JP6500458B2 - PHOTOSENSITIVE RESIN COMPOSITION, CURING MEMBER COMPRISING THE SAME, AND IMAGE DISPLAY DEVICE PROVIDED WITH THE SAME - Google Patents

Description

  In the present invention, a member such as a protective film, an insulating film, a planarizing film, a column spacer, a bank, a color filter, a resin black matrix and the like used in an image display device such as a liquid crystal display or an organic EL display is patterned by photolithography. The present invention relates to a photosensitive resin composition that can be formed. More specifically, the present invention relates to a photosensitive resin composition that can be formed at a low temperature, a curing member configured thereof, and an image display apparatus 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. Also, from the viewpoint of printing electronics for cost reduction and for dealing with a large amount of small quantities, flexible plastic substrates that can be used for roll-to-roll and the like are being studied.

As such flexible plastic substrates, polycarbonate, polyethylene terephthalate and the like have been studied, but they are inferior in heat resistance to conventional glass substrates. Therefore, in order to reduce the thermal stress applied to the plastic substrate, in the manufacturing process of the flexible display, it is required to lower the temperature than before. A baking process for forming a member such as a protective film or an insulating film is one of the processes that require the highest temperature in manufacturing a flexible display, and the baking process needs to be performed at a low temperature.
In addition to this, for example, there is a movement for weight reduction and cost reduction by forming a polarizing film of a liquid crystal display by a coating method, but a protective film formed on the coating type polarizing film is also a polarizing film or a liquid crystal layer It is necessary to form it at a temperature which does not damage etc., and low temperature (low temperature curing) is required.
Furthermore, in color filters used in, for example, image display devices, various studies have been conducted to transfer a coloring material from a pigment type to a dye type as a method for achieving high contrast, but dyes are more thermally sensitive than pigments. The low temperature curing property of the material for forming a color filter is also required from that point. In addition, even when a pigment is used as the coloring material, it is known that high-temperature curing can obtain high contrast, and low-temperature curing is also required from that viewpoint.

As such a low-temperature curable photosensitive resin composition, various reports using a cationic polymerization of an epoxy or an oxetane, and further a combination of a radical polymerizable material with these are seen.
For example, Patent Document 1 shows a combination of an epoxy group-containing polymer and a cationic polymerization initiator, and Patent Document 2 shows a combination of an epoxy group and an 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 photosensitive acid generator such as an onium salt, and an epoxy compound.
Patent documents 4 and 5 show combinations of cationic polymerization systems and radical polymerization systems using an epoxy group-containing copolymer, and patent documents 6 and 7 show cationic polymerization systems and radical polymerization systems using an oxetane compound. A combination of is disclosed.

Unexamined-Japanese-Patent No. 11-5816 JP 2005-84415 A WO 2006/006581 pamphlet JP 2008-260909 A JP 2012-150180 A JP, 2011-48064, A Unexamined-Japanese-Patent No. 2003-255531

In recent years, the market demand for simplification of the process and panel structure has been increased, and a material having both photolithotropy and sufficient strength is required also in a low temperature manufacturing process.
As examined by the present inventor, the photosensitive resin compositions described in Patent Documents 1 to 7 do not have sufficient electrical reliability, and when used in liquid crystal displays or organic EL displays, image sticking and reduction of life are caused. It has been found that there is an adverse effect such as an increase in driving voltage, and there is also a problem that the mobility is lowered or hysteresis is generated when in proximity to the organic TFT semiconductor.

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

  The inventor made various studies in order to solve the problems. As a result, a photosensitive resin composition containing a vinyl polymer having 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. In addition, it has been found that it is possible to simultaneously achieve high electrical reliability at low temperature curing, and the present invention has been completed. That is, the gist of the present invention is as follows.

[1] A vinyl polymer containing a side chain α having an epoxy group, (B) a cationic photopolymerization initiator, (C) an ethylenically unsaturated group-containing compound, and (D) a thermal radical polymerization initiator Photosensitive resin composition characterized by having.
[2] The photosensitive resin composition according to [1], wherein the (D) thermal radical polymerization initiator comprises 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 the thermal radical polymerization initiator (D) contains 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 alkyl group having 1 to 10 carbon atoms which may have a substituent, and X represents O or NH.)

[4] The composition according to any one of [1] to [3], further comprising a naphthalene compound or an anthracene compound having two or more substituents selected from the group consisting of (E) alkyl ether group and acyloxyl group Photosensitive resin composition.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein (A) the vinyl polymer comprises a side chain β having a cyclic aliphatic group.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the vinyl polymer (A) contains 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], which further comprises (F) a colorant.
[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], which further comprises (H) a liquid repellent.
[10] A cured member composed of the photosensitive resin composition according to any one of [1] to [9].
[11] The curing member according to [10], having one or more protrusions.
The image display apparatus provided with the hardening member as described in [12] [10] or [11].

[13] A protective layer formed on an 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 formed into a wet film on an anisotropic dye film, and after exposure, the anisotropic dye film and photosensitive resin are exposed with a developer. A method of manufacturing a polarizing element, which develops both of the composition films.
[17] An image display device comprising the polarizing element according to [15].

  According to the photosensitive resin composition of the present invention, a curable member which can be patterned by photolithography and has good electric reliability can be formed 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 the embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist.
In the present invention, “(meth) acrylic acid” includes both acrylic acid and methacrylic acid, and “(meth) acrylate”, “(meth) acryloyl” and the like also have the same meaning. Moreover, what attached "(poly)" in front of a monomer name means this monomer and this polymer.
In the present invention, "total solids" means all components of the photosensitive resin composition of the present invention excluding the solvent.

[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 cationic photopolymerization initiator, (C) an ethylenically unsaturated group-containing compound, and (D) It contains a thermal radical polymerization initiator. The photosensitive resin composition of the present invention may further contain a naphthalene compound or an anthracene compound having two or more substituents selected from the group consisting of (E) an alkyl ether group and an acyloxyl group, (F) It may contain a colorant, (G) inorganic nanoparticles, and (H) liquid repellent agent. In addition, it may contain silicon and / or a fluorine-based surfactant, and may contain other additives as appropriate.

[(A) Vinyl Polymer Containing a Side Chain α Having an Epoxy Group]
The photosensitive resin composition of the present invention comprises (A) a vinyl polymer containing a side chain α having an epoxy group, whereby the photocurability at the time of photolithography, the development pattern formation, and the shrinkage at the time of light and heat curing. It is possible to achieve excellent film quality and the like by reducing the film thickness and suppressing the flexibility and the permeability.

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

In the above 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 which is not bonded to α of the epoxy group in the formula (2) may bond to α to form a ring.

Examples of the divalent linking group in α include an alkylene group which may have a substituent, and a methylene group in the alkylene group is an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide It may be substituted by at least one type of bond selected from the group consisting of a bond and a urethane bond. For example, a linking group containing an ester bond or an amide bond can be mentioned.
The carbon number of the alkylene group is not particularly limited, but is preferably 1 or more from the viewpoint of easiness of synthesis, and 9 or less from the viewpoint of film formability, and 7 or less. Is more preferable, 5 or less is more preferable, and 3 or less is particularly preferable.
Examples of the substituent which the alkylene group may have include 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, a cyano Group, acetyloxy group, alkylcarbonyloxy group having 2 to 9 carbon atoms, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetyl An amide group, a dialkylaminoethyl group formed by combining 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, etc. And preferably an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, and an alkyl carboxyl group having 2 to 8 carbon atoms. , Sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, a halogen atom. From the viewpoint of easiness of synthesis, the alkylene group is preferably unsubstituted.

Among α, in view of easiness of synthesis, a direct bond, an alkylene group interrupted by an ether bond, or an alkylene group interrupted by an ester bond is preferable, and an alkylene group interrupted by an ester bond is more preferable, - (C = O) -O- CH 2 - and more preferably a group. In addition, the alkylene group interrupted by the ether bond means the alkylene group which has an ether bond (-O- bond) between C-C bond which comprises an 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 is mentioned. Examples of the epoxy group-containing vinyl compound include the following compounds.

  As the epoxy group-containing vinyl compound, allyl glycidyl ether, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, α-n-propyl glycidyl (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, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, o-vinyl Aliphatic epoxy group-containing epoxy group-containing vinyl compounds such as glycidyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc., 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 cycloaliphatic epoxy group-containing vinyl compounds and the like.

  One of these may be used alone, or two or more 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, and it is more preferable to use a (meth) acrylate compound, and glycidyl (meth) acrylate or 4-hydroxybutyl ( It is further preferred to use meta) acrylate glycidyl ether.

