JP2017181617A - Photosensitive resin composition and cured film thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent curability, excellent solvent resistance after curing, and excellent heat resistance; a cured product formed from the photosensitive resin composition; and a color filter and a display device prepared with the cured product, wherein, particularly in a composition comprising a dye to achieve higher luminance and contrast of a color filter, the solvent resistance and adhesion are improved.SOLUTION: A photosensitive resin composition comprises a specific alkali-soluble resin (A), preferably an alkali-soluble resin obtained by adding a vinyl ether compound to a carboxyl group-containing polymer (A), a polymerizable monomer (B), a dye (C) and a photo-radical initiator (D).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition containing a specific alkali-soluble resin, a cured film using the photosensitive resin composition, a display device member, and a display device.

  Alkali-soluble resins are compounds used in various fields from civil engineering and building materials to electronic information materials. For example, they are preferably used as materials for alkali-developable resist compositions (also referred to as photosensitive resin compositions). Has been. The photosensitive resin composition is a composition whose physical properties are changed by irradiating the coating film with light or an electron beam, that is, for example, the exposed portion is cured and the other portion is soluble. It is a composition, and is used in various fields such as electronic information materials and optical materials by utilizing this characteristic. One of the main uses is a color filter. The color filter is usually composed of three primary color (RGB) pixels, a resin black matrix, a protective film, a columnar spacer, and the like, and is a main member of a liquid crystal display device and an imaging tube element.

  Photosensitive resin compositions are usually composed of a colorant such as a pigment in addition to an alkali-soluble resin, a polymerizable monomer, etc., but in recent years, display quality and imaging in liquid crystal display devices, imaging tube elements, etc. In order to improve the quality, demands for higher brightness and higher contrast are increasing, and the demand for miniaturization of the pixels constituting the color filter is also remarkable.

  As a photosensitive resin composition, for example, in Patent Document 1, a color filter containing a polymer obtained by reacting a carboxyl group-containing polymer with a compound having a vinyl ether group and a (meth) acryloyl group as a binder resin component A photosensitive resin composition is disclosed, and it has been found that the resin composition has excellent alkali developability when combined with a pigment dispersion. However, the physical properties such as brightness and contrast of the color filter cannot be sufficiently satisfied.

  Further, Patent Document 2 discloses a thermosetting resin composition comprising the above-described polymer and a polyvalent glycidyl ether compound as a photosensitive resin composition. This is because the carboxyl group regenerated by the elimination of the vinyl ether compound by heat and the epoxy group in the polyvalent glycidyl ether compound react to crosslink, resulting in excellent shape controllability and elastic recovery. Columnar spacers are obtained. However, since the same reaction proceeds at room temperature during long-term storage, the resin composition is very poor in storage stability and there is room for improvement in handling properties.

JP-A-2005-202134 Japanese Patent No. 5181613

  In recent years, the blending of dyes has been studied in order to achieve high brightness and high contrast of color filters. However, the present inventors have insufficient solvent resistance when a cured product (cured film) is formed. In addition, when the cured film was washed with a solvent, a problem was found that the coloring material was eluted in the solvent, and the adhesion did not reach a sufficient level. As described above, the pixels constituting the color filter are remarkably miniaturized. However, due to the miniaturization, there is a problem in adhesion, and there is a concern that the yield may be reduced.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a specific alkali-soluble resin (A), for example, an alkali-soluble resin (A) obtained by adding a vinyl ether compound to a carboxyl group-containing polymer, polymerization To obtain the knowledge that the above-mentioned problems can be solved by using a photosensitive resin composition containing a photosensitive monomer (B), a dye (C) and a photoradical initiator (D), and to complete the present invention. It came.

That is, the object of the present invention is achieved by the following <1> to <10>.
<1> Alkali-soluble resin (A) and polymerization having a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2) as essential structural units A photosensitive resin composition comprising a photosensitive monomer (B), a dye (C), and a photoradical initiator (D).

（式中のＲ_１は水素原子または炭素数１〜３のアルキル基を表す。Ｘはカルボキシル基、スルホン酸基、フェノール性水酸基、カルボン酸無水物基、リン酸基を表す。）

(R ₁ in the formula represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group.)

（式中のＲ_１は前記（１）中のＲ_１と同様であり、Ｒ_２は水素原子または有機残基を表す。Ｙは有機残基を表す。）
＜２＞前記式（２）中のＹは、（メタ）アクリロイル基を有する有機残基であることを特徴とする＜１＞に記載の感光性樹脂組成物。
＜３＞前記アルカリ可溶性樹脂（Ａ）は，ガラス転移温度が０℃以下であることを特徴とする＜１＞又は＜２＞に記載の感光性樹脂組成物。
＜４＞前記アルカリ可溶性樹脂（Ａ）は、主鎖に環構造を有することを特徴とする＜１＞〜＜３＞の何れか一つに記載の感光性樹脂組成物。
＜５＞カラーフィルタ用の感光性樹脂組成物であることを特徴とする＜１＞〜＜４＞の何れか一つに記載の感光性樹脂組成物。
＜６＞前記＜１＞〜＜５＞の何れかに記載の感光性樹脂組成物を硬化してなることを特徴とする硬化膜。
＜７＞前記＜６＞に記載の硬化膜を有することを特徴とする表示装置用部材。
＜８＞前記＜６＞に記載の硬化膜を有することを特徴とする表示装置。
＜９＞下記式（１）で表される構成単位（ａ−１）と下記式（２）で表される構成単位（ａ−２）を必須構成単位とするアルカリ可溶性樹脂（Ａ）、重合性単量体（Ｂ）、染料（Ｃ）及び光ラジカル開始剤（Ｄ）を混合することを特徴とする感光性樹脂組成物の製造方法。

(R ₁ in the formula is the same as R ₁ in the (1), R ₂ represents .Y represents a hydrogen atom or an organic residue represents an organic residue.)
<2> The photosensitive resin composition according to <1>, wherein Y in the formula (2) is an organic residue having a (meth) acryloyl group.
<3> The photosensitive resin composition according to <1> or <2>, wherein the alkali-soluble resin (A) has a glass transition temperature of 0 ° C. or lower.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the alkali-soluble resin (A) has a ring structure in the main chain.
<5> The photosensitive resin composition according to any one of <1> to <4>, which is a photosensitive resin composition for a color filter.
<6> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <5>.
<7> A display device member comprising the cured film according to <6>.
<8> A display device comprising the cured film according to <6>.
<9> Alkali-soluble resin (A) and polymerization having a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2) as essential structural units A photosensitive resin composition is produced by mixing a photosensitive monomer (B), a dye (C) and a photoradical initiator (D).

（式中のＲ_１は水素原子または炭素数１〜３のアルキル基を表す。Ｘはカルボキシル基、スルホン酸基、フェノール性水酸基、カルボン酸無水物基、リン酸基を表す。）

(R ₁ in the formula represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group.)

