the viewpoint that sufficient solubility during development can be secured. More preferably, it is 60 mass% or less.

[(H) Liquid repellent]
Examples of the liquid repellent that may be used in the photosensitive resin composition of the present invention include fluorine-containing compounds and silicon-containing compounds. The liquid repellent can be used also for the purpose of antifouling, but is particularly preferably used when the photosensitive resin composition of the present invention is used for, for example, an ink jet bank. A silicon-containing compound is preferable when the ink ejected by inkjet is an aqueous solution, and a fluorine-containing compound is preferable when the ink is an organic solvent solution.

  The fluorine-containing compound is not particularly limited, and may be a low molecular compound or a high molecular compound. For example, the fluorine-containing compound has a crosslinking group such as an ethylenically unsaturated double bond or an epoxy group, and has a fluoroalkyl group. And a compound containing a fluoropolyether group. Specific examples include RS series from DIC, Optool DAC and Optoace series from Daikin Industries.

  The silicon-containing compound is not particularly limited, and may be a low molecular compound or a high molecular compound. Examples thereof include silicon-modified polyacryl, silicon-based block copolymer, and graft polymer having a silicon resin in the side chain. Specifically, for example, BYK-SILCLEAN 3700 manufactured by Big Chemie, Modiper FS series manufactured by NOF Corporation, Soken Chemical Co., Ltd. Chemistry LSI-60, and the like can be mentioned.

One of the above liquid repellents may be used alone, or two or more may be used in combination.
The concentration of the liquid repellent is not particularly limited. For example, in the case of forming a bank or the like, when the fluorine atom content or the silicon content in the liquid repellent is 10% by mass or more, the entire photosensitive resin composition is used. It is 0.001 mass% or more normally with respect to solid content, Preferably it is 0.05 mass% or more, and is 10 mass% or less normally, Preferably it is 6 mass% or less.
When the fluorine atom content or silicon content is less than 10% by mass, it is usually 0.1% by mass or more, preferably 1% by mass or more, and usually based on the total solid content of the photosensitive resin composition. It is 70 mass% or less, Preferably it is 50 mass% or less.
By setting it to the lower limit value or more, the ink repellency is likely to be sufficient, and there is a tendency that the ink can be prevented from flowing out of the area partitioned by the bank. In addition, by setting it to the upper limit value or less, development at the time of bank formation is facilitated, and it is possible to avoid a residual liquid repellant or ooze out on the inner side partitioned by the bank. There is a tendency to supply uniformly. The liquid repellent used in the bank is preferably a fluorine-containing compound when the ink ejected inside the bank is an organic solvent, and a silicon-containing compound is preferably used when the ink is an aqueous solution.

[Photo radical polymerization initiator]
In the photosensitive resin composition of the present invention, a radical photopolymerization initiator is preferably used for the purpose of imparting photopolymerizability to the (C) ethylenically unsaturated group-containing compound. Examples of the radical photopolymerization initiator include metallocene compounds including titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; and hexaarynes described in JP-A-2000-56118. Rubiimidazole derivatives; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, and N-aryl-α-amino acids described in JP-A-10-39503 Salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750 A, etc. Can be mentioned. Among these, it is preferable that the radical polymerization initiator includes oxime ester derivatives and / or α-aminoalkylphenone derivatives.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

  Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is.

Furthermore, for example, oxime and ketoxime ester compounds described in JP-A No. 2000-80068 and JP-A No. 2006-36750 can be mentioned.
Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p- Methoxyph Yl) acridine derivatives acridine like; 9,10-dimethyl-benz phenazine phenazine derivatives such as; anthrone derivatives such as benzanthrone etc. may be mentioned.

  Among these radical photopolymerization initiators, oxime ester derivatives are preferred, ketoxime ester derivatives are more preferred, and ketoximes having a benzoyl group, particularly when a colorant such as a dye or pigment is added from the viewpoint of sensitivity. Derivatives are particularly preferred. In the case of forming a thin film of 1 μm or less, α-aminoalkylphenone derivatives are preferable because they are relatively excellent in surface curability.

A radical photopolymerization initiator may be used individually by 1 type, and may use 2 or more types together. The combination when two or more kinds of radical photopolymerization initiators are used in combination is not particularly limited.
The content ratio of the photo radical polymerization initiator in the photosensitive resin composition of the present invention is preferably 0.5% by mass or more based on the total solid content of the photosensitive resin composition of the present invention. % Or more, more preferably 2% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 10% by mass or less. It is preferably 8% by mass or less. There exists a tendency which can fully express photocurability by setting it as the said lower limit or more, and there exists a tendency which can suppress the deterioration of developability by making it below the said upper limit. In addition, when using the photosensitive resin composition of the present invention for a low light-transmitting application such as a resin black matrix, it is easier to ensure photocurability by using a larger amount of the photoradical polymerization initiator. is there.