  The content ratio of the repeating unit structure derived from the epoxy group-containing vinyl compound (the repeating unit structure represented by the general formula (2)) in the vinyl polymer (A) is preferably 30 mol% or more, 40 mol% or more The content is more preferably 50 mol% or more. Also, it is usually 100 mol% or less, preferably 99 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less, and particularly preferably 70 mol% or less. The exposure sensitivity, the electrical reliability, and the chemical resistance tend to be secured by setting the lower limit value or more, and the excellent film quality and the patterning property during development tend to be secured by setting the upper limit value or less. is there.

  The (A) vinyl polymer may further contain a side chain β having a cyclic aliphatic group. The inclusion of the side chain β tends to result in uniform excellent film quality.

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

In the above 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 which may have a substituent. A part of methylene groups in the alkylene group may be substituted by at least one bond selected from the group consisting of unsaturated bonds, ether bonds, thioether bonds, ester bonds, thioester bonds, amide bonds and urethane bonds. For example, a linking group containing an ester bond or an amide bond can be mentioned.
The carbon number of the alkylene group is not particularly limited, but is preferably 1 or more from the viewpoint of easiness of synthesis, and 9 or less from the viewpoint of film formability, and 7 or less. Is more preferred.
Examples of the substituent which the alkylene group may have include 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, a cyano Group, acetyloxy group, alkylcarbonyloxy group having 2 to 9 carbon atoms, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetyl An amide group, a dialkylaminoethyl group formed by combining 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, etc. And preferably an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, and an alkyl carboxyl group having 2 to 8 carbon atoms. , Sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, a halogen atom. From the viewpoint of easiness of synthesis, the alkylene group is preferably unsubstituted.

  Among β, from the viewpoint of easiness 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. In addition, the alkylene group interrupted by the ether bond means the alkylene group which has an ether bond (-O- bond) between C-C bond which comprises an 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 carbon number of the cyclic aliphatic group in R ⁶ is not particularly limited, but is preferably 5 or more, more preferably 6 or more, and still more preferably 8 or more, from the viewpoint of film strength. And from the viewpoint of the reactivity of the vinyl polymer, 20 or less is preferable, 15 or less is more preferable, and 12 or less is more preferable.
The cyclic aliphatic group may be monocyclic or polycyclic, but is preferably polycyclic from the viewpoint of film strength.
Specific examples of the cyclic aliphatic group include cyclohexyl group, dicyclopentanyl group, adamantyl group, norbornyl group, tetracyclodecanyl group and the like, and among them, from the viewpoint of film strength, dicyclopentanyl group Or an adamantyl group is preferred.

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

  The content ratio of the repeating unit structure (the repeating unit structure represented by the general formula (3)) derived from the cyclic aliphatic group-containing vinyl compound in the vinyl polymer (A) is preferably 1 mol% or more, and 10 mol % Or more is more preferable, and 15 mol% or more is more preferable. Moreover, it is preferable that it is 40 mol% or less, It is more preferable that it is 35 mol% or less, It is more preferable that it is 20 mol% or less. There is a tendency that the strength and the electric reliability of the film formed by coating can be secured by setting the above lower limit value or more, and the exposure sensitivity can be secured by setting the above upper limit value or less.

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

  Although 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, it has the following general formula (4) including a side chain γ having a carboxyl group or an aromatic hydroxyl group Mention may be made of those which contain a recurring unit structure which is represented.

In the above 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 in γ include an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, a urethane bond, and an alkylene group which may have a substituent. A part of methylene groups in the alkylene group may be substituted by at least one bond selected from the group consisting of unsaturated bonds, ether bonds, thioether bonds, ester bonds, thioester bonds, amide bonds and urethane bonds. For example, a linking group containing an ester bond or an amide bond can be mentioned.
The carbon number of the alkylene group is not particularly limited, but is preferably 1 or more from the viewpoint of easiness of synthesis, and 9 or less from the viewpoint of film formability, and 7 or less. Is more preferred.
Examples of the substituent which the alkylene group may have include 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, a cyano Group, acetyloxy group, alkylcarbonyloxy group having 2 to 9 carbon atoms, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetyl An amide group, a dialkylaminoethyl group formed by combining 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, etc. And preferably an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, and an alkyl carboxyl group having 2 to 8 carbon atoms. , Sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, a halogen atom. From the viewpoint of easiness of synthesis, the alkylene group is preferably unsubstituted.

  Among the γ, in view of easiness 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 a direct bond or an ester bond More preferred is direct binding. In addition, the alkylene group interrupted by the ether bond means the alkylene group which has an ether bond (-O- bond) between C-C bond which comprises an 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.

As a group containing an aromatic hydroxyl group in R ⁸ , for example, hydroxyphenyl group, hydroxycarboxyl phenyl group, dihydroxyphenyl group, trihydroxyphenyl group, bromophenyl group, dibromophenyl group, hydroxynaphthyl group, hydroxynitrophenyl group, hydroxy A benzyl group etc. are mentioned. Among R ^8, a hydroxyphenyl group is preferable and a p-hydroxyphenyl group is more preferable from the viewpoint of cost and film forming property.

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 carboxyl group-containing vinyl compounds include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and the like. Also, as the aromatic hydroxyl group-containing vinyl compound, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxyphenyl ( Meta) acrylate, N- (4-hydroxyphenyl) (meth) acrylamide, etc. are mentioned.
One of these may be used alone, or two or more 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, and on the other hand, to achieve higher electric reliability, it is preferable to use an aromatic hydroxyl group-containing vinyl compound, It is more preferable to use (meth) acrylic acid as the carboxyl group-containing vinyl compound, and p-hydroxystyrene or p-hydroxyphenyl (meth) acrylate as the aromatic hydroxyl group-containing vinyl compound.

  (A) A repeating unit structure derived from a carboxyl group-containing vinyl compound or an aromatic hydroxyl group-containing vinyl compound in the case where an alkali developability is provided by introducing a carboxyl group or an aromatic hydroxyl group into a vinyl polymer The content ratio of the repeating unit structure (4) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more 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 more preferable that it is 30 mol% or less. The alkali developability tends to be easily secured by setting the content to the lower limit or more, and the production stability of the polymer (A) tends to be easily secured by setting the content to the upper limit or less.

  When obtaining a vinyl polymer (A), other vinyl compounds may be used as other copolymerization components in addition to the three types of polymerization components. As other vinyl compounds, for example, 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 (meth) ) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloyl morpholine, (meth) acrylonitrile, (meth) acrylamide, N-methacrylic acid 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 is less than 50 mol% as a repeating unit structure derived therefrom in the (A) vinyl polymer. 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 cyclic aliphatic group-containing vinyl compound, the carboxyl group-containing vinyl compound, the aromatic hydroxyl group-containing vinyl compound, and other vinyl compounds is not limited in any way, but It can be synthesized by a known method using, for example, a polymerization initiator, adding a chain transfer agent as necessary, and heating at the activation temperature of the radical polymerization initiator.

  It is preferable that it is 3000 or more, and, as for the weight average molecular weight of (A) vinyl polymer of this invention, it is more preferable that it is 5000 or more. Further, it is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000 or less, and particularly preferably 20,000 or less. There is a tendency that film strength such as chemical resistance can be secured by setting it to the above lower limit value, and there is a tendency that excellent patterning characteristics can be secured by setting it to the above upper limit value.

  In addition, let the weight average molecular weight in this invention be a value of polystyrene conversion measured using "column GPC-804" by Shimadzu Corporation by "gel permeation chromatography system LS Solution" by Shimadzu Corporation.

  The content ratio of the vinyl polymer (A) in the photosensitive resin composition of the present invention is preferably 20% by mass or more and 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 By setting it to the above lower limit value or the like, securing of the patterning property by photolithography tends to be facilitated, and by setting it to the above upper limit or less, it tends to be easy to secure sufficient curability.

[(B) Photocationic polymerization initiator]
The cationic photopolymerization initiator (B) contained in the photosensitive resin composition of the present invention generates an acid by irradiation with visible light, ultraviolet light and the like to initiate a polymerization reaction of an epoxy group. Examples of the cationic photopolymerization 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, sulfone imide compounds, diazomethane compounds and the like. And is not particularly limited, but aromatic iodonium salts and aromatic sulfonium salts are preferable from the viewpoint of curability.

The aromatic iodonium salt is a compound having a diaryliodonium cation, and the aromatic sulfonium salt is a compound having a triaryl sulfonium cation. These cations are paired with anions (anions) to constitute a photocationic polymerization initiator.
Examples of the diaryliodonium cation include diphenyliodonium cation having an alkyl group, an ether group or the like as a substituent, and specifically, (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, Examples include (2,4,6-trimethylphenyl) [4- (1-methylacetic acid ethyl ether) phenyl] iodonium cation and the like.
Examples of the triarylsulfonium cation include triphenylsulfonium cation having an alkyl group, a thioether group, an ether group or the like as a substituent, and examples thereof include diphenyl [4- (phenylthio) phenyl] sulfonium cation, triphenylsulfonium cation, and alkyltri And phenyl sulfonium cation and the like.