（式中のＲ_１は前記（１）中のＲ_１と同様であり、Ｒ_２は水素原子または有機残基を表す。Ｙは有機残基を表す。）
＜１０＞前記アルカリ可溶性樹脂（Ａ）は、カルボキシル基含有重合体と、ビニルエーテル基を有する化合物を反応させて得られるアルカリ可溶性樹脂であることを特徴とする＜９＞に記載の感光性樹脂組成物の製造方法。

(R ₁ in the formula is the same as R ₁ in the (1), R ₂ represents .Y represents a hydrogen atom or an organic residue represents an organic residue.)
<10> The photosensitive resin composition according to <9>, wherein the alkali-soluble resin (A) is an alkali-soluble resin obtained by reacting a carboxyl group-containing polymer with a compound having a vinyl ether group. Manufacturing method.

  In the alkali-soluble resin obtained by the reaction of the carboxyl group-containing polymer and the vinyl ether compound contained in the photosensitive resin composition of the present invention, the vinyl ether compound is desorbed by heat in the post-baking step during film formation, and the carboxyl group is regenerated. Crosslinks between molecules by reaction with a hydroxy group and the like, and the curability of the coating film is improved. In addition, since the detached units are excluded from the composition, the dye, which is a coloring material component, is highly concentrated in the cured film, and exhibits unprecedented high brightness, high contrast and high adhesion. I came up with the idea that the above-mentioned problem can be solved brilliantly.

  In addition, the alkali-soluble resin of the present invention can introduce a photosensitive double bond into the side chain by addition of a vinyl ether compound. For this reason, it has been found that in the exposure process during film formation, the polymerizable monomer and the like are cross-linked between molecules, and the curability of the coating film is improved. This effect also contributes to the above problem.

Although the preferable form of this invention is demonstrated concretely below, this invention is not limited only to the following description, In the range which does not change the summary of this invention, it can change suitably and can apply. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more also corresponds to the preferable form of this invention.
[Photosensitive resin composition]
The photosensitive resin composition of the present invention (also simply referred to as a resin composition) comprises a structural unit (a-1) represented by formula (1) and a structural unit (a-2) represented by formula (2). It contains at least the components (A) to (D) of the alkali-soluble resin (A), the polymerizable monomer (B), the dye (C), and the photoradical initiator (D) as essential constituent units. If necessary, one or more other components may be further contained, and one or two or more of each component may be used.

In the present specification, the “total amount of solid content” means the total amount of components that form a cured product, that is, the total amount of components (solid content and non-volatile content) excluding the solvent that volatilizes when the cured product is formed. Specifically, the total of the alkali-soluble resin, the polymerizable monomer, the coloring material, and other components when other cured product forming components (for example, photo radical initiator, dispersant, etc.) are included. The solid content mass of
[Alkali-soluble resin (A)]
The alkali-soluble resin contained in the photosensitive resin composition of the present invention requires a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2). It is an alkali-soluble resin as a structural unit.

（式中のＲ_１は水素原子または炭素数１〜３のアルキル基を表す。Ｘはカルボキシル基、スルホン酸基、フェノール性水酸基、カルボン酸無水物基、リン酸基などの酸性基を表す。）

(In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents an acidic group such as a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group. )

（式中のＲ_１は前記（１）中のＲ_１と同様であり、Ｒ_２は水素原子または有機残基を表す。Ｙは有機残基を表す。有機残基としては炭素数２〜１８の直鎖状、分岐状又は環状のアルキル基、炭素数２〜２０のアルコキシアルキル基、炭素数２〜８のハロゲン化（例えば、塩素化、臭素化又はフッ素化）アルキル基、末端に水酸基または（メタ）アクリレート基を有するポリエチレングリコール骨格、末端に水酸基または（メタ）アクリレート基を有するポリプロピレングリコール骨格、末端に水酸基または（メタ）アクリレート基を有するポリブチレングリコール骨格、置換基を有しても良い芳香環基、置換基を有しても良い脂肪族環基、置換基を有しても良いヘテロ環基、アリル基が挙げられる。なお、前記式（１）中のＲ_１と前記式（２）中のＲ_１は各々独立している。）
上記アルカリ可溶性樹脂としては、まず、重合工程で酸基含有重合体、好ましくはカルボキシル基含有重合体（ベースポリマーとも称する）を合成し、続く付加工程でビニルエーテル基を有する化合物を付加して得られるものが付加に伴うヒドロキシ基の生成がないため貯蔵安定性の点で好ましい。

(R ₁ in the formula is the same as R ₁ in the (1), R ₂ represents .Y represents a hydrogen atom or an organic residue represents an organic residue. Examples of the organic residue having 2 to 18 carbon atoms A linear, branched or cyclic alkyl group, an alkoxyalkyl group having 2 to 20 carbon atoms, a halogenated (for example, chlorinated, brominated or fluorinated) alkyl group having 2 to 8 carbon atoms, a hydroxyl group at the terminal or It may have a polyethylene glycol skeleton having a (meth) acrylate group, a polypropylene glycol skeleton having a hydroxyl group or a (meth) acrylate group at the terminal, a polybutylene glycol skeleton having a hydroxyl group or a (meth) acrylate group at the terminal, or a substituent. Examples thereof include an aromatic ring group, an aliphatic ring group which may have a substituent, a heterocyclic group which may have a substituent, and an allyl group, wherein R ₁ in the above formula (1) and the above formula ( 2) R ₁ in each is independent.
The alkali-soluble resin is obtained by first synthesizing an acid group-containing polymer, preferably a carboxyl group-containing polymer (also referred to as a base polymer) in a polymerization step, and adding a compound having a vinyl ether group in a subsequent addition step. This is preferable in terms of storage stability because there is no formation of hydroxy groups upon addition.

  The alkali-soluble resin is a resin (polymer) exhibiting alkali-solubility and preferably has an acid group in the molecule. Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and has only one of these. You may have, and you may have 2 or more types. Of these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable. In addition, alkali-soluble resin can act as binder resin in the photosensitive resin composition mentioned later.

The acid value (AV) of the alkali-soluble resin is preferably 20 mgKOH / g or more, for example. Thereby, sufficient alkali solubility is expressed, and it becomes possible to give a cured product having better developability. More preferably, it is 30 mgKOH / g or more. The upper limit of the acid value is preferably 300 mgKOH / g or less from the viewpoint of further improving curability, water resistance of the cured product, developability, and the like. More preferably, it is 250 mgKOH / g or less, More preferably, it is 200 mgKOH / g or less, Most preferably, it is 180 mgKOH / g or less. Among these, from the viewpoint of further improving the developability, 160 mgKOH / g or less and 150 mgKOH / g or less are more preferable (a range with a lower upper limit is more preferable).
In the present specification, the acid value of the polymer can be determined by the method described in Examples described later.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5000 or more, for example. Thereby, the hardened | cured material which is more excellent in heat resistance or mechanical strength can be given. More preferably, it is 8000 or more, More preferably, it is 10,000 or more. Such a high molecular weight is very suitable because the dispersibility and heat resistance of the coloring material are improved and the deterioration of the alkali-soluble resin is sufficiently suppressed to improve the reliability. The upper limit of Mw is not particularly limited, but is preferably 300,000 or less, more preferably 250,000 or less, still more preferably 100,000 or less, and particularly preferably from the viewpoint of further achieving low viscosity and further improving developability. 50,000 or less, most preferably 40,000 or less.
In this specification, molecular weight can be measured by the method as described in the Example mentioned later.