[Leveling agent]
Although the photosensitive resin composition of this invention can be apply | coated on a board | substrate by wet application | coating or printing, it is preferable to use a leveling agent in order to avoid defects, such as a repellency, and film thickness nonuniformity. Examples of the leveling agent include various surfactants, but it is preferable to use silicon and / or fluorine-based surfactants from the viewpoint of ensuring electrical reliability.

  Fluorosurfactants include, for example, Big Chemie's BM series, DIC's MegaFuck series (MegaFuck is a registered trademark), Sumitomo 3M's Florad series, AGC's Surflon series (Surflon is a registered trademark), Neos Corporation's Aftergent series (Futterent is a registered trademark) and the like can be mentioned.

  Examples of silicon surfactants include BYK series from BYK Chemie, series such as SH, SZ, and DC from Toray Dow Corning, TSF series from Toshiba Silicone, and the like.

  The content of the leveling agent in the photosensitive resin composition of the present invention is preferably 0.01% by mass or more and preferably 0.02% by mass or more with respect to the total solid content of the photosensitive resin composition. Is more preferably 0.05% by mass or more, more preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. . By setting it to the above lower limit value or more, a sufficient leveling effect tends to be obtained, and by setting the upper limit value or less, foaming is suppressed and the appearance of coating defects such as repellency tends to be suppressed. is there.

[Organic solvent]
The photosensitive resin composition of the present invention is preferably diluted with an organic solvent.
In the case of using an organic solvent, it is preferably used so that the total solid content in the photosensitive resin composition of the present invention is 3% by mass or more, and more preferably 5% by mass or more. Preferably, it is more preferably used so as to be 10% by mass or more, particularly preferably used so as to be 15% by mass or more, and preferably used so as to be 40% by mass or less, and 35% by mass. It is more preferable to use the following. There exists a tendency which can make control of a film thickness easy by setting it as the said lower limit or more, and the tendency which can make it easy to maintain the pot life of the photosensitive resin composition by setting it as the said upper limit or less. There is. In addition, total solid content shows the sum total of components other than the organic solvent.

  The organic solvent used in the present invention is, for example, glycol monoalkyl ethers; glycol dialkyl ethers; glycol diacetates; alkyl acetates; ethers; ketones; monohydric or polyhydric alcohols; Alicyclic hydrocarbons; aromatic hydrocarbons; chain or cyclic esters; alkoxycarboxylic acids; halogenated hydrocarbons; ether ketones; nitriles, etc., specifically, isopropyl alcohol, ethylene glycol Dimethyl ether, propylene glycol dimethyl ether, 1,4-dioxane, methyl isobutyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl Ether acetate, methyl lactate), dimethylformamide, ethyl lactate, cyclohexanone, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diisobutyl ketone, diacetone alcohol, 3-ethoxypropionate, dipropylene glycol dimethyl ether, butyl cellosolve, 3-methoxy-3- Examples thereof include methyl-1-butanol, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether and the like. Suitable organic solvents include propylene glycol monomethyl ether acetate and ethylene glycol monomethyl ether acetate. These organic solvents may be used alone or in combination of two or more, and should be determined in consideration of the balance of applicability, surface tension, boiling point and the like.

[Other ingredients]
If the photosensitive resin composition of this invention does not prevent the outstanding effect of this invention significantly, it can contain another component as needed. Other components include, for example, epoxy compounds other than (A), oxetane compounds, resins, sensitizers other than (E), thermal cationic polymerization initiators, melamine crosslinking agents, adhesion improvers such as silane coupling agents, Examples thereof include development accelerators such as acids.
Epoxy compounds include, for example, Mitsubishi Chemical's JER series, Daicel's Celoxide series (Celoxide is a registered trademark), Nippon Steel & Sumikin Chemical's Epototo series (Epototo is a registered trademark), Nippon Kayaku's NC- , XD-, EPPN-, EOCN-, and the like, EPICLON (registered trademark) of DIC, and the like.
Examples of oxetane include OXT series manufactured by Toa Gosei Co., Ltd., OXE-10 and 30 manufactured by Osaka Organic Chemical Co., Ltd.
Moreover, as a resin, an acrylic resin, a urethane resin, a novolak resin, etc. are mentioned as a preferable example. In addition, radical polymerizable unsaturated groups, cationic polymerizable groups, and other crosslinking groups may be introduced into these resins. As the radical polymerizable unsaturated group-containing resin, for example, Nippon Kayaku's ZAR, ZCR, CCR and other epoxy (meth) acrylate resins, as well as resins obtained by polymerizing glycidyl (meth) acrylate as a copolymerization component Examples thereof include resins opened by (meth) acrylic acid and the like.