Examples of anions constituting the photocationic polymerization initiator include hexafluorophosphate anion PF ^6- , hexafluoroantimonate anion SbF ^6- , pentafluorohydroxyantimonate anion SbF ₅ (OH) ^- , hexafluoroarsenate anion AsF ⁶⁻ , tetrafluoroborate anion BF ⁴⁻ , tetrakis (pentafluorophenyl) borate anion B (C ₆ F ₅ ) ^{4−, and the} like, and hexafluorophosphate anion PF ⁶⁻ is preferable. These anions become an acid generation source, and the stronger the acidity of the generated acid, the higher the efficiency of the polymerization reaction, but on the other hand, problems such as deterioration of the electrical reliability and corrosion of the electrode tend to occur. Depending on the application, it may be used properly.

As an aromatic sulfonium salt, CPI-100P, CPI-101A, CPI-200K, CPI-210S of San-Apro Corporation, Adeka optomer SP-150, SP-170, SP-171 of ADEKA, etc. are specifically mentioned as a specific example. It can be mentioned.
Also, as aromatic iodonium salts, PHOTOINITIATOR 2074 from Solvay Japan, IRGACURE 250 (IRGACURE is a registered trademark) from BASF Japan, CI-5102 from Nippon Soda Co., Ltd., WPI-113 from Wako Pure Chemical Industries, etc. A specific example is given.

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

  Also, as the s-triazine derivative, for example, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloro) Examples include methyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine and the like.

  As a sulfone compound, the (beta) -keto sulfone compound, the (beta)-sulfonyl sulfone compound, and the (alpha) -diazo compound of these compounds are mentioned, for example. Specific examples of preferable sulfone compounds include 4-trisphenacyl sulfone, mesityl phenacyl sulfone and bis (phenacylsulfonyl) methane.

  Examples of sulfonic acid compounds include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate.

  Examples of sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) B) 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 cationic photopolymerization initiator (B) in the photosensitive resin composition of the present invention is 0.05% by mass in the case of using an aromatic sulfonium salt with respect to the total solid content of the photosensitive resin composition It is preferable that it is more than 0.1 mass%, It is preferable that it is 3 mass% or less, It is more preferable that it is 1 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, 5 mass% or less is more preferable . By setting the content to the above lower limit or more, sufficient photocurability tends to be easily ensured, and by setting the above upper limit or less, it is possible to suppress deterioration in film performance such as deterioration of electric reliability and coloring. is there.

[(C) Ethylenically Unsaturated Group-Containing Compound]
The photosensitive resin composition of the present invention comprises (C) an ethylenically unsaturated group-containing compound. The (C) 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 tends to obtain the effect of improving chemical resistance as well as improving the patterning property of the photosensitive resin composition by containing the (C) ethylenically unsaturated group-containing compound. is there.

The more ethylenic unsaturated groups are in the molecule, the denser the network at the time of crosslinking (curing) becomes, and it tends to be easy to secure chemical resistance and electrical reliability. In addition, even if the crosslinking ratio in all the ethylenically unsaturated groups is lowered due to the low temperature baking, it is advantageous from the point that a proper network is secured.
From this, the (C) ethylenically unsaturated group-containing compound preferably has a large number of ethylenically unsaturated groups, and specifically, preferably has two or more, and three or more. It is more preferable to have 5 or more. There is no upper limit to the number of ethylenically unsaturated bonds, but it is usually 12 or less, preferably 6 or less. In addition, you may use what has many ethylenically unsaturated bonds like a dendrimer.

From the viewpoint of reactivity, the ethylenically unsaturated group (C) contained in the ethylenically unsaturated group-containing compound is preferably an allyl group and / or a (meth) acryloyl group.
The (C) ethylenically unsaturated group-containing compound may be used alone or in combination of two or more with an arbitrary ratio. In addition, when using multiple types of ethylenically unsaturated group-containing compounds, with regard to the number of ethylenically unsaturated groups, the molar average number of ethylenically unsaturated groups possessed by the multiple types of ethylenically unsaturated group-containing compounds The value may be in the preferred range described above.

  Hereinafter, among the (C) ethylenically unsaturated group-containing compounds, particularly preferable 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) (C3) ( Epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound, etc. are mentioned.

(C1) As esters of unsaturated carboxylic acid and polyhydroxy compound, for example, reaction product of unsaturated carboxylic acid and sugar alcohol, reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol, The reaction product of saturated carboxylic acid and alcohol amine etc. are mentioned.
Here, specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid and itaconic acid.

  Specific examples of sugar alcohols 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 adducts of sugar alcohols include compounds in which ethylene oxide or propylene oxide is added to the above-mentioned sugar alcohols.
Specific examples of alcohol amines include polyhydric alcohol amines such as diethanolamine and triethanolamine.

  And, as esters of unsaturated carboxylic acid and polyhydroxy compound, specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di ( Meta) 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 also include derivatives of these compounds. Among the derivatives, from the viewpoint of patterning properties, derivatives having an acid group are preferable. For example, those in which a part of the polyhydroxy compound in the ester is replaced with a compound having an acid group, specifically a carboxyl group-containing compound It is preferable to replace by

  In addition, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compounds such as hydroquinone, resorcinol, pyrogallol, bisphenol F, bisphenol A or ethylene oxide adducts thereof The reaction products of Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate] and the like can be mentioned.

Also, a reaction product of the above-mentioned unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, Also, tri (meth) acrylate and the like can be mentioned.
Also, a reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, a condensation product of (meth) acrylic acid, phthalic acid and ethylene glycol, (meth) acrylic acid, maleic acid and diethylene glycol Also included are condensates, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, and condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin.

  Examples of urethane (meth) acrylates of (C2) hydroxy (meth) acrylate compound and polyisocyanate compound include, for example, hydroxy (meth) acrylate compound, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate or The reaction product with polyisocyanate compounds, such as heterocyclic polyisocyanate, etc. are mentioned.

  Specifically, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylol ethane tri (meth) acrylate and the like can be mentioned as the hydroxy (meth) acrylate compound. Polyisocyanate compounds are aliphatic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanatomethyloctane; cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexylisocyanate), isophorone diisocyanate, bicyclo Alicyclic polyisocyanates such as heptane triisocyanate; aromatic polyisocyanates such as 4, 4-diphenylmethane diisocyanate and tris (isocyanatophenyl) thiophosphate; and heterocyclic polyisocyanates such as isocyanurate.

As a commercial item of urethane (meta) acrylates of a hydroxy (meta) acrylate compound and a polyisocyanate compound, for example, Shin Nakamura Chemical Co., Ltd. "U-4HA", "UA-306A", "UA-MC340H", " UA-MC340H "and" U6LPA "etc. are mentioned.
As urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, four or more urethane bonds [-NH-CO-O- to ensure sufficient chemical resistance of the cured product etc. And compounds having 4 or more (meth) acryloyloxy groups are preferred. Such a compound is, for example, a compound having two or more hydroxyl groups, a compound having four or more hydroxyl groups, and a compound having three or more isocyanate groups, and a compound having two or more hydroxyl groups. Or a compound having one or more hydroxyl groups and two or more (meth) acryloyloxy groups, or the like.

  Specifically, the following compounds may, for example, be mentioned. That is, as a compound obtained by reacting a compound having 4 or more hydroxyl groups with a diisocyanate compound, a compound having 4 or more hydroxyl groups such as pentaerythritol or polyglycerin, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate And compounds obtained by reacting with a diisocyanate compound 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 Biuret types such as 24A-100 (registered trademark), "Duranate (registered trademark) 22A-75PX", "Duranate (registered trademark) 21S-75E", "Duranate (registered trademark) 18H-70B", and the like Three or more of adduct type such as "Duranate (registered trademark) P-301-75E", "Duranate (registered trademark) E-402-90T", and "Duranate (registered trademark) E-405-80T", etc. The compound etc. which are obtained by making the compound which has an isocyanate group react are mentioned.

  As a compound obtained by reacting a compound having four or more isocyanate groups with a compound having one or more hydroxyl groups and two or more (meth) acryloyloxy groups, isocyanatoethyl (meth) acrylate or the like is polymerized Or compounds having 4 or more, preferably 6 or more, isocyanate groups such as compounds obtained by copolymerization, "Duranate (registered trademark) ME 20-100" manufactured by Asahi Kasei Chemicals, and pentaerythritol di (meth) And one or more hydroxyl groups such as acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. and two or more, preferably three or more (meth) acryloyl groups With a compound having an oxy group And compounds obtained by reacting the like.