  The alkali-soluble resin may have a ring structure in the main chain. By having a ring structure in the main chain, it is possible to give a cured product that is excellent in heat resistance, surface hardness, and adhesion, can suppress changes with time after high-temperature exposure, and can stably exhibit various physical properties. In recent display devices, tempered glass is sometimes used for a substrate in order to give various members strength to withstand external impacts, but a polymer having a ring structure in the main chain is used as an alkali-soluble resin. Since a cured product that can exhibit excellent adhesion to tempered glass even after high temperature exposure is obtained, it is very useful.

  The glass transition temperature (Tg) of the alkali-soluble resin is preferably 100 ° C. or less, more preferably 80 ° C. or less, further preferably 50 ° C. or less, particularly preferably 30 ° C. or less, most preferably 0 ° C. or less, and most particularly preferably. Is −10 ° C. or lower. With such a glass transition temperature, it is considered that the crosslink density is increased because the alkali-soluble resin facilitates the generation of molecular movement during heating and causes an intermolecular reaction.

  The alkali-soluble resin may have a photosensitive double bond in the side chain. The side chain double bond-containing polymer preferably has a double bond equivalent of 100 to 5000 g / mol. By setting it as such a range, it is expected that the sufficient storage stability of the polymer and the good plate-making characteristics in the sensitivity and pattern shape of the curable resin composition of the present invention will be compatible at a higher level. it can. Especially preferably, it is 200 or more. Moreover, 2500 g / mol or less is particularly preferable.

The double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of the double bond of the polymer. The mass of the solid content of the polymer solution here means the mass of the base polymer component, the mass of the compound having a functional group capable of binding to an acid group and a polymerizable double bond group, and the mass of a chain transfer agent. And a thermal polymerization initiator. It can be determined by dividing the mass of the solid content of the polymer solution by the double bond amount of the polymer. The double bond amount of the polymer can be determined from the amount of the charged acid group and the compound having a functional group capable of bonding and a polymerizable double bond.
-Polymerization process-
(I) Monomer having an acid group The monomer component for producing the above base polymer is a monomer having an acid group in addition to a monomer capable of introducing a ring structure into the main chain skeleton of the polymer. It preferably includes a body.
The monomer having an acid group is a compound having an acid group and a polymerizable double bond in the molecule. For example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; Unsaturated monocarboxylic acids in which the chain between an unsaturated group and a carboxyl group, such as acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyloxyethyl); maleic anhydride, itaconic anhydride Unsaturated acid anhydrides such as phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); Among these, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferable are unsaturated monocarboxylic acids in terms of reactivity, alkali solubility, etc., and (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid) is still more preferable.

The blending ratio of the monomer having an acid group is preferably, for example, 5% by mass or more with respect to 100% by mass of the total amount of the base polymer component. Thereby, the solubility with respect to an alkali becomes more sufficient, and it becomes a more useful resin composition for the use where developability is required. In addition, it is preferably 90% by mass or less, more preferably 80% by mass, and still more preferably 70% by mass or less from the viewpoint that the excellent appearance and adhesion of the cured product can be maintained even after high temperature exposure. .
(Ii) Monomers other than acids The base polymer component may also include other monomers (also referred to as other monomers) that can be copolymerized with at least one of the above-described monomers, if necessary. You may contain a seed or two or more sorts. Other monomers are not particularly limited, and examples thereof include cyclic structure-containing (meth) acrylic acid ester monomers; cyclic structure-free (meth) acrylic acid ester monomers; aromatic vinyl compounds; Other examples include butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride, and acrylonitrile; vinyl esters such as vinyl acetate; Excluding those that correspond to a mass).

  Examples of the cyclic structure-containing (meth) acrylic acid ester monomer include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, ( (Meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, o-biphenyloxyethoxy Ethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) Acrylate, m-biphenyloxy-2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl = carbamate, N- (meth) acryloyloxyethyl-p-biphenyl = carbamate, N- (meth) ) Biphenyl group-containing monomers such as acryloyloxyethyl-m-biphenyl = carbamate, o-phenylphenol glycidyl ether acrylate, naphthalene ring-containing monomers such as vinylnaphthalene, terphenyl (meth) acrylate, o-terphenyloxyethyl (meth) An acrylate etc. are mentioned.

  Examples of the cyclic structure-free (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Examples include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and the like.

  Examples of the aromatic vinyl compound include styrene, vinyl toluene, α-methylstyrene, and the like.

  Among the other monomers described above, a cyclic structure-containing (meth) acrylic acid ester monomer or an aromatic vinyl compound is preferable in terms of good transparency and resistance to heat resistance. More preferred are cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, and butyl (meth) acrylate.

Although the blending ratio of the other monomer is not particularly limited, for example, it is preferably 0 to 70% by mass with respect to 100% by mass of the total amount of the base polymer component. Among them, when a cyclic structure-containing (meth) acrylic acid ester monomer and / or an aromatic vinyl compound are included, the content ratio is from the viewpoint of heat resistance, hardness, colorant dispersibility, development speed, transparency, and the like. Is preferably 1 to 50% by mass.
(Iii) Monomer capable of introducing a ring structure into the main chain skeleton of the polymer As a monomer capable of introducing a ring structure into the main chain skeleton of the polymer, for example, it has a double bond-containing ring structure in the molecule. Examples thereof include a monomer and a monomer that forms a polymer having a cyclic structure in the main chain by cyclopolymerization. Such a monomer is preferably at least one selected from the group consisting of N-substituted maleimide monomers, acrylic ether dimers, and α- (unsaturated alkoxyalkyl) acrylate monomers. is there. In this case, the alkali-soluble resin is a polymer having an N-substituted maleimide monomer unit, an acrylic ether dimer unit, and / or an α- (unsaturated alkoxyalkyl) acrylate monomer unit.