[Preparation of photosensitive resin composition]
Although the preparation method of the photosensitive resin composition of this invention is not specifically limited, For example, it can prepare by mixing each above-mentioned component with an organic solvent, and making it melt | dissolve or disperse | distribute by stirring or ultrasonic application. In addition, when preparing a composition, when using (C) ethylenically unsaturated group containing compound, a liquid epoxy compound, and an oxetane compound, they are good also as a substitute for an organic solvent.

  When preparing, each component may be added and mixed simultaneously, but may be added and mixed sequentially in any order. The order of sequential addition is not particularly limited. For example, first, (B) a photocationic polymerization initiator, (D) a thermal radical polymerization initiator, (E) a naphthalene compound or anthracene compound, and a photoradical polymerization initiator are mixed with an organic solvent to obtain a mixture 1, Thereafter, (A) a vinyl polymer solution and (C) an ethylenically unsaturated group-containing compound are added and mixed to obtain a mixture 2, and (F) a coloring material and (G) an inorganic nanoparticle are further added to the mixture 2. A dispersion of particles may be added and mixed.

In addition, the photosensitive resin composition of the present invention is a mixture of the above-described components together with an organic solvent, followed by filtration using a filter, whereby gel components and dust that may occur during synthesis of insoluble materials, resins, etc. It is preferable to remove trace metals and the like. As the filter, for example, an Entegris optimizer, a CUNO nanoshield, a zeta plus EC, or the like can be used. Insoluble matter, gel components, dust, trace metals, etc. cause repelling when a thin film is formed. Therefore, it is necessary to select the roughness of the filter according to the film thickness, for example, a film of 500 nm or less. When it is desired to form the film with a large thickness and it does not include pigments, inorganic nanoparticles, etc., fine ones such as 0.02 μm or less are preferable.
The chemical structure of each component contained in the photosensitive resin composition of the present invention can be confirmed by analysis by NMR, GPC, IR, or the like.

[Curing member composed of photosensitive resin composition]
The photosensitive resin composition of the present invention is used by patterning with photolithography, so that a protective film (protective layer), an insulating film (insulating layer), a flattened film (flattened layer), a column spacer, a bank, a color filter, It is possible to form a cured member such as a resin black matrix. Since the photosensitive resin composition of this invention can form the hardening member excellent in electrical reliability at low temperature, it can be used suitably also as a protective layer comprised on an anisotropic pigment | dye film | membrane.

[Method of manufacturing cured member]
Examples of the method for applying the photosensitive resin composition of the present invention include a spinner method, a wire bar method, a flow coating method, a die coating method, a blade coating method, a rod coating method, a roll coating method, a spray coating method, an inkjet method, Electrospray deposition method and the like. Among them, the die coating method is preferable because it can be applied in a small amount, has a lower risk of mist adhesion, and hardly generates foreign matter compared to a method such as a spin coating method.
In addition, printing may be performed by offset printing, gravure printing, flexographic printing, screen printing, stencil printing, ink jet printing, nozzle printing, stamping (microcontact printing), and the like.

  When the photosensitive resin composition of the present invention contains an organic solvent, it is usually dried after coating or printing. Drying can be performed by heating using a heating device such as a clean oven, a hot plate, an infrared ray, a halogen heater, or microwave irradiation. Among these, a clean oven and a hot plate are preferable because the entire film can be easily heated uniformly. What is necessary is just to select drying conditions suitably according to the kind etc. of organic solvent. It is preferable to dry at a high temperature for a long time because it is easier to obtain stable curability when sufficiently dried, but on the other hand, the time required for drying is short, the productivity is excellent, and the photosensitive resin. In order to prevent the dark reaction of the composition from proceeding, it is preferable to dry at a low temperature for a short time. Therefore, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and is usually 120 ° C. or lower, preferably 100 ° C. or lower. The drying time is preferably 15 seconds or longer, more preferably 30 seconds or longer. On the other hand, it is preferably 5 minutes or shorter, more preferably 3 minutes or shorter. Moreover, drying may be performed by a reduced pressure drying method, and a heating method and a reduced pressure drying method may be used in combination.

  The coated photosensitive resin composition layer (which is further dried if it contains an organic solvent) is exposed through an exposure mask or directly drawn with a laser to insolubilize the exposed portion, and then light exposure is blocked by the exposure mask. In order to remove the photosensitive resin composition layer that has been applied or has not been irradiated with the laser, development processing is performed.

The light source used for exposure is not particularly limited as long as it can insolubilize the photosensitive resin composition of the present invention. Specifically, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source such as an LED, and an argon ion laser, YAG Laser light sources such as lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers can be used.
Here, when using light of a specific wavelength, an optical filter may be used.
Exposure is usually 0.01 mJ / cm ² or more, preferably 0.1 mJ / cm ² or more, more preferably 1 mJ / cm ² or more, whereas, typically 1000 mJ / cm ² or less, preferably 800 mJ / cm ² or less, more preferably 500 mJ / cm ² or less.