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

  Specifically, for example, (meth) acrylic acid or the above-mentioned 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, ( Aliphatic polyepoxy compounds such as sorbitol polyglycidyl ether; phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds , Aromatic polyepoxy compounds such as (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds; sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris ( The compound etc. which are obtained by reaction with polyepoxy compounds, such as heterocyclic polyepoxy compounds, such as 2-hydroxyethyl) isocyanurate, etc. are mentioned.

Examples of the ethylenically unsaturated group-containing compounds other than (C1) to (C3) include (meth) acrylamides such as ethylene bis (meth) acrylamide, allyl esters such as diallyl phthalate, and vinyl groups such as divinyl phthalate And compounds having a thioether bond in which the ether bond of an ethylenically unsaturated compound having an ether bond is sulfurized by phosphorus pentasulfide or the like to convert it to a thioether bond.
In addition to these, special ethylenically unsaturated group-containing compounds such as macromonomers and dendrimer acrylates may be used according to the required properties. For example, as dendrimer, STAR-501 and SIRIUS-501 of Osaka Organic Co., Ltd. may be mentioned. As a macromonomer, AA-6, AS-6, AB-6, AN-6S etc. of Toagosei Co., Ltd. are mentioned, for example.

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

  The photosensitive resin composition of the present invention is preferably used after development after exposure and developed with a developing solution, but when an alkaline developing solution is used, a carboxyl group, a hydroxyl group, polyethylene glycol or Alternatively, an ethylenically unsaturated group-containing compound having a polypropylene glycol group introduced may be used.

  The content ratio of the (C) ethylenic 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 preferred. By setting the content to the above lower limit or more, the effect of using the ethylenically unsaturated group-containing compound tends to be sufficiently exhibited, and by setting the above upper limit or less, the sufficient low temperature curability tends to be easily secured. There is.

[(D) thermal radical polymerization initiator]
The photosensitive resin composition of the present invention contains (D) a thermal radical polymerization initiator. The thermal radical polymerization initiator (D) is a compound which can be decomposed by thermal energy to generate a radical, and conventionally known organic peroxides, azo compounds and the like can be used.
Among these, it is preferable that 10 hour half life temperature is 70 degreeC or more, it is more preferable that it is 80 degreeC or more, and it is especially preferable that it is 90 degreeC or more. The temperature is preferably 140 ° C. or less, more preferably 130 ° C. or less, and particularly preferably 120 ° C. or less. If it is above the lower limit value, storage stability tends to be easily secured, and if it is below the upper limit value, it tends to be easy to secure sufficient low temperature curability.
Moreover, you may use that whose 10-hour half-life temperature is out of the said range as (D).

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

In the general formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R ¹ attached to the same carbon atom R ² and R ² may combine to form a ring. R ³ represents an alkyl group having 1 to 10 carbon atoms 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 preferably 3 or less, more preferably 2 or less from the viewpoint of reaction efficiency.
The substituent which the alkyl group may have is not particularly limited as long as it is inert to the reaction, and examples thereof include a phenyl group, a tolyl group and a xylyl group. From the viewpoint of easiness of synthesis, unsubstituted is preferable.
Specific examples of the alkyl group which may have a substituent include methyl group, ethyl group, propyl group, butyl group, benzyl group and the like, and from the viewpoint of reaction efficiency, methyl group and ethyl group are preferable. And more preferably a methyl group.

Also, R ¹ and R ² bonded to the same carbon atom may form a ring. For example, R ¹ and R ² may combine to form a cycloalkyl group.
Examples of the ring formed include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like, and among these, from the viewpoint of reaction efficiency as an initiator and production, a cyclopentyl group and a cyclohexyl group are preferable. Is a cyclohexyl group.

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

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 the content to the above lower limit or more, the affinity with the solvent and the other components of the photosensitive composition tends to be improved, and by setting the above upper limit or less, the radicals are easily moved and the reaction efficiency is improved. Tend.
As a substituent which the alkyl group may have, a hydroxyl group etc. are mentioned, for example. From the viewpoint of easiness of synthesis, unsubstituted is preferable.
Specific examples of the alkyl group which may have a substituent include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, s-butyl group, Tert-butyl group , 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 And 2-butenyl group, 3-butenyl group, isobutenyl group, cyclopentyl group, cyclohexyl group and the like, preferably methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, isopropyl group, isobutyl group, 2-propypenyl group, more preferably propyl , Butyl group, hexyl group, a cyclohexyl group, an isopropyl group, an isobutyl group.

  In addition, X is O or NH, and is more preferably NH from the viewpoint of easily designing a 10-hour half temperature to 70 ° C. to 140 ° C.

  Specific examples of the compound represented by the general formula (1) include, for example, 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-hydroxye) C) 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, the inside of () represents a 10-hour half-life temperature.

  Among the above-mentioned examples, particularly preferred are 2,2′-azobis (N-butyl-2-methylpropionamide) and 2,2′-azobis (N— in view of half-life temperature, solubility, safety and the like. Hexyl-2-methylpropionamide), 2,2'-azobis (N-propyl-2-methylpropionamide).

As the thermal radical polymerization initiator (D), one type may be used alone, or two or more types may be used in combination.
The content ratio of the (D) thermal 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 The content is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The content is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less. By setting the content to the above lower limit or more, sufficient chemical resistance tends to be easily obtained. On the other hand, by setting the above upper limit or less, deterioration of developability tends to be suppressed.
In addition, the content ratio of the thermal radical polymerization initiator in which the 10-hour half-life temperature temperature satisfies the above range in the thermal radical polymerization initiator (D) is usually 100% by mass or less, and sufficiently cured at low temperature, Also, from the viewpoint of developing the part to be removed during development without leaving any residual, it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and most preferably 100% by mass. %.

[A naphthalene compound or anthracene compound having two or more substituents selected from the group consisting of (E) alkyl ether group and acyloxyl group]
In the photosensitive resin composition of the present invention, a naphthalene compound having two or more substituents selected from the group consisting of (E) alkyl ether group and acyloxyl group for the purpose of enhancing the sensitivity of (B) photo cationic polymerization initiator Alternatively, an anthracene compound may be included. By using the component (E), sufficient sensitivity tends to be secured even if a photocationic polymerization initiator which is not high in sensitivity but advantageous in electric reliability, for example, a hexafluorophosphate salt of aromatic iodonium is used.

The carbon number of the alkyl ether group is not particularly limited, but is preferably 1 or more from the viewpoint of solubility, and 10 or less from the viewpoint of sensitivity, more preferably 8 or less, and still more preferably 5 or less. 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, an octoxy group and the like, and from the viewpoint of balance of solubility and sensitivity, an ethoxy group More preferably, it is a propoxy group or a butoxy group.
The carbon number 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 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, decananoyloxy group, dodecanoyloxy group, etc. From the viewpoint of balance between the properties and the sensitivity, an octanoyloxy group or an ethylpentanoyloxy group is preferable, and an octanoyloxy group is more preferable.

The naphthalene ring or anthracene ring in the naphthalene compound or the anthracene compound may be substituted by any substituent other than two or more substituents selected from the group consisting of an alkyl ether group and an acyloxyl group. The optional substituent includes an alkyl group, a halogen atom, an amino group and the like. From the viewpoint of easiness of synthesis, it is preferable not to have any substituent.
As a combination of the alkyl ether group and / or the acyloxyl group which a naphthalene compound or an anthracene compound has, 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 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 Is preferred.

  Examples of naphthalene compounds or anthracene compounds having two or more substituents selected from the group consisting of (E) alkyl ether groups and acyloxyl groups include, for example, naphthalene-1,4-diether, anthracene-9,10-diether, 9, 9, 10-Bisacyloxylanthracene etc. are mentioned.

Specific examples of naphthalene-1,4-diether include, for example, 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 the anthracene-9,10-diether include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di (n-propoxy) anthracene, 9,10-di (i-propoxy) Anthracene, 9,10-di (n-butoxy) anthracene and the like can be mentioned.

Further, specific examples of 9,10-bisacyloxyanthracene include 9,10-bis (n-pentanoyloxy) anthracene, 9,10-bis (n-hexanoyloxy) anthracene, 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, 9,10-bis (n-dodecanoyloxy) anthracene and the like.
Among naphthalene compounds or anthracene compounds having two or more substituents selected from the group consisting of (E) alkyl ether group and acyloxyl group, 1,4-dimethoxynaphthalene, 1,4-diethoxy from the viewpoint of sensitivity. Preferred are naphthalene, 9,10-di (n-butoxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene and the like.