In particular, a resin (polymer) containing an N-substituted maleimide monomer unit and / or an acrylic ether dimer unit is cured with improved heat resistance, dispersibility (for example, colorant dispersibility), hardness, and the like. It becomes possible to give a film. In addition, resins containing α- (unsaturated alkoxyalkyl) acrylate monomer units can contribute to plate-making properties such as adhesion, curability, and dry redissolvability, colorant dispersibility, heat resistance, and transparency. It is possible to provide a cured film with improved properties and the like.
The resin (polymer) containing the above-mentioned monomer unit means a resin containing a structural unit derived from the monomer by, for example, a monomer polymerization reaction or a crosslinking reaction.
(Iii-1) N-substituted maleimide monomers As N-substituted maleimide monomers, for example, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N -T-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, p-methylbenzylmaleimide, p-butylbenzylmaleimide, p-hydroxybenzylmaleimide, o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide , P-dichlorobenzylmaleimide, and the like. Among them, N-phenylmaleimide and N-benzylmaleimide are preferable from the viewpoint of transparency, and N-benzylmaleimide is particularly preferable. Examples of N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide; halogen-substituted benzylmaleimide such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide; and the like.
(Iii-2) Acrylic ether dimer As an acrylic ether dimer, for example, the following general formula (3):

（式中、Ｒ１及びＲ２は、同一又は異なって、水素原子、又は、置換基を有していてもよい炭素数１〜２５の有機基を表す。）で表される化合物が好適である。

(Wherein R1 and R2 are the same or different and each represents a hydrogen atom or an organic group having 1 to 25 carbon atoms which may have a substituent).

In the general formula (3), R ₁ and R ₂ may represent a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. . For example, a linear or branched alkyl group; an aryl group; an alicyclic group; an alkyl group substituted with alkoxy; an alkyl substituted with an aryl group exemplified in JP2013-061599A [0037] Group; etc. are mentioned. Of these, primary or secondary carbon hydrocarbon groups which are difficult to be removed by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl and the like, are preferable in terms of heat resistance.
Note that R ₁ and R ₂ may be the same type of organic group or different organic groups.

  Among the acrylic ether dimers, dialkyl-2,2 '-(oxydimethylene) diacrylate monomers are preferable. Specifically, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-propyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2 ′-[ Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (stearyl)- , 2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2'- [Oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2′- [Oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, Dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) -2 2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like.

Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[ Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. From the viewpoint of little coloring, dispersibility, industrial availability, etc., dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate is more preferable.
(Iii-3) α- (Unsaturated alkoxyalkyl) acrylate monomer As the α- (unsaturated alkoxyalkyl) acrylate monomer, for example, alkyl- (α-methallyloxymethyl) acrylate, α -(Allyloxymethyl) acrylate is preferred. Of these, α- (allyloxymethyl) acrylate is more preferable.

  Examples of the α- (allyloxymethyl) acrylate include the following general formula (2):

（式中、Ｒ１は、水素原子、又は、置換基を有していてもよい炭素数１〜３０の有機基を表す。）で表される化合物が好適である。なお、本明細書では、「α−（アリルオキシメチル）アクリレート」に、Ｒ_１が水素原子である化合物（すなわちα−アリルオキシメチルアクリル酸）も含むものとする。

A compound represented by the formula (wherein R 1 represents a hydrogen atom or an organic group having 1 to 30 carbon atoms which may have a substituent) is preferable. In the present specification, “α- (allyloxymethyl) acrylate” includes a compound in which R ₁ is a hydrogen atom (that is, α-allyloxymethylacrylic acid).

R ₁ may be appropriately selected according to the purpose and application, but the organic group having 1 to 30 carbon atoms that R ₁ may represent may have a substituent, and may have 1 to 30 carbon atoms. The hydrocarbon group is preferably. Specifically, for example, a chain saturated hydrocarbon group exemplified in JP2013-061599A [0037]; an alkoxy-substituted chain in which a part of the hydrogen atoms of the chain saturated hydrocarbon group is replaced with an alkoxy group Linear saturated hydrocarbon group; hydroxy-substituted chain saturated hydrocarbon group in which part of chain saturated hydrocarbon group hydrogen atom is replaced with hydroxy group; part of chain saturated hydrocarbon group hydrogen atom is replaced with halogen Halogen-substituted chain saturated hydrocarbon group; chain unsaturated hydrocarbon group, and chain unsaturated hydrocarbon group in which part of the hydrogen atom is replaced with an alkoxy group, hydroxy group or halogen; alicyclic hydrocarbon group And an alicyclic hydrocarbon group in which a part of the hydrogen atom is replaced with an alkoxy group, a hydroxy group or a halogen; an aromatic hydrocarbon group and a part of the hydrogen atom are substituted with an alkoxy group, a hydroxy group And aromatic hydrocarbon groups substituted with halogen; and the like. Moreover, arbitrary substituents may be further bonded to these organic groups.

  Specific examples of the α- (allyloxymethyl) acrylate include, for example, α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid. n-propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α- N-amyl allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate , Α-allyloxymethyl acrylate s-hexyl, -N-heptyl allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 2-ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α -Tridecyl allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxy Contains chain saturated hydrocarbon groups such as stearyl dimethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, etc. α- (allyloxymethyl) acrylate is preferred. In addition, compounds exemplified in JP2013-061599A [0037] (for example, alkoxyalkyl-α- (allyloxymethyl) acrylate) are also suitable. Among these, methyl α-allyloxymethyl acrylate (also referred to as α- (allyloxymethyl) methyl acrylate) is particularly preferable.

  The α- (unsaturated alkoxyalkyl) acrylate can be produced, for example, by a production method disclosed in International Publication No. 2010/114077.

  The content ratio of the monomer capable of introducing a ring structure into the main chain skeleton of the polymer (total ratio when two or more are used) is, for example, 1 to 40 mass with respect to 100 mass% of the base polymer component. % Or more is preferable. Thereby, heat resistance, a dispersibility, surface hardness, etc. can be improved further. In particular, the content ratio of N-substituted maleimide monomer, acrylic ether dimer, and / or α- (unsaturated alkoxyalkyl) acrylate (total ratio when two or more are used) is the above base polymer component. It is preferable that it is 1-40 mass% with respect to 100 mass%. When the content of the main chain ring structure derived from these monomer components increases, the adhesion tends to be improved. Further, when the addition amount of the N-substituted maleimide monomer is further increased, a cured product having higher hardness can be obtained, and when an acrylic ether dimer is used, a cured product having better heat resistance colorability can be obtained. If the content ratio of the N-substituted maleimide monomer is too large, the development speed may not be more appropriate. The content ratio of the N-substituted maleimide monomer, acrylic ether dimer, and / or α- (unsaturated alkoxyalkyl) acrylate is more preferably 2 to 30% by mass.

  As a method for polymerizing the monomer component, a commonly used technique such as bulk polymerization, solution polymerization, emulsion polymerization or the like can be used, and it may be appropriately selected according to the purpose and application. Among these, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. The polymerization mechanism of the monomer component may be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, but the polymerization method based on the radical polymerization mechanism is cyclized. The ratio (for example, (iii) the rate at which a monomer capable of introducing a ring structure into the main chain skeleton of the polymer is cyclized by a polymerization reaction) is high, and this is preferable because it is industrially advantageous. The polymerization concentration and polymerization temperature vary depending on the type and ratio of the monomers used and the molecular weight of the target polymer. Preferably, the polymerization temperature is 40 to 150 ° C., and the polymerization concentration is 20 to 80% by mass. More preferably, the polymerization temperature is set to 60 to 130 ° C., and the polymerization concentration is set to 30 to 60%.