  The photosensitive resin composition of the present invention can be used by adjusting the light curing degree by changing the light transmittance depending on the part using a halftone exposure mask and adjusting the film thickness after development depending on the part. it can. For example, the protective layer and the column spacer thereon can be obtained by a single exposure and development process. In this way, a cured member having one or more convex portions can be obtained by using a halftone exposure mask. In addition, although the height difference between a convex part and other site | parts is not specifically limited, It is preferable that it is 1 micrometer or more. Although an upper limit is not specifically limited, Usually, it is 20 micrometers or less.

The photosensitive resin composition of the present invention can be used by patterning by removing a portion that has not been irradiated with light during exposure by development processing. As the developer used for development, an organic solvent or an alkali developer is used. Alkaline developer is preferable in terms of handling and environmental problems, but for example, organic solvents are used in the case where it is produced at a low temperature in applications where residual moisture such as organic EL has an adverse effect. It is preferable.
Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and sodium metasilicate, aliphatic secondary amines such as ethylamine and n-propylamine, trimethylamine, Aliphatic tertiary amines such as methyldiethylamine, dimethylethylamine, triethylamine, aromatic tertiary amines such as pyridine, collidine, lutidine, quinoline, alkanolamines such as ethanoldimethylamine, methyldiethanolamine, triethanolamine, tetra Examples include aqueous solutions of alkaline compounds such as quaternary ammonium salts such as methylammonium hydroxide and tetraethylammonium hydroxide.
Examples of the organic solvent include those listed in the section of coating solvent.
These may be used alone or mixed and adjusted, or an alkali developer and a water-soluble organic solvent may be mixed and used.

In addition, the developer used in the present invention may contain a surfactant, an antifoaming agent, a buffering agent, a complexing agent, and the like. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; alkylbenzenesulfonic acid Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids.
There are no particular restrictions on the development method and its conditions.

Examples of the development method include immersion development, paddle development, spray development, brush development, and ultrasonic development. Of these, immersion development and spray development are preferred because they are difficult to get smudged, hardly cause damage, and are easily developed uniformly, and paddle development is preferred in that the amount of developer used can be suppressed. The development temperature is usually 10 ° C. or higher, preferably 15 ° C. or higher, and is usually 50 ° C. or lower, preferably 45 ° C. or lower.
After development, the substrate is washed with water or an organic solvent and then dried.
After development, if necessary, additional exposure may be performed to promote photopolymerization. The additional exposure may be performed by a method similar to the above exposure method. However, in the case of additional exposure, the entire surface may be exposed without using a mask.

  The photosensitive resin composition of the present invention is preferably used after being developed and baked to accelerate curing and increase the film strength.

  The baking temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, 200 ° C. or lower, more preferably 180 ° C. or lower. If the temperature is lower than this, the time required for curing tends to be longer, and the productivity tends to deteriorate or the resin is not sufficiently cured. If the temperature is higher than this, the substrate is deformed when a plastic substrate is used. And tend to cause problems such as coloring. A shorter baking time is more preferable, but 3 minutes to 2 hours is appropriate in terms of ensuring sufficient curability, and 10 minutes to 1 hour is particularly optimal.

  The substrate used as the support for the photosensitive resin composition of the present invention is not particularly limited, but is preferably a substrate having good surface properties, contact angle characteristics, and water absorption characteristics. As a base material for forming such a substrate, for example, inorganic materials such as glass; triacetate resin, acrylic resin, polyester resin, polycarbonate resin, polyethylene terephthalate resin, triacetyl cellulose resin, norbornene resin And polymer materials such as cyclic polyolefin resin, polyimide resin, and urethane resin. These may be used alone or in combination of two or more. In particular, the substrate is preferably a substrate including a polymer base material containing a polymer material.

[Production method of polarizing element]
The photosensitive resin composition of this invention can be used in order to form the protective layer comprised on an anisotropic dye film, and can manufacture a polarizing element provided with a protective layer on an anisotropic dye film. it can. In particular, it is preferably used as a protective layer formed on an anisotropic dye film formed by coating (hereinafter sometimes abbreviated as “coating-type polarizing film”).