  In the photosensitive resin composition of the present invention, one kind of naphthalene compound or anthracene compound having two or more substituents selected from the group consisting of (E) alkyl ether group and acyloxyl group may be used alone, Two or more 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, and more preferably 1% by mass, with respect to the total solid content of the photosensitive resin composition. % Or more is more preferable, 5% by mass or less is preferable, and 4% by mass or less is more preferable. If it is above the above lower limit, sufficient photocurability tends to be secured easily, and if it is below the above 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 purposes such as color filters, resin black matrix and the like for preventing light leakage and reflection, it is preferable to use the (F) coloring material. As the coloring material, known materials such as dyes, organic pigments and inorganic pigments can be appropriately used according to the application, but since the photosensitive resin composition of the present invention can be cured at low temperature, it is easily decomposed or deteriorated under high temperature conditions Dyes 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, phthalocyanine dyes and the like. In particular, when forming blue pixels, xanthene dyes, triarylmethane dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, cyanine dyes, phthalocyanine dyes and the like can be mentioned. Dyes are preferably used in color filter applications such as liquid crystal displays and organic EL displays because they can achieve high brightness.

  Organic pigments tend to have higher heat resistance compared to dyes, and thus are usually used suitably for color filters, but tend to have lower luminance than dyes. However, when the composition containing the pigment can be cured at low temperature to form a color filter, the decrease in the brightness of the pigment due to heat can be suppressed, so that the photosensitive resin composition of the present invention that can be cured at low temperature can be suitably used. There is a tendency to be able to obtain a color filter with higher brightness than ordinary high temperature cured products. In addition, since the photosensitive resin composition of the present invention is excellent in electric reliability, a color filter on array requiring high electric reliability, a black column spacer or black rib in a liquid crystal cell, black for organic EL It can 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, and as the chemical structure, for example, phthalocyanine type, quinacridone type, benzimidazolone And organic pigments such as dioxazines, indanthrenes, perylenes, azos, quinophthalones, anthraquinones, anilines, and cyanines. 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, if necessary, other components, and used as a pigment dispersion mixed with the photosensitive resin composition.

  Examples of inorganic pigments include carbon black, titanium black, ultramarine blue, Prussia blue, yellow lead, zinc yellow, red lead, iron oxide red, zinc white, lead white, lithopone, titanium dioxide and the like. Among these, carbon black is particularly excellent in light blocking ratio and image formation, and can be suitably used for resin black matrix applications and the like. However, since carbon black has conductivity, it may be insulated and used, for example, by covering it with a resin if it becomes a problem. It is preferable to use these inorganic pigments as a pigment dispersion as well as the organic pigments and then mix them with the photosensitive resin composition.

In the present invention, the colorant (F) may be, for example, an appropriate combination of a dye and an organic pigment, an organic pigment of a plurality of colors, and an organic pigment and an inorganic pigment.
Although the content ratio of the (F) coloring material which may be contained in the photosensitive resin composition of the present invention is not particularly limited, in the case of a dye, it is preferably 1 mass from the viewpoint of securing sufficient luminance and light shielding properties. % Or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and from the viewpoint that photocurability is hardly reduced and sufficient film strength can be maintained, preferably 40% by mass or less More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less. Further, in the case of a pigment, from the viewpoint of securing sufficient brightness and light shielding property, the photo-curing property is hardly reduced, preferably 3% by mass or more, more preferably 6% by mass or more, and further preferably 10% by mass or more. Further, from the viewpoint of easily securing the developer solubility, the content 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. As the filler, kaolinite, calcium carbonate and the like can be mentioned, and since it has the effect of improving the physical strength of the cured member, it may be suitably used in the case where hard coatability is desired. Further, examples of the metal oxide particles include oxide nanoparticles of metals such as aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium, and among them, oxide particles of zirconium, titanium or zinc are mentioned. It is preferable to use for applications where high refractive index and high dielectric constant are required. Examples of applications in which a high dielectric constant is required include a gate insulating film and the like. Like the pigments, 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 the leak due to the conductivity or the like becomes a problem, the surface can be insulated by covering with a resin.
The content ratio of the (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 to be added can be sufficiently exhibited. More preferably, it is 1% by mass or more, more preferably 3% by mass or more, and from the viewpoint that the solubility during development can be sufficiently secured, it is preferably 80% by mass or less, more preferably 70% by mass or less More preferably, it is 60 mass% or less.

[(H) liquid repellent agent]
As a liquid repellent which may be used for the photosensitive resin composition of this invention, a fluorine-containing compound and a silicon containing compound are mentioned. The liquid repellent agent can be used also for the purpose of antifouling, but it is particularly suitably used, for example, when the photosensitive resin composition of the present invention is used for a bank application for inkjet. In the case where the ink ejected by the inkjet is an aqueous solution, a silicon-containing compound is preferable, and in the case of an organic solvent solution, a fluorine-containing compound is preferable.

  The fluorine-containing compound is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound, and has, for example, a crosslinking group such as an ethylenically unsaturated double bond or an epoxy group, and a fluoroalkyl group And compounds containing a fluoropolyether group and the like. Specifically, for example, RS series of DIC Corporation, Optool DAC of Daikin Industries Co., Ltd., Opto Ace series, etc. may be mentioned.

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

The liquid repellents may be used alone or in combination of two or more.
The concentration of the liquid repellent agent is not particularly limited. For example, in the case of forming a bank, when the fluorine atom content and the silicon content in the liquid repellent agent are to be 10% by mass or more, the entire photosensitive resin composition The amount is usually 0.001% by mass or more, preferably 0.05% by mass or more, and usually 10% by mass or less, preferably 6% by mass or less, based on the solid content.
When the fluorine atom content and the silicon content are less than 10% by mass, the content is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 0.1% by mass or more based on the total solid content of the photosensitive resin composition. It is 70% by mass or less, preferably 50% by mass or less.
By setting the lower limit value or more, the ink repellency tends 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 the upper limit value or less, development at the time of bank formation becomes easy, and it is possible to avoid residual or repellent residual liquid repellent agent in the inside divided by the bank, so It tends to be easy to supply uniformly. As the liquid repellent agent used for the bank, it is preferable to use a fluorine-containing compound when the ink to be discharged inside divided by the bank is an organic solvent type, and it is preferable to use a silicon containing compound in the case of an aqueous solution type.

[Photo radical polymerization initiator]
In the photosensitive resin composition of the present invention, it is preferable to use a photoradical polymerization initiator for the purpose of making the (C) ethylenically unsaturated group-containing compound also photopolymerizable. As photo radical polymerization initiators, for example, metallocene compounds containing titanocene derivatives described in JP-A-59-152396 and JP-A-61-151197; Hexaary described in JP-A-2000-56118 Rubiimidazole derivatives; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acids as 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-A-2000-80068, JP-A-2006-36750, etc. It can be mentioned. Among these, it is preferable that the radical polymerization initiator contains oxime ester derivatives and / or α-aminoalkylphenone derivatives.

  Specifically, for example, as titanocene derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro) Phenyl-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluoropheny-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny-) 1-yl), dicyclopentadienyl titanium di (2, 6-difluoro phen- 1-yl), dicyclopenta dienyl titanium di (2, 4- difluoro phen- 1-yl), di (methyl cyclopenta) (Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-l-yl), di (methyl) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl], etc. It can be mentioned.

  Moreover, as biimidazole derivatives, 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.)-4, 5- diphenyl imidazole dimer etc. are mentioned.

  Also, as halomethylated oxadiazole derivatives, 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- (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.

  Moreover, as halomethyl-s-triazine derivatives, 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) -triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) And -s-triazine and the like.

  Further, as α-aminoalkylphenone derivatives, 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-dimethylaminoethyl benzoate, 4-dimethylaminoisoamylbenzoe 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, oximes and ketoxime ester compounds described in JP-A-2000-80068 and JP-A-2006-36750 can be mentioned.
In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; anthraquinone derivatives such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone and the like Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, etc .; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenyl Nilpropanone, 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 4-diethylthioxanthone and 2,4-diisopropylthioxanthone; Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p-) Methoxyv 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 photo radical polymerization initiators, from the viewpoint of sensitivity, particularly when a coloring agent such as dye or pigment is added, oxime ester derivatives are preferable, ketooxime ester derivatives are more preferable, and keto oxime having a benzoyl group Derivatives are particularly preferred. When 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. It does not specifically limit about the combination in the case of using 2 or more types of optical radical polymerization initiators together.
It is preferable that the content rate of the radical photopolymerization initiator in the photosensitive resin composition of this invention is 0.5 mass% or more with respect to the total solid of the photosensitive resin composition of this invention, and 1 mass % Or more is more preferable, 2% by mass or more is more preferable, 15% by mass or less is preferable, 12% by mass or less is more preferable, and 10% by mass or less is more preferable. Preferably, it is 8% by mass or less. By setting it as the said lower limit or more, there exists a tendency which can fully express photocurability, and on the other hand, there exists a tendency which can suppress deterioration of developability by below the said upper limit. In addition, when using the photosensitive resin composition of this invention for the use with low light transmittance like resin black matrix etc., there is a tendency for it to be easy to secure photocurability, when using a radical photopolymerization initiator more. is there.