  The polymerization time in the polymerization step is preferably 1 minute to 100 hours, more preferably 0.1 to 30 hours.

The polymerization step may be performed in the absence of a solvent or in the presence of a solvent, but it is preferable to perform the polymerization in the presence of a solvent, that is, to perform polymerization by a solution polymerization method. As the solvent, it is preferable to use an inactive compound in the polymerization and addition step. For example, benzene, toluene, N, N-dimethylformamide, dimethyl sulfoxide, acetone, 2-butanone (methyl ethyl ketone), methyl isobutyl ketone, methyl amyl Ketone, 1,4-dioxane, chloroform, carbon tetrachloride, tetrahydrofuran, ethyl acetate, trifluoromethylbenzene, 1-methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate, ethyl cellosolve, butyl cellosolve, 1-methoxy-2- Examples include organic solvents such as propanol and diacetone alcohol.
-Additional process-
(Iv) Compound having a vinyl ether group In a preferred embodiment of the present invention, by adding a vinyl ether compound to the carboxyl group-containing polymer, the glass transition temperature is lowered, and the effect of improving curability at the time of heating in the film forming step is obtained. Be expected. As a compound having a vinyl ether group to be added to a carboxyl group-containing polymer, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl Vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl Alkyl vinyl ethers such as vinyl ether; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether; cyclohexyl vinyl ether, cyclohexane dimethanol mono Examples include vinyl ethers containing alicyclic compounds such as vinyl ether; and allyl group-containing vinyl ethers such as allyl vinyl ether.
Moreover, it becomes possible to introduce | transduce a photosensitive group into the side chain of the said carboxyl group containing polymer by using the compound which has a (meth) acryloyl group as a vinyl ether compound. That is, Y in the above formula (2) as a structural unit is preferably an organic residue having a (meth) acryloyl group. Thereby, the sensitivity with respect to light becomes high, and the effect which improves the developability at the time of film-forming and the crosslinking | crosslinked property of a coating film can be anticipated. Examples of the compound having a (meth) acryloyl group and a vinyl ether group include the following general formula (5);

（式中、Ｒ_１は、水素原子又はメチル基を表す。Ｒ_２は、有機残基を表す。Ｒ_３は、水素原子又は有機残基を表す。）で表される（メタ）アクリル酸エステル類等が好適である。

(In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents an organic residue. R ₃ represents a hydrogen atom or an organic residue.) (Meth) acrylic acid ester Etc. are preferred.

Examples of the organic residue represented by R ₂ include a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, and a halogenated group having 2 to 8 carbon atoms ( For example, a chlorinated, brominated or fluorinated alkylene group, a polyethylene glycol skeleton excluding a terminal hydroxyl group, a polypropylene glycol skeleton excluding a terminal hydroxyl group, a polybutylene glycol skeleton excluding a terminal hydroxyl group, and an aryl group are preferred. Among these, a skeleton excluding terminal hydroxyl groups from polyethylene glycol having a polymerization degree of 20,000 to 10,000, a skeleton excluding terminal hydroxyl groups from polypropylene glycol having a polymerization degree of 20,000 to 10,000, and a polybutylene having a polymerization degree of 20,000 to 10,000. A skeleton excluding the terminal hydroxyl group from glycol and an alkylene group having 2 to 4 carbon atoms are preferably used. More preferably, a skeleton excluding a terminal hydroxyl group from a polyethylene glycol having a polymerization degree of 2 to 100, a skeleton excluding a terminal hydroxyl group from a polypropylene glycol having a polymerization degree of 2 to 100, and a terminal from a polybutylene glycol having a polymerization degree of 2 to 100. skeleton excluding the hydroxyl group, an alkylene group having 2 carbon atoms _(-CH 2 _CH 2 -), an alkylene group having 3 carbon atoms _{(-CH 2 CH 2 CH 2 -} ), an alkylene group having 4 carbon atoms _(-CH 2 CH ₂ CH ₂ CH ₂ -) a. Most preferably, a skeleton excluding a terminal hydroxyl group from a polyethylene glycol having a polymerization degree of 2 to 15, a skeleton excluding a terminal hydroxyl group from a polypropylene glycol having a polymerization degree of 2 to 15, and a terminal from a polybutylene glycol having a polymerization degree of 2 to 15 skeleton excluding the hydroxyl group, an alkylene group having 2 carbon atoms _(-CH 2 _CH 2 -), an alkylene group having 3 carbon atoms _{(-CH 2 CH 2 CH 2 -} ), an alkylene group having 4 carbon atoms _(-CH 2 CH ₂ CH ₂ CH ₂ -) a.

The organic residue represented by R ₃ is not particularly limited. For example, the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and the aromatic group having a substituent having 6 to 11 carbon atoms. Etc. Among these, an alkyl group having 1 to 2 carbon atoms and an aromatic group having 6 to 8 carbon atoms are preferably used.

Specific examples of the compound represented by the general formula (5) include those described below.
(Meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4 -Vinyloxybutyl, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, (meth) acrylic acid 1,1-dimethyl-2-vinyloxyethyl, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate, 4- (meth) acrylic acid 4- Vinyloxycyclohexyl, 6-vinyloxyhexyl (meth) acrylate, (meth) acrylic 4-vinyloxymethylcyclohexylmethyl oxalate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, ( (Meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenylmethyl.
2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- (Vinyloxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) Ethyl, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate , (Meth) acrylic acid 2- (vinyloxyethoxyethoxy) pro 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, (meta ) 2- (vinyloxyisopropoxyisopropoxy) isopropyl acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) Acrylic acid -(Vinyloxyisopropoxyethoxy) ethyl, 2- (vinyloxyisopropoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid polyethylene glycol monovinyl ether, (meth) acrylic acid polypropylene glycol monovinyl ether, (meth) acrylic acid polybutylene glycol monovinyl ether.

  It is preferable to perform the said addition process in 0-150 degreeC temperature range. More preferably, it is 20-100 degreeC, More preferably, it is 20-80 degreeC. The polymerization time is preferably 1 minute to 100 hours, more preferably 0.1 to 30 hours.

  The addition reaction between the carboxyl group-containing polymer and the compound having a vinyl ether group is not particularly limited, and as an addition method when the addition reaction is performed, it may be charged all at the beginning of the reaction, either or both of them being continuously or You may add to a reaction system intermittently. In the above addition reaction, since the carboxyl group-containing polymer itself becomes a catalyst, the reaction can be carried out without a catalyst, but a catalyst can also be used in combination. Examples of the catalyst that can be used in the present invention include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, trichloroacetic acid, dichloroacetic acid, pyruvic acid, and glycolic acid; oxalic acid, maleic acid, and oxaloacetic acid. Aliphatic polycarboxylic acids such as malonic acid, fumaric acid, tartaric acid and citric acid; aromatic carboxylic acids such as benzoic acid and terephthalic acid; benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, Aromatic sulfonic acids such as p-toluenesulfonic acid quinolinium salt or salts thereof; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate; sodium hydrogen sulfate, potassium hydrogen sulfate, etc. Hydrogen sulphate; sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid Mineral acids such as polyphosphoric acid; heteropolyacids such as phosphovanadide molybdic acid, phosphotungstomolybdic acid, and cytungstomolybdic acid; acidic zeolite; base resin is phenolic resin or styrenic resin, gel type, porous type or macroporous Examples thereof include an acidic ion exchange resin having any form of a mold and having at least one ion exchange group selected from the group consisting of a sulfonic acid group and an alkylsulfonic acid group. These may be used alone or in combination of two or more. When a catalyst is used in combination, a hydrogen halide such as hydrochloric acid is preferable because the reaction can be accelerated without causing a cationic polymerization reaction.