  When patterning a polarizing element using the photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is wet-formed on an anisotropic dye film (polarizing film) formed on a substrate. After the exposure, (i) both the polarizing film and the photosensitive resin composition film are developed with a developer, or (ii) only the photosensitive resin composition film is developed first, and then this is used as a resist for the photosensitive resin. Examples include a method in which a part of the polarizing film not covered with the composition film is dissolved in a developing solution and developed. Since the photosensitive resin composition of the present invention can impart alkali developability as described in the section of (A) vinyl polymer, it is developed together with the polarizing film having alkali solubility by the method (i). This is preferable in terms of process reduction. After the pattern is formed by development, the photosensitive resin composition film is further cured by baking to form a protective layer. In this case, if necessary, the side surface of the polarizing film may be blocked by melt-flowing. . The polarizing film as the lower layer is often difficult to pattern by itself, and tends to have insufficient chemical resistance and heat resistance.

  The substrate used as the support for the polarizing film in the method for producing a polarizing element of the present invention is not particularly limited, but is preferably a substrate having good surface properties, contact angle characteristics and water absorption characteristics. . As a base material for forming such a substrate, for example, inorganic materials such as glass; triacetate resin, acrylic resin, polyester resin, polycarbonate resin, polyethylene terephthalate resin, triacetyl cellulose resin, norbornene resin And polymer materials such as cyclic polyolefin resin, polyimide resin, and urethane resin. These may be used alone or in combination of two or more. In particular, the substrate is preferably a substrate including a polymer base material containing a polymer material.

  The water absorption rate of the substrate is usually 5% or less, preferably 3% or less, more preferably 1% or less. If the water absorption is excessively large, the substrate may absorb moisture when the anisotropic polarizing material film is formed by a wet film formation method, and the substrate may be warped, which may easily cause coating defects. In addition, after the polarizing film is formed by a coating method, the substrate may swell and optical defects may occur. The “water absorption rate” is a value obtained by measuring the weight change rate when immersed in water at 23 ° C. for 4 hours using the test method of ASTM D570.

  An orientation treatment layer or the like may be provided in advance on the surface of the substrate surface on which the polarizing film is formed from the viewpoint of better orienting an anisotropic polarizing material such as a dye contained in the polarizing film in a certain direction. it can. About the formation method of an orientation processing layer, it can be based on the well-known method as described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000) pp. 226-239. Moreover, as a shape of a board | substrate, the film form (sheet-fed form) of a fixed dimension may be sufficient, and a continuous film form (strip | belt shape) may be sufficient. Moreover, as a film thickness of a board | substrate, it is 0.01 mm-3 mm normally, Preferably it is 0.02 mm-2 mm.

  The total light transmittance of the substrate is usually 80% or more, preferably 85% or more, more preferably 90% or more. The “total light transmittance” is measured using an integrating sphere color measuring device, and is a value obtained by combining diffuse transmission light and parallel light transmission light.

[Other hardened members]
Although it does not specifically limit as other hardening members which can be formed using the photosensitive resin composition of this invention, For example, a protective film, an insulating film, a planarization film | membrane, a column spacer, a bank, a color filter, a resin black matrix etc. are mentioned. It is done. The protective film is used, for example, for the purpose of protecting functional members such as a semiconductor layer and a polarizing film. If necessary, the protective film may be used by imparting hard coat properties with a filler (G) that is inorganic nanoparticles. good. The insulating layer is used, for example, for the purpose of insulating between wirings and electrodes or between the TFT substrate and wirings. When used as a gate insulating film or a capacitor, (G) a metal oxide which is an inorganic nanoparticle as required. For example, the dielectric constant may be increased. The flattening film is applied, for example, to the surface of a flexible substrate having a rough surface, and is used for smoothing or flattening the unevenness of the member. For example, the column spacer serves as a replacement rod for securing a gap between the liquid crystal cells, and may be colored with black or the like using a dye or a pigment (F) as necessary. The bank serves as a threshold when, for example, ink is separately applied by ink jet. For the purpose of preventing the ink from overflowing outside the bank, (H) a liquid repellent may be added to impart liquid repellency. . The color filter plays a role of developing colors of a liquid crystal display, an organic EL display, and the like, and expresses and uses the three primary colors of light by further using (F) a dye or pigment as a color material. The resin black matrix is used for the purpose of preventing light leakage of a liquid crystal display and reflection from a general electrode of the display, and is used by further blackening further using a dye or pigment which is a color material (F). These members may be formed by photolithography for each member, but if possible, such as being on the same surface on the substrate, adjust the exposure intensity for each part using a half-tone mask. Thus, a plurality of types of members can be formed together.

[Image display device]
The image display device of the present invention includes at least a cured member obtained by using the photosensitive resin composition of the present invention and a polarizing element. Specifically, a liquid crystal display device is mentioned. As a configuration example of a liquid crystal display device, a TFT element array substrate having an interlayer insulating film, ITO wiring, and a polarizing element, and a color filter substrate having an alignment film and a polarizing film with a protective layer are opposed to each other with a spacer interposed therebetween. Liquid crystal is injected into the gap. Furthermore, the thing comprised by having arrange | positioned the backlight outside the TFT element array substrate is mentioned. The display device of the present invention is not limited to this, and other examples include an organic EL display device.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist thereof.