[Leveling agent]
The photosensitive resin composition of the present invention can be coated on a substrate by wet coating or printing, but it is preferable to use a leveling agent for the purpose of avoiding defects such as repelling and thickness unevenness. Although various surfactants may be mentioned as the leveling agent, it is preferable to use a silicon and / or fluorine surfactant in order to ensure the electric reliability.

  Examples of fluorine-based surfactants include BM series by Big Chemie, Megafuck series by DIC (Megafuck is a registered trademark), Florard series by Sumitomo 3M, Surfron series by AGC (Surflon is a registered trademark), The Tergent series by Neos (Horgent is a registered trademark) and the like can be mentioned.

  Further, examples of the silicone surfactant include BYK series of BICK CHEMY, series of SH · SZ · DC of Toray Dow Corning, and TSF series of Toshiba Silicone.

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

[Organic solvent]
The photosensitive resin composition of the present invention is preferably diluted with an organic solvent.
When using an organic solvent, it is preferable to use so that the content rate of the total solid in the photosensitive resin composition of this invention may be 3 mass% or more, and using it so that it may be 5 mass% or more It is more preferable to use 10% by mass or more, and it is particularly preferable to use 15% by mass or more, and it is preferable to use 40% by mass or less, 35% by mass It is more preferable to use it as follows. There is a tendency that the film thickness can be easily controlled by setting it to the lower limit value or more, and the pot life of the photosensitive resin composition can be easily maintained by setting the upper limit value or less. There is. In addition, a total solid shows the sum total of components other than the organic solvent.

  The organic solvents used in the present invention are, for example, glycol monoalkyl ethers, glycol dialkyl ethers, glycol diacetates, alkyl acetates, ethers, ketones, monohydric or polyhydric alcohols, aliphatic hydrocarbons, and the like. Alicyclic hydrocarbons; aromatic hydrocarbons; linear 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 Ether acetate, methyl lactate), dimethylformamide, ethyl lactate, cyclohexanone, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diisobutyl ketone, diacetone alcohol, 3-ethoxy propionate, dipropylene glycol dimethyl ether, butyl cellosolve, 3-methoxy-3- 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, and diethylene glycol monomethyl ether. The organic solvent preferably used is propylene glycol monomethyl ether acetate or ethylene glycol monomethyl ether acetate. These organic solvents may be used alone or in combination of two or more, and may be determined in consideration of the balance of coating property, surface tension, boiling point and the like.

[Other ingredients]
The photosensitive resin composition of the present invention can contain other components as needed, as long as the excellent effects of the present invention are not significantly impaired. 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, etc. Examples thereof include development accelerators such as acids.
As an epoxy compound, for example, Mitsubishi Chemical's JER series, Daicel's Celoxide series (Celoxide is a registered trademark), Nippon Steel Sumikin Chemical's Epototh series (Epototh is a registered trademark), Nippon Kayaku Co., Ltd. , XD-, EPPN-, EOCN- and the like, EPICLON (registered trademark) of DIC Corporation, and the like.
Examples of the oxetane include OXT series manufactured by Toa Gosei Co., Ltd. and OXE-10 and 30 manufactured by Osaka Organic Co., Ltd.
Moreover, as resin, an acrylic resin, a urethane resin, a novolak resin etc. are mentioned as a preferable example. In these resins, radically polymerizable unsaturated groups, cationically polymerizable groups, and other crosslinking groups may be introduced. As the radically polymerizable unsaturated group-containing resin, for example, a resin obtained by polymerizing glycidyl (meth) acrylate as a copolymerization component in addition to epoxy (meth) acrylate resins such as ZAR, ZCR, CCR, etc. of Nippon Kayaku Co., Ltd. Resin etc. which were made to ring-open with (meth) acrylic acid etc. are mentioned.

[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, dissolving or disperse | distributing by stirring or an ultrasonic wave application. In addition, when using a (C) ethylenic unsaturated group containing compound, a liquid epoxy compound, and an oxetane compound when preparing a composition, it is good also considering them as an organic solvent.

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

Further, the photosensitive resin composition of the present invention is a gel component which may be generated at the time of synthesis of insoluble matter, resin and the like by mixing the above-mentioned components together with an organic solvent and filtering it using a filter. It is preferable to remove trace metals and the like. As a filter, for example, an integritis optimizer, CUNO nanoshield, Zeta Plus EC, etc. can be used. In addition, since insoluble matter, gel components, dust, trace metals, etc. cause repelling when the thin film is formed, it is necessary to select the roughness of the filter eye according to the film thickness, for example, a film of 500 nm or less When it is desired to form with a thickness, and when it does not contain a pigment, 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.

[Cured member composed of photosensitive resin composition]
The photosensitive resin composition of the present invention is patterned by photolithography and used to form a protective film (protective layer), an insulating film (insulating layer), a planarization film (planarization layer), a column spacer, a bank, a color filter, It is possible to form a hardened member, such as a resin black matrix. The photosensitive resin composition of the present invention can be suitably used as a protective layer formed on an anisotropic dye film, because a cured member excellent in electrical reliability can be formed at low temperature.

[Method of Manufacturing Hardened Member]
As a method of applying the photosensitive resin composition of the present invention, for example, spinner method, wire bar method, flow coating method, die coating method, blade coating method, rod coating method, roll coating method, spray coating method, inkjet method, An electrospray deposition method etc. are mentioned. Among them, the die coating method is preferable because a small amount of application is possible, there is less risk that mist adheres, and foreign matter is less likely to be generated, as compared with 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, inkjet printing, nozzle printing, stamping (microcontact printing) or the like.

  When the photosensitive resin composition of the present invention contains an organic solvent, it is usually dried after application or printing. Drying can be performed by heating using a heating apparatus such as a clean oven, a hot plate, an infrared ray, a halogen heater, or microwave irradiation. Above all, a clean oven and a hot plate are preferable because they easily heat the entire film evenly. The drying conditions may be appropriately selected according to the type of organic solvent and the like. It is preferable to dry at a high temperature for a long time from the viewpoint that it is easy to obtain stable curability if it is sufficiently dried, but on the other hand, the time required for drying is short and excellent in productivity, and photosensitive resin It is preferable to dry at a low temperature for a short time in order to prevent the dark reaction of the composition from proceeding. Therefore, the drying temperature is usually 40 ° C. or more, preferably 50 ° C. or more, and is usually 120 ° C. or less, preferably 100 ° C. or less. The drying time is preferably 15 seconds or more, more preferably 30 seconds or more, and, on the other hand, preferably 5 minutes or less, more preferably 3 minutes or less. 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 photosensitive resin composition layer applied (or dried further if it contains an organic solvent) is exposed directly through an exposure mask with an exposure mask or is drawn directly with a laser to insolubilize the exposed portion, and then light irradiation is blocked by the exposure mask. A development process is performed to remove the photosensitive resin composition layer of the portion which has been or has not been irradiated with the laser.

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, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp, lamp light source such as LED, argon ion laser, YAG Laser light sources such as lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, near-infrared semiconductor lasers, etc. may be mentioned.
Here, when light of a specific wavelength is used, 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 ^{It is 2} or less, more preferably 500 mJ / cm ² or less.

  The photosensitive resin composition of the present invention can also be used by adjusting the light curing degree by changing the light transmittance depending on the site using a halftone exposure mask, and adjusting the film thickness after development depending on the site. it can. For example, it is possible to obtain the protective layer and the column spacer thereon in one exposure and development step. As described above, by using a halftone exposure mask, a cured member having one or more convex portions can be obtained. The height difference between the convex portion and the other portion is not particularly limited, but is preferably 1 μm or more. The upper limit is not particularly limited, but is usually 20 μm or less.

The photosensitive resin composition of this invention can be patterned and used by removing the part which did not receive irradiation of light at the time of exposure by development process. As a developing solution used for development, an organic solvent and an alkaline developing solution are used. An alkaline developer is preferable in terms of handleability and environmental problems, but for example, in the case where it is produced at low temperature in applications where residual moisture has an adverse effect such as organic EL etc, an organic solvent is used Is preferred.
Examples of the alkali 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 methyl diethylamine, dimethylethylamine and triethylamine, aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline, alkanolamines such as ethanoldimethylamine, methyldiethanolamine and triethanolamine Mention may be made of aqueous solutions of alkaline compounds such as quaternary ammonium salts such as methyl ammonium hydroxide, tetraethyl ammonium hydroxide and the like.
As the organic solvent, those mentioned in the section of coating solvent can be mentioned.
These may be used singly or in combination as a mixture, or may be used as a mixture of an alkali developer and a water-soluble organic solvent.