  The amount of the catalyst used may be appropriately set depending on the compound having a vinyl ether group or the type or combination of the carboxyl group-containing polymer, from the viewpoint of yield, butterfly stability, productivity and economy. For example, it is preferable to set it as 0.0005-1 mass part with respect to 100 mass parts of compounds which have a vinyl ether group. More preferably, it is 0.001-0.5 mass part.

Before the addition reaction, a dehydration step in the reaction system may be performed. When water is present in the reaction system, the decomposition of the acetal compound produced by the reaction of adding a compound having a vinyl ether group to a carboxyl group-containing polymer proceeds, and a problem arises that a vinyl ether adduct cannot be obtained stably. . In order to suppress the decomposition of the acetal compound, a dehydration step may be performed before the addition reaction.
[Polymerizable monomer (B)]
A polymerizable monomer means a compound having a polymerizable group. A compound having a polymerizable double bond is preferable. Among these, from the viewpoint of photosensitivity and curability, a compound having two or more polymer double bonds in the molecule, that is, a bifunctional or higher polyfunctional polymerizable compound is preferable, and a trifunctional or higher polyfunctional compound is more preferable. A functional polymerizable compound, more preferably a polyfunctional compound having 4 or more functional groups.

  As the polyfunctional polymerizable compound, a compound having a (meth) acryloyl group is particularly preferable. Thereby, it becomes more excellent in photosensitivity and curability, and it becomes possible to give a hardened film with higher hardness. The (meth) acryloyl group means a methacryloyl group and / or an acryloyl group. In the present invention, those containing at least an acryloyl group are preferred from the viewpoint of better reactivity.

  The polyfunctional polymerizable compound preferably has a molecular weight (meaning an atomic weight equivalent (meaning a mass number of carbon atoms of 12.01)) of 700 or less, more preferably 650 or less, and even more preferably 600 or less. is there. Moreover, it is preferable that a double bond equivalent is 150 or less, More preferably, it is 140 or less, More preferably, it is 110 or less. The lower limit of the molecular weight and the double bond equivalent is not particularly limited as long as it can be cured. From the viewpoint of improving sensitivity, the molecular weight is preferably more than 250. Among them, a compound having a relatively small molecular weight and a small double bond equivalent is preferable from the viewpoint that an excellent pixel can be formed.

Preferable specific examples of the polymerizable compound include, for example, the following compounds.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meta) such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene ) Acrylate compounds;
Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Trifunctional or more polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;

  Among these, from the viewpoint of improving the balance of various physical properties, a trifunctional or higher polyfunctional (meth) acrylate compound is preferable, such as pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol tetra (meth) acrylate. It is particularly preferred to use dipentaerythritol penta (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate.

The content ratio of the polymerizable monomer is not particularly limited, and is preferably set as appropriate in consideration of the ratio of other components such as a coloring material. For example, the total solid content of the photosensitive resin composition is 100 parts by mass. On the other hand, it is preferably 5 to 90 parts by mass. Thereby, sclerosis | hardenability and transparency become higher. More preferably, it is 7-70 mass parts.
[Dye (C)]
In the present invention, a dye is preferably used as the coloring material. Although it does not specifically limit as said dye, For example, the organic dye described in Unexamined-Japanese-Patent No. 2010-9033, Unexamined-Japanese-Patent No. 2010-211198, Unexamined-Japanese-Patent No. 2009-51896, and Unexamined-Japanese-Patent No. 2008-50599 is used. Can be used. Of these, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like are preferable.

  The total amount of the dye is preferably 1% by mass or more with respect to 100% by mass of the total solid content of the photosensitive resin composition. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, and it becomes possible to fully respond to the recent demand for higher color purity and higher luminance. Although an upper limit is not specifically limited, From a viewpoint of fully exhibiting image forming properties, such as photosensitivity, solubility, and sclerosis | hardenability resulting from other containing components (for example, alkali-soluble resin and a polymerizable monomer), 80 It is preferable that it is below mass%. More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.

  You may mix | blend a pigment as coloring materials other than dye. Examples of the pigment include, but are not limited to, azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, Organic pigments such as quinophthalone, metal complex, diketopyrrolopyrrole, and dye lake pigments; white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), Chromatic pigments (yellow lead, cadmium, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, bengara, zinc chromate, red lead, ultramarine, bitumen, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.) , Black pigment (carbon black, bone black, graphite, iron , Titanium black, etc.), the luminous material pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, inorganic pigments strontium aluminate, etc.) and the like; and the like. Of these, organic pigments are preferred. The usage-amount of the said pigment can be suitably set according to the objective, for example, 1-90 mass parts can be mix | blended with respect to 100 mass parts of coloring materials.

The photosensitive resin composition of the present invention is characterized by containing at least the dye described above. For example, 10-100 mass parts is contained with respect to 100 mass parts of coloring materials. Thereby, it discovered that the brightness | luminance and contrast after film-forming were exhibited notably.
[Photoradical initiator (D)]
The photosensitive resin composition of the present invention preferably also contains a photoradical initiator (photopolymerization initiator).

Although it does not specifically limit as a photoinitiator, For example, the following compounds etc. are mentioned.
2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropane-1-one ON, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- (4-ethylphenyl) -2-methylpropan-1-one, 2- Dimethylamino-1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1 -(4-Methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- Benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Α-aminoketone compounds such as phenyl] -1-butanone; 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenylketone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propyl Lopan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4- Alkylphenone compounds such as methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone;
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and other halomethylated triazine compounds 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4 Halomethylated oxadiazole compounds such as oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole compounds such as biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and other oxime ester compounds; bis (η5-2,4-cyclopentadien-1-yl) -bis (2, 6-Difluoro-3- (1H-pyrrole-1- Yl) -phenyl) titanium compounds such as titanium; p-dimethylaminobenzoic acid, benzoic acid ester compounds such as p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; 1-hydroxycyclohexyl phenyl ketone, 1 -[4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl) Α-hydroxy ketone compounds such as -propionyl) -benzyl] phenyl} -2-methyl-propan-1-one;

  Among the above photopolymerization initiators, it is particularly preferable to use at least an α-aminoketone compound from the viewpoint of excellent adhesion and a cured film shape. Among the α-amino ketone compounds, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one and 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone are preferred, and 2-methyl-1 is more preferred. -(4-Methylthiophenyl) -2-morpholinopropan-1-one. As a commercially available product, for example, IRGACURE (registered trademark) 907, 369, 379 (all manufactured by BASF Japan Ltd.) and the like are preferable.