[Example 1 and Comparative Example 1]
Details of each component used in Example 1 and Comparative Example 1 are as follows.
<Polymer-1>
In a flask equipped with a reflux condenser, a stirrer, and a nitrogen blowing tube, 47 parts by mass of monomethacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.), 61 parts by mass of glycidyl methacrylate, propylene glycol monomethyl After charging 400 parts by mass of ether acetate and 8.0 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), and replacing with nitrogen, the liquid temperature was raised to 80 ° C. while stirring, After reacting for 1 hour and further decomposing dimethyl-2,2′-azobis (2-methylpropionate) at 100 ° C. for 1 hour, propylene glycol monomethyl ether acetate was distilled under reduced pressure at 80 ° C. The polymer was concentrated to a partial concentration of about 50% by mass to obtain polymer-1. The weight average molecular weight (Mw) of this resin was about 11,000.

The weight average molecular weight was measured using “Column GPC-804” manufactured by Shimadzu Corporation with “Gel Permeation Chromatograph System LS Solution” manufactured by Shimadzu Corporation.
The structure of the repeating unit contained in polymer-1 is as follows.
The content ratio of the repeating unit structure derived from the epoxy group-containing vinyl compound (glycidyl methacrylate) in Polymer-1 is 67 mol%, and the content of the repeating unit structure derived from the cyclic aliphatic group-containing vinyl compound (dicyclopentanyl methacrylate). The proportion is 33 mol%.

<Irg-250 (manufactured by BASF)>

<VAm-110 (Wako Pure Chemical Industries, Ltd.)>

<Irg907 (made by BASF)>

<BYK-330 (by Big Chemie)>
Polyether-modified polymethylalkylsiloxane

<Preparation of photosensitive resin compositions 1 and 2>
Each component in Table 1 was weighed and stirred using a magnetic stirrer to completely dissolve it, and stirring was further continued for 10 minutes. Next, it filtered using the optimizer V47 0.02 micrometer FD5A XFR of Entegris, and obtained the photosensitive resin compositions 1 and 2.

<Evaluation of patterning properties>
About 0.5 cc of each photosensitive resin composition is dropped on a glass substrate (10 × 10 cm, thickness 0.7 mm), and the rotation speed of the spin coater is adjusted so that the film thickness after baking becomes 500 nm, The coating was performed by rotating for 50 seconds. Then, it heated and dried on the hotplate at 90 degreeC for 90 second, and formed the protective layer. This sample was passed through a mask having a negative pattern of 5 and 6, 7, 8, 9, 10, ²⁰ , 30, 40, and 50 μm lines and dots at an exposure amount of 200 mJ / cm ² using a 3 kW high-pressure mercury lamp. And exposed.
Next, this sample was immersed and developed for 30 seconds using propylene glycol monomethyl ether acetate as a developing solution. After development, the film was poured with propylene glycol monomethyl ether acetate and then dried with compressed air.
The state of the pattern at this time was observed with an optical microscope, and the size of the finest pattern formed is shown in Table 1. If development was not possible, development was impossible. The smaller the value, the better.

<Evaluation of chemical resistance>
The sample obtained by the patterning evaluation was baked in a clean oven at 180 ° C. for 15 minutes, and then immersed in N-methylpyrrolidone for 15 minutes. The film thickness of the 50 μm line part before and after immersion was measured using Dektak (manufactured by Bruker). The calculated results are shown in Table 1 as the film thickness residual ratio = (film thickness after immersion / film thickness before immersion) × 100.

<Evaluation of voltage holding ratio (VHR)>
A substrate A in which an ITO film is formed on one whole surface of a washed 2.5 cm square alkali-free glass substrate ("AN-100" manufactured by Asahi Glass Co., Ltd.) and a central portion of one side of the 2.5 cm square glass substrate. A substrate B on which a 1 cm square ITO film with a 2 mm wide extraction electrode connected was prepared.
On the surface of the substrate A on which the ITO film is formed, each photosensitive resin composition shown in Table 1 is applied with a spin coater so that the film thickness after baking is 1 μm. After drying at 90 ° C. for 90 seconds, the photosensitive resin composition in the contact portion was wiped off with a cotton swab soaked in acetone, exposed to 200 mJ / cm ² using a 3 kW high-pressure mercury lamp, and then 180 ° C. in an oven. By baking for 15 minutes, the board | substrate A with which the photosensitive resin composition was formed into a film on the whole surface was obtained.

Next, a UV curable sealant containing silica beads having a diameter of 5 μm is applied to the outer periphery of the surface of the substrate B on which the ITO film is formed using a dispenser, and then the photosensitive resin composition of the substrate A is used. The surface on which the product was formed was placed oppositely so that the outer edge was shifted by 3 mm, pressed, and irradiated with ultraviolet rays.
Liquid crystal (MLC-6846-000 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the periphery was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell.