The developer used in the present invention may further contain a surfactant, an antifoaming agent, a buffer, a complexing agent and the like. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, etc .; alkyl benzene sulfonic acid Anionic surfactants such as salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids.
There is no particular limitation on the developing method and its conditions.

Examples of the development method include immersion development, paddle development, spray development, brush development, ultrasonic development and the like. Among them, immersion development and spray development are preferable because they are not easily stained, are not easily damaged, and easily develop uniformly, and paddle type development is preferable in that the amount of developer used can be reduced. The development temperature is usually 10 ° C. or more, preferably 15 ° C. or more, and is usually 50 ° C. or less, preferably 45 ° C. or less.
After development, it is washed with water or an organic solvent and dried.
After development, if necessary, additional exposure may be performed to accelerate photopolymerization. The additional exposure may be performed by the same method as the above-described exposure method. However, in the case of the additional exposure, the entire surface exposure may be performed without using a mask.

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

  The baking temperature is preferably 100 ° C. or more, more preferably 120 ° C. or more, and preferably 200 ° C. or less, more preferably 180 ° C. or less. If the temperature is lower than this range, the time required for curing tends to be long and the productivity may be poor or the film may not be sufficiently cured. If the temperature is higher than this range, the substrate is deformed when a plastic substrate is used. It tends to cause problems such as coloration. In addition, although a shorter baking time is preferable for efficiency, it is suitably 3 minutes to 2 hours, particularly 10 minutes to 1 hour, in terms of securing sufficient curability.

  The substrate used as the support of 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. Examples of the substrate for forming such a substrate include inorganic materials such as glass; triacetate resins, acrylic resins, polyester resins, polycarbonate resins, polyethylene terephthalate resins, triacetylcellulose resins, norbornene resins And polymeric materials such as cyclic polyolefin resin, polyimide resin, or urethane resin. These may be used alone or in combination of two or more. In particular, the substrate is preferably a substrate containing a polymer base containing a polymer material.

[Method of Manufacturing Polarizing Element]
The photosensitive resin composition of the present invention can be used to form a protective layer formed on an anisotropic dye film, and to manufacture a polarizing element provided with a protective layer on the anisotropic dye film. it can. In particular, it is preferable to use as a protective layer formed on an anisotropic dye film (hereinafter sometimes referred to as “coated polarizing film”) formed by coating.

  When pattern-forming a polarizing element using the photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is wet-deposited on an anisotropic dye film (polarizing film) formed on a substrate. After exposure, either (i) develop both the polarizing film and the photosensitive resin composition film with a developer, or (ii) develop only the photosensitive resin composition film first, and then use this as a resist to form a photosensitive resin. The method of melt | dissolving and developing the polarizing film of the part which is not covered with a composition film with a developing solution is mentioned. Since the photosensitive resin composition of the present invention can impart alkali developability as described in the paragraph of (A) vinyl polymer, it develops with the polarizing film having alkali solubility by the method of (i) Is preferable in terms of process reduction. After forming a pattern by development, the photosensitive resin composition film is further cured by baking to form a protective layer. At this time, melt flow may be performed to block the side surface of the polarizing film, if necessary. . The polarizing film to be the lower layer often has difficulty in patterning in itself, and the chemical resistance and the heat resistance tend to be insufficient.

  The substrate used as a support for the polarizing film in the method for producing a polarizing element of the present invention is not particularly limited, but preferably is a substrate having good surface properties, contact angle characteristics and water absorption characteristics. . Examples of the substrate for forming such a substrate include inorganic materials such as glass; triacetate resins, acrylic resins, polyester resins, polycarbonate resins, polyethylene terephthalate resins, triacetylcellulose resins, norbornene resins And polymeric materials such as cyclic polyolefin resin, polyimide resin, or urethane resin. These may be used alone or in combination of two or more. In particular, the substrate is preferably a substrate containing a polymer base 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 rate is excessively large, the substrate may absorb moisture when forming a film of the anisotropic polarizing material by a wet film formation method, and the substrate may be warped to cause a coating defect. Moreover, after a polarizing film is formed by the apply | coating method, a board | substrate may swell and an optical defect may generate | occur | produce. In addition, "water absorption" is the value which measured the weight change rate when making it immersed in water of 23 degreeC for 4 hours using the test method of ASTMD570.

  An alignment treatment layer or the like may be provided in advance on the surface on which the polarizing film is to be formed, which is a substrate surface, in order to better orient an anisotropic polarizing material such as a dye contained in the polarizing film in a certain direction. it can. The alignment treatment layer can be formed by a known method described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000), pp. 226-239. Moreover, as a shape of a board | substrate, the film form (sheet-like form) of a fixed dimension may be sufficient, and a continuous film form (strip | belt shape) may be sufficient. The thickness of the substrate is usually 0.01 mm to 3 mm, preferably 0.02 mm to 2 mm.

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

[Other hardening members]
Although it does not specifically limit as another hardening member which can be formed using the photosensitive resin composition of this invention, For example, a protective film, an insulating film, a planarizing film, a column spacer, a bank, a color filter, resin black matrix etc. are mentioned. Be The protective film is used, for example, for the purpose of protecting functional members such as a semiconductor layer and a polarizing film, and, if necessary, hard coatability may be imparted by using a filler or the like which is (G) inorganic nanoparticles. good. The insulating layer is used, for example, to insulate between wiring and electrodes, between the TFT substrate and the wiring, etc. When used as a gate insulating film or a capacitor, it is a metal oxide that is (G) inorganic nanoparticles as needed. The dielectric constant may be increased, for example. The flattening film is applied, for example, to the surface of a rough flexible substrate, and is used to smooth or flatten the unevenness of the member. For example, the column spacer plays the role of a stick to secure the gap of the liquid crystal cell, and if necessary, it may be colored such as black using a dye or pigment which is a coloring material (F). The bank serves as a threshold when, for example, the ink is separately applied by ink jet, and may be added with a liquid repellent (H) to impart liquid repellency in order to prevent the ink from overflowing out of the bank. . The color filter plays a role of expressing a color of a liquid crystal display, an organic EL display or the like, and expresses and uses the three primary colors of light by further using a dye or pigment which is a (F) coloring material. The resin black matrix is used for the purpose of preventing light leakage of a liquid crystal display and reflection from electrodes of a display in general, and is further blackened by further using a dye or pigment which is a (F) coloring material. These members may be formed by photolithography for each member, but if it is possible that they exist on the same surface on the substrate, adjust the exposure intensity for each part using a half tone mask. Thus, multiple types of members can be formed at one time.

[Image display device]
The image display apparatus of the present invention is provided with a curing member obtained by using at least the photosensitive resin composition of the present invention, and a polarizing element. Specifically, a liquid crystal display device can be mentioned. As a configuration example of a liquid crystal display device, a TFT element array substrate having an interlayer insulating film, an 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 with a spacer interposed therebetween. The liquid crystal is injected into the gap. Furthermore, there is one in which a backlight is disposed outside the TFT element array substrate. The display device of the present invention is not limited to this, and other examples include an organic EL display device and the like.

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

Example 1 and Comparative Example 1
The details of each component used in Example 1 and Comparative Example 1 are as follows.
<Polymer-1>
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, in a flask equipped with a reflux condenser, a stirrer, and a nitrogen blowing pipe After charging 400 parts by mass of ether acetate and 8.0 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate) and substituting with nitrogen, the liquid temperature is raised to 80 ° C while stirring, After reaction for 1 hour and decomposition of dimethyl-2,2'-azobis (2-methylpropionate) at 100 ° C. for 1 hour, propylene glycol monomethyl ether acetate is distilled under a reduced pressure of 80 ° C. The partial concentration was concentrated to about 50% by mass to obtain polymer-1. The weight average molecular weight (Mw) of this resin was about 11,000.

In addition, a weight average molecular weight was measured using Shimadzu Corp. "gel permeation chromatograph system LS Solution" using Shimadzu Corp. "column GPC-804."
The structure of the repeating unit contained in the polymer-1 is as follows.
The content ratio of the repeating unit structure derived from the epoxy group-containing vinyl compound (glycidyl methacrylate) in the 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 (manufactured by Wako Pure Chemical Industries, Ltd.)>

<Irg 907 (manufactured by BASF)>

<BYK-330 (made by BIC Chemie)>
Polyether modified polymethyl alkyl siloxane

Preparation of Photosensitive Resin Compositions 1 and 2
Each component in Table 1 was weighed, stirred using a magnetic stirrer to dissolve completely, and stirring was continued for another 10 minutes. Next, filtration was carried out using an Integras company optimizer V47 0.02 μm FD5A XFR to obtain photosensitive resin compositions 1 and 2.