The content ratio of the photopolymerization initiator is not particularly limited, and is preferably set as appropriate in consideration of the ratio of other components such as a coloring material. For example, the total content of the photosensitive resin composition is 100 parts by mass. It is preferable that it is 0.5-30 mass parts. Thereby, sclerosis | hardenability and transparency are improved further. More preferably, it is 1-25 mass parts, More preferably, it is 1.5-20 mass parts.
[Solvent (E)]
It is preferable that the resin composition of the present invention also contains a solvent.
It does not specifically limit as a solvent, The various compounds mentioned above are mentioned as a specific example of the polymerization solvent at the time of obtaining alkali-soluble resin. Among these, it is preferable to use glycol monoether esters, monoalcohols, and / or glycol monoethers. More preferably, glycol monoether esters are used at least, and it is also suitable to use glycol monoether esters in combination with glycol monoethers.

The content rate of the said solvent is not specifically limited, It is preferable to set suitably according to the usage form (for example, application | coating etc.) of the photosensitive resin composition. For example, the content ratio of the solvent is preferably set so that the total solid content (solid content concentration) in 100% by mass of the photosensitive resin composition is 1 to 90% by mass. The total solid content in 100% by mass of the photosensitive resin composition is more preferably 5 to 70% by mass.
[Dispersant (F)]
It is preferable that the photosensitive resin composition of the present invention also contains a dispersant. The dispersant is not particularly limited. For example, it has an interaction site to the color material and an interaction site to the dispersion medium (alkali-soluble resin, solvent, etc.), and stabilizes the dispersion of the color material in the dispersion medium. What has the function to do is preferable. In general, a dispersant that is classified into a resin-type dispersant (polymer dispersant), a surfactant (low-molecular dispersant), and a pigment derivative and that is usually used may be used.

  Examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , Long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, or a salt thereof, (meth) acrylic acid-styrene Copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide adduct, etc. All It is. Among them, from the structural aspect, a resin having a graft structure in which the main chain is an anchor chain having an interaction site with a coloring material and the graft chain is a compatible chain having an interaction property with a dispersion medium, A resin having a block structure with a compatible chain is particularly preferably used.

  Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate Surfactants; cationic boundaries such as alkyl quaternary ammonium salts and their ethylene oxide adducts Alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazolines; active agents.

  The dye derivative is a compound having a structure in which a functional group is introduced into the dye. Examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, and a phthalimide group. Examples thereof include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, and diketopyrrolopyrrole.

The content of the dispersant is not particularly limited, and may be set as appropriate depending on the purpose and application. For example, the balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.), transparency, and the like. In consideration of the above, it is preferable that the solid content of the dispersant is 0.01 to 60 parts by mass with respect to 100 parts by mass of the total solid content of the coloring material. More preferably, it is 0.1-50 mass parts, More preferably, it is 0.5-40 mass parts.
[Other ingredients (G)]
The photosensitive resin composition of the present invention may also contain one or more other components as long as the effects of the present invention are not impaired. For example, binder resins other than alkali-soluble resins; heat resistance improvers; leveling agents; coupling agents; development aids; fillers such as aluminum hydroxide, talc, clay and barium sulfate; antifoaming agents; sensitizers; Agents; lubricants; plasticizers; antioxidants; ultraviolet absorbers; flame retardants; polymerization inhibitors; thickeners;

  Although the usage-amount of said other component should just be suitably set according to the objective and a use, it is preferable that it is 0-70 mass% in 100 mass% of solid content total amount of the photosensitive resin composition, for example. More preferably, it is 0.01-70 mass%, More preferably, it is 0.1-60 mass%, Most preferably, it is 0.3-50 mass%.

In addition to the components described above, fillers, epoxy resins, other epoxy group-containing compounds, phenol resins, thermosetting compounds such as polyvinylphenol, and curing aids such as polyfunctional thiol compounds may be included. The thermosetting compound in the photosensitive resin composition of the present invention is preferably 5% by mass or less, more preferably 3% by mass or less, and most preferably based on 100% by mass of the total solid content of the photosensitive resin composition. Is preferably 1% by mass or less.
[Method for producing photosensitive resin composition]
It does not specifically limit as a manufacturing method of the photosensitive resin composition of this invention, For example, it can prepare by mixing and disperse | distributing the component mentioned above using various mixers and a disperser. A dispersion process and a mixing process are not specifically limited, What is necessary is just to perform by a normal method and may further include the other process normally performed.

  That is, an alkali-soluble resin (A) having a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2) as essential structural units, polymerizable It is a manufacturing method of the photosensitive resin composition which has the process of mixing a monomer (B), dye (C), and photoradical initiator (D).

（式中のＲ_１は水素原子または炭素数１〜３のアルキル基を表す。Ｘはカルボキシル基、スルホン酸基、フェノール性水酸基、カルボン酸無水物基、リン酸基などの酸性基を表す。）

(In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents an acidic group such as a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group. )

（式中のＲ_１は前記（１）中のＲ_１と同様であり、Ｒ_２は水素原子または有機残基を表す。Ｙは有機残基を表す。）
また、上記アルカリ可溶性樹脂（Ａ）は、カルボキシル基含有重合体と、上述したビニルエーテル基を有する化合物を反応させて得られるアルカリ可溶性樹脂であることが好ましい形態である。

(R ₁ in the formula is the same as R ₁ in the (1), R ₂ represents .Y represents a hydrogen atom or an organic residue represents an organic residue.)
The alkali-soluble resin (A) is preferably an alkali-soluble resin obtained by reacting a carboxyl group-containing polymer with the above-described compound having a vinyl ether group.

  Specifically, for example, after preparing a color material dispersion (mill base) containing a color material, a dispersant, a binder resin (alkali-soluble resin, etc.) and a solvent, a polymerizable monomer, a photopolymerization initiator is further prepared. It is preferable to prepare by adding a transparent resist solution (also referred to as a clear resist solution) containing a binder resin (alkali-soluble resin or the like) and a solvent. The obtained resin composition is preferably filtered with a filter or the like to remove fine dust.

In preparing the color material dispersion, it is preferable to finely disperse the color material using a disperser such as a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, or a blender. More preferably, after kneading and dispersing with a roll mill, kneader, blender or the like, fine dispersion with a media mill such as a bead mill filled with 0.01 to 1 mm beads.
[Use of photosensitive resin composition]
The photosensitive resin composition of the present invention is excellent in various physical properties such as transparency and heat resistance, and can provide a cured product having excellent solvent resistance and high level of surface smoothness. It can be used for various applications such as materials, various coating agents, and paints. Preferable uses include various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices and solid-state imaging devices, and electrical / electronic devices. Among these, the photosensitive resin composition is useful as a material for producing a color filter, an optical waveguide, and the like (for example, an alkali developing negative resist material). The display quality of various display devices and the reliability of imaging quality can be sufficiently enhanced to the extent that they can be sufficiently handled. In particular, the photosensitive resin composition is extremely useful for color filter applications.