  The liquid crystal cell was annealed (heated in a hot-air circulating furnace at 105 ° C. for 2.5 hours), then applied with pulse voltages of 60 Hz, 2 Hz, and 0.6 Hz at a voltage of 5 V, an application time of 16.67 msec, and a span of 500 msec. The voltage holding ratio was measured with “VHR-1” manufactured by Toyo Corporation, and the results are shown in Table 1. The larger the value, the better.

[Example 2]
Details of each component used in Example 2 are as follows.

<Polymer-2>
In a flask equipped with a reflux condenser, a stirrer, and a nitrogen blowing tube, 16 parts by mass of monomethacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.), 61 parts by mass of glycidyl methacrylate, and methacrylic acid 12 Parts by weight, 300 parts by weight of diethylene glycol methyl ethyl ether, 9 parts by weight of dimethyl 2,2′-azobis (2-methylpropionate), and after replacing with nitrogen, the liquid temperature was raised to 80 ° C. while stirring, The mixture was reacted at 0 ° C. for 6 hours to obtain a polymer-2. The weight average molecular weight (Mw) of this resin was about 8,000.

The weight average molecular weight was measured using “Column GPC-804” manufactured by Shimadzu Corporation with “Gel Permeation Chromatograph System LS Solution” manufactured by Shimadzu Corporation.
The structure of the repeating unit contained in the polymer-2 is as follows.
In Polymer-2, the content of the repeating unit structure derived from the epoxy group-containing vinyl compound (glycidyl methacrylate) is 67 mol%, and the content of the repeating unit structure derived from the cyclic aliphatic group-containing vinyl compound (dicyclopentanyl methacrylate) is included. The ratio was 11 mol%, and the content ratio of repeating units derived from methacrylic acid was 22 mol%.

<TO1382 (Toagosei Co., Ltd.)>

<UVS-1331 (manufactured by Kawasaki Kasei Co., Ltd.)>

<ET-2201 (manufactured by Kawasaki Kasei Co., Ltd.)>

<Preparation of photosensitive resin composition 3>
Each component of Table 2 was weighed out, and a photosensitive resin composition 3 was obtained in the same manner as in the photosensitive resin compositions 1 and 2.

<Evaluation of patterning properties>
The same procedure was performed except that the developer in the patterning property evaluation of Example 1 was changed to 0.4 mass% TMAH (tetrahydroammonium hydroxide) and the film thickness was adjusted to 1 μm after coating and drying. The patterning property of the photosensitive resin composition 3 was evaluated, and the results are shown in Table 2.
<Evaluation of chemical resistance>
The chemical resistance of the photosensitive resin composition 3 was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

<Evaluation of voltage holding ratio (VHR)>
The voltage holding ratio of the photosensitive resin composition 3 was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

From Table 1, it can be seen from the comparison between Example 1 and Comparative Example 1 that the photosensitive resin composition of the present invention can ensure a high level of electrical reliability even under extremely severe conditions of 0.6 Hz. This is considered to be a result of promoting a more precise curing reaction during baking by containing a thermal radical polymerization initiator. It turns out that the photosensitive resin composition of this invention is useful when manufacturing a hardening member with higher electrical reliability on low temperature conditions. Furthermore, since the minimum resolution size is 10 μm or less, it can be seen that the photosensitive resin composition of the present invention can be stably and highly accurately patterned by photolithography.
Further, from Table 1 and Table 2, it can be seen from the comparison between Example 1 and Example 2 that Example 2 has a higher level of VHR (electrical reliability), which generates an acid. Therefore, it is considered that the amount of the cationic photopolymerization initiator that can affect the electrical reliability is suppressed by adding the compound (E).

[Example 3]
<Preparation of anisotropic dye film composition 1>
An anisotropic dye film is obtained by stirring and dissolving 20 parts by mass of a lithium salt of a dye represented by the following formula (I) and 1 part by mass of a dye represented by the following formula (II) in 79 parts by mass of water. Composition 1 was prepared.

<Adjustment of insolubilized liquid 1>
Insoluble solution 1 was prepared by adding 75.6 parts by mass of 6N sulfuric acid to 24.4 parts by mass of bis (hexamethylene) triamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolving with stirring. The viscosity of insolubilized solution 1 was 50 cP.

<Adjustment of photosensitive resin composition 4>
Photosensitive resin composition 4 was obtained in the same manner except that TO-1382 of photosensitive resin composition 3 was changed to dipentaerythritol hexaacrylate.