<Evaluation of patternability>
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 spin was applied for 50 seconds. After that, it was dried by heating on a hot plate at 90 ° C. for 90 seconds to form a protective layer. This sample was passed through a mask having a negative pattern of 5, 6, 7, 8, 9, 10, ²⁰ , 30, 40, 50 μm lines and dots at an exposure of 200 mJ / cm ² using a 3 kW high pressure mercury lamp. Exposure.
The sample was then immersed and developed for 30 seconds with shaking using propylene glycol monomethyl ether acetate as a developer. After development, it was flushed with propylene glycol monomethyl ether acetate and then dried with compressed air.
At this time, the appearance of the pattern was observed with an optical microscope, and the size of the finest pattern formed is shown in Table 1. In addition, when development was not completed, it was considered as development impossible. The smaller the number, the better.

<Evaluation of chemical resistance>
The sample obtained in the evaluation of the patterning property 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 portion 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)>
Substrate A with an ITO film formed on the entire surface of a cleaned 2.5 cm square alkali-free glass substrate ("AN-100" manufactured by Asahi Glass Co., Ltd.), and the center of one side of the same 2.5 cm square glass substrate A substrate B was prepared on which a 1 cm square ITO film was formed, to which 2 mm wide extraction electrodes were connected.
Each photosensitive resin composition shown in Table 1 is coated with a spin coater so that the film thickness after baking becomes 1 μm on the surface of the substrate A on which the ITO film is formed, and 90 on a hot plate. After drying at 90 ° C for 90 seconds, the photosensitive resin composition of the contact portion is wiped off with a cotton swab containing acetone, and exposed at a dose of 200 mJ / cm ² using a 3 kW high pressure mercury lamp, and then heated at 180 ° C in an oven. By baking for 15 minutes, the board | substrate A with which the photosensitive resin composition was film-formed on the whole surface was obtained.

Next, a UV-curable sealant containing silica beads of 5 μm in diameter is coated on the outer periphery of the surface of the substrate B on which the ITO film is formed, using a dispenser. The surface on which the film was formed was placed so as to be offset by 3 mm at the outer edge, and was pressed and irradiated with ultraviolet light.
Liquid crystal (MLC-6846-000 manufactured by Merck Japan, Inc.) was injected into the empty cell thus obtained, and the peripheral portion was sealed with a UV-curable sealant to complete a liquid crystal cell for voltage retention measurement.

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

Example 2
The details of each component used in Example 2 are as follows.

<Polymer-2>
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, methacrylic acid 12 in a flask equipped with a reflux condenser, a stirrer, and a nitrogen blowing pipe After charging in parts by mass, 300 parts by mass of diethylene glycol methyl ethyl ether, and 9 parts by mass of dimethyl 2,2′-azobis (2-methylpropionate) and substituting with nitrogen, the liquid temperature is raised to 80 ° C. while stirring, It reacted for 6 hours at ° C to obtain polymer-2. The weight average molecular weight (Mw) of this resin was about 8,000.

In addition, a weight average molecular weight was measured using Shimadzu Corp. "gel permeation chromatograph system LS Solution" using Shimadzu Corp. "column GPC-804."
The structure of the repeating unit contained in the polymer-2 is as follows.
The content ratio of the repeating unit structure derived from the epoxy group-containing vinyl compound (glycidyl methacrylate) in the polymer-2 is 67 mol%, and the content of the repeating unit structure derived from the cyclic aliphatic group-containing vinyl compound (dicyclopentanyl methacrylate) The ratio was 11 mol%, and the content ratio of the repeating unit derived from methacrylic acid was 22 mol%.

<TO1382 (made by Toagosei Co., Ltd.)>

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

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

Preparation of Photosensitive Resin Composition 3
Each component in Table 2 was weighed, and in the same manner as Photosensitive Resin Compositions 1 and 2, Photosensitive Resin Composition 3 was obtained.

<Evaluation of patternability>
The developer was changed to 0.4% by mass TMAH (tetrahydroammonium hydroxide) in the evaluation of the patterning properties of Example 1, and the film thickness was adjusted to be 1 μm after coating and drying. The patterning properties of the photosensitive resin composition 3 were 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. 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. 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 high level of electrical reliability even under extremely severe conditions of 0.6 Hz. This is considered to be the result of containing a thermal radical polymerization initiator and promoting a more precise curing reaction at the time of baking. The photosensitive resin composition of the present invention is found to be useful when producing a cured member with higher electric reliability under low temperature conditions. Furthermore, since the minimum resolution size is 10 μm or less, it is understood that the photosensitive resin composition of the present invention is capable of stable and highly accurate patterning by photolithography.
Table 1 and Table 2 also show that Example 2 has a higher level of VHR (electrical reliability) from a comparison of Example 1 and Example 2, but this generates an acid. Therefore, it is considered that the amount of the photocationic polymerization initiator which can affect the electrical reliability is suppressed by adding the compound (E).

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

<Preparation of insolubilization liquid 1>
75.6 parts by mass of 6 N sulfuric acid was added to 24.4 parts by mass of bis (hexamethylene) triamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred and dissolved to prepare Insolubilized solution 1. The viscosity of the insolubilizing liquid 1 was 50 cP.

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

((I) Process)
An alignment film (a polyimide film having a film thickness of about 60 nm) was formed on a glass substrate (10 × 10 cm, thickness 0.7 mm), and was rubbed in a direction horizontal to the end face to prepare a substrate.
The composition 1 for an anisotropic dye film is coated on this alignment film by a die coater (wet film thickness 2 μm, head speed 15 mm / s) and naturally dried to obtain a polarizing film with a film thickness of about 0.4 μm. Formed. The environmental conditions at the time of application were 23 ° C. and 50 RH%.

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

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

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

  Next, this sample was heated in an oven at 180 ° C. for 15 minutes to obtain a sample of a coated protective film with a protective layer patterned. The polarizing film under the protective layer was a uniform and good film without cracking, detachment of the film, and the like.

<Evaluation of polarization characteristics>
About the coating type polarizing film with a protective layer of Example 3, the obtained sample was divided in half, and it was observed that the respective polarizing films were superimposed so as to be orthogonal or parallel. It was confirmed that the light was uniformly blocked or transmitted.

  Thus, it turns out that it is possible to pattern, without giving a damage to a coating type polarizing film by using the photosensitive resin composition of this invention as a protective layer.

  Since the photosensitive resin composition of the present invention can be patterned by photolithography and can form a cured member with good electrical reliability at low temperature, the cured member can be formed in the presence of a material having low high temperature resistance, It is useful for manufacture of a flexible display etc.

Claims (17)

(A) a vinyl polymer containing a side chain α having an epoxy group, (B) photo-cationic polymerization initiator, (C) an ethylenically unsaturated group-containing compound, and (D) a photosensitive containing thermal radical polymerization initiator A resin composition,
The (B) photo cationic polymerization initiator contains an aromatic iodonium salt and / or an aromatic sulfonium salt,
A photosensitive resin composition which is used after baking at a temperature of 200 ° C. or less .   The photosensitive resin composition according to claim 1, wherein the thermal radical polymerization initiator (D) comprises a thermal radical polymerization initiator having a 10-hour half-life temperature of 70 to 140 ° C. The photosensitive resin composition of Claim 1 or 2 in which the (D) 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 alkyl group having 1 to 10 carbon atoms which may have a substituent, and X represents O or NH.)   The photosensitive resin according to any one of claims 1 to 3, further comprising a naphthalene compound or an anthracene compound having two or more substituents selected from the group consisting of (E) alkyl ether group and acyloxyl group. Composition.   The photosensitive resin composition according to any one of claims 1 to 4, wherein the vinyl polymer (A) contains a side chain β having a cyclic aliphatic group.   The photosensitive resin composition according to any one of claims 1 to 5, wherein the vinyl polymer (A) contains a side chain γ having a carboxyl group or an aromatic hydroxyl group.   The photosensitive resin composition according to any one of claims 1 to 6, further comprising (F) a colorant.   The photosensitive resin composition according to any one of claims 1 to 7, further comprising (G) inorganic nanoparticles.   The photosensitive resin composition according to any one of claims 1 to 8, further comprising (H) a liquid repellent agent.   The cured 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 film, 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.   The photosensitive resin composition according to any one of claims 1 to 6 is formed into a wet film on an anisotropic dye film, and after exposure, the anisotropic dye film and the photosensitive resin composition film are developed with a developer. A method of manufacturing a polarizing element, which develops both.   The image display apparatus provided with the polarizing element of Claim 15.