(Process (I))
An alignment film (polyimide film having a film thickness of about 60 nm) was formed on a glass substrate (10 × 10 cm, thickness 0.7 mm), and a substrate subjected to rubbing treatment in a horizontal direction was prepared as a substrate.
A polarizing film having a film thickness of about 0.4 μm is applied on the alignment film by applying the anisotropic dye film composition 1 with a die coater (wet film thickness 2 μm, head speed 15 mm / s) and naturally drying. Formed. In addition, the environmental conditions at the time of application | coating were 23 degreeC and 50RH%.

  The substrate on which the polarizing film was formed in the insolubilized solution 1 was impregnated for 5 seconds. After removing the substrate, it was washed with demineralized water, and then the substrate was air-dried.

(Process (II))
About 0.5 cc of the photosensitive resin composition 4 is dropped onto the insolubilized polarizing film in the step (I), and the spin coater is adjusted so that the film thickness after development in the step (III) described later becomes 1 μm. The number of rotations was adjusted, and the coating was performed by rotating for 50 seconds. Thereafter, it was dried by heating on a hot plate at 90 ° C. for 90 seconds to form a protective layer.

(Process (III))
The substrate on which the protective layer was formed in the step (II) was exposed through a mask having a negative pattern at an exposure amount of 200 mJ / cm ² using a 3 kW high-pressure mercury lamp.
Next, the substrate after exposure was developed by immersing it with 0.4% by mass TMAH for 30 seconds, sufficiently rinsed with water, and then dried.

  Next, this sample was heated in an oven at 180 ° C. for 15 minutes to obtain a patterned coated polarizing film sample with a protective layer. The polarizing film under the protective layer was a uniform and good film with no cracks and no film dropping.

<Evaluation of polarization characteristics>
About the coating type polarizing film with a protective layer of Example 3, when the obtained sample was divided | segmented into half and it overlapped so that each polarizing film might become orthogonal or parallel, the mode when it observed was observed It was confirmed that the light could be uniformly blocked or transmitted.

  Thus, it turns out that it can pattern without damaging a coating type polarizing film by using the photosensitive resin composition of this invention as a protective layer.

  The photosensitive resin composition of the present invention can be patterned with photolithography, and can form a cured member with good electrical reliability at low temperatures, so when forming a cured member in the presence of a material with low high temperature resistance, This is useful for manufacturing flexible displays.

Claims (17)

  (A) containing a vinyl polymer containing a side chain α having an epoxy group, (B) a photocationic polymerization initiator, (C) an ethylenically unsaturated group-containing compound, and (D) a thermal radical polymerization initiator. A photosensitive resin composition.   (D) The photosensitive resin composition of Claim 1 in which a thermal radical polymerization initiator contains the thermal radical polymerization initiator whose 10-hour half-life temperature is 70-140 degreeC. (D) The photosensitive resin composition of Claim 1 or 2 in which a thermal radical polymerization initiator contains the azo compound shown by following General formula (1).

(In the general formula (1), each independently of R ¹ and R ² represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, R ¹ attached to the same carbon atom And R ² may combine to form a ring, R ³ represents an optionally substituted alkyl group having 1 to 10 carbon atoms, and X represents O or NH.   The photosensitive resin according to any one of claims 1 to 3, further comprising (E) a naphthalene compound or an anthracene compound having two or more substituents selected from the group consisting of an alkyl ether group and an acyloxyl group. Composition.   (A) The photosensitive resin composition of any one of Claims 1 thru | or 4 in which a vinyl polymer contains the side chain (beta) which has a cyclic aliphatic group.   (A) The photosensitive resin composition of any one of Claims 1 thru | or 5 in which a vinyl polymer contains the side chain (gamma) which has a carboxyl group or an aromatic hydroxyl group.   The photosensitive resin composition according to claim 1, further comprising (F) a color material.   The photosensitive resin composition according to any one of claims 1 to 7, further comprising (G) inorganic nanoparticles.   The photosensitive resin composition according to claim 1, further comprising (H) a liquid repellent.   The hardening member comprised with the photosensitive resin composition of any one of Claims 1 thru | or 9.   The hardening member according to claim 10 which has one or more convex parts.   The image display apparatus provided with the hardening member of Claim 10 or 11.   It is a protective layer comprised on an anisotropic pigment | dye film | membrane, Comprising: The protective layer formed using the photosensitive resin composition of any one of Claims 1 thru | or 6.   The protective layer according to claim 13, wherein the anisotropic dye film is formed by coating.   A polarizing element comprising the protective layer according to claim 13 or 14 on an anisotropic dye film.   A photosensitive resin composition according to any one of claims 1 to 6 is wet-deposited on an anisotropic dye film, and after exposure, the anisotropic dye film and the photosensitive resin composition film are developed with a developer. The manufacturing method of a polarizing element which develops both.   An image display device comprising the polarizing element according to claim 15.