  As described above, the photosensitive resin composition is preferably used as a raw material for a color filter or a raw material for an optical waveguide. In addition to these, a protective film (a protective film for a color filter, a touch panel display) It is also suitable to use as a protective film for devices, etc.) or an insulating film (insulating film for touch panel display devices, etc.).

<Curing film>
The cured film of the present invention is obtained by curing the above-described photosensitive resin composition of the present invention, and can be obtained by irradiating (exposing) an active energy beam to the resin composition. Specifically, for example, the resin composition is preferably applied on a substrate (also referred to as a base material), dried, and irradiated (exposed) with an active energy ray on the coated surface. Since the photosensitive resin composition of the present invention is suitably used as a resist material, the form in which the cured film obtained by curing the photosensitive resin composition is a resist cured film is one of the preferred forms of the present invention. is there.

An example of an embodiment having the cured film is a color filter having the cured film on a substrate. This production method will be described in detail below.
The members constituting the color filter specifically include three primary color (RGB) pixels, a resin black matrix, a protective film, a columnar spacer, etc. At least one of these members constituting the color filter is a book. It is preferable to have a cured film formed by the photosensitive resin composition of the invention. Here, when forming RGB pixels, the resin composition of the present invention contains three primary colors of red, green, and blue, and when forming a resin black matrix, it contains a black color.

The color filter can be produced as follows, for example.
1) A photosensitive resin composition is coated (coated) on a substrate by a known coating method and dried to prepare a coating film. A transparent substrate is preferable as the substrate, and specific examples include glass (preferably non-alkali glass) and transparent plastic. Known coating methods include spin coating and spraying, with spin coating being preferred. Regarding the drying conditions, the drying temperature is preferably room temperature to 120 ° C, more preferably 60 to 100 ° C. The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 10 minutes. Moreover, it is preferable to heat-dry under a normal pressure or a vacuum.
2) Then, a photomask (patterning film) provided with an opening corresponding to the desired pattern shape is placed on the coating obtained in 1) in a contact state or in a non-contact state and irradiated with light. , Cure. Light means not only visible light but also radiation such as ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are most preferred. In general, a high-pressure mercury lamp is preferably used as the ultraviolet ray source.
3) After the light irradiation of 2), development is performed with a solvent, water, an alkaline aqueous solution or the like. Among these, an aqueous alkali solution is preferable because it has a low environmental load and can be developed with high sensitivity. Although it does not specifically limit as an alkali component in alkaline aqueous solution, A potassium hydroxide, sodium hydroxide, and / or sodium carbonate etc. are preferable. The concentration of the alkali component is preferably 0.01 to 5% by mass in 100% by mass of the alkaline aqueous solution. When the concentration of the alkali component is within this range, the solubility of the alkali-soluble resin is further improved, and the developability (development speed) can be further increased. More preferably, it is 0.05-3 mass%, More preferably, it is 0.1-1 mass%. A surfactant may be added to the alkaline aqueous solution.
4) The above steps 1) to 3) are performed using a photosensitive resin composition containing a black color material to form a resin black matrix on the substrate.
5) Next, the colorants of the photosensitive resin composition are sequentially changed to red (R), green (G), and blue (B), and the above steps 1) to 3) are repeated, and R, G, B These pixels are formed to produce RGB pixels.
6) Next, a protective film is formed as necessary for the purpose of protecting the RGB pixels formed on the substrate and improving the surface smoothness.
7) When the color filter is a color filter for a liquid crystal display device, it is preferable to further form a column spacer. The columnar spacer can be produced by applying the photosensitive resin composition to a thickness that is the height of the desired spacer on the surface on which the spacer is to be formed, and performing the steps 1) to 3).

Here, when producing a color filter, when each member is produced, post-development heating (post-bake) is performed to further cure, and if the solvent remains, it can be completely removed. preferable. The temperature during post-baking is preferably 120 to 300 ° C. When this temperature is set, the smoothness of the coating film due to coloring and thermal decomposition of the pixels can be more sufficiently suppressed, and the curing further proceeds and the coating film strength is further increased. More preferably, it is 150-250 degreeC, More preferably, it is 180-230 degreeC. The post-baking may be performed after development in the formation of each member (after the above-mentioned 3 at the time of creating each member) or after all the members are formed.
<Display device member and display device>
The member for a display device and the display device of the present invention have the cured film, but may further include one or more other constituent members. In recent years, with the advancement of technology of display devices and the like, there is a strong demand for higher performance for each member used. However, if the photosensitive resin composition of the present invention is used, such needs are increased. Therefore, the display quality and imaging quality of various display devices can be sufficiently improved. Although it does not specifically limit as a display apparatus, For example, a liquid crystal display device, a solid-state image sensor, a touchscreen display apparatus etc. are suitable. As the touch panel display device, a capacitance type device is particularly preferable.

  The display device member may be a film-like single layer or multilayer member composed of the cured film, or a member in which another layer is combined with the single layer or multilayer member. Moreover, the member (for example, color filter etc.) which contains the said cured film in a structure may be sufficient.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight”, “%” means “% by weight (mass%, wt%)”, and “v” means “volume”.
1. Physical property evaluation of copolymer solution (alkali-soluble resin) (1) Weight average molecular weight: Mw
Tetrahydrofuran (THF) was used as an eluent with GPC (trade name: HLC-8220 GPC, manufactured by Tosoh Corporation), TSKgel SuperHZM-N (manufactured by Tosoh Corporation) was used as a column, and calculation was performed in terms of standard polystyrene.
(2) Concentration of solid content (nonvolatile content) About 0.3 g of the copolymer solution prepared in each production example was weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Thereafter, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Corp.), it was dried at 100 ° C. for 1.5 hours, and then allowed to cool in a desiccator, and the weight was measured. From the weight reduction amount, the weight (solid content concentration) of the solid content (resin) of the copolymer solution was calculated.
(3) Acid value 1.5 g of the copolymer solution prepared in each production example was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1 N aqueous KOH solution. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was determined from the solid content concentration (mgKOH / g).
2. Evaluation of physical properties of coating film (cured film) (1) Evaluation of adhesion The photosensitive resin composition was applied on a 10 cm square glass substrate by a spin coater and dried in an oven at 90 ° C. for 3 minutes. After drying, by a UV aligner (trade name: TME-150RNS, manufactured by TOPCON Co., Ltd.) equipped with a 2.0 kW ultra high pressure mercury lamp, with a photomask having a 100 μm line and space at a distance of 100 μm from the coating film , And irradiated with ultraviolet rays at an intensity of 100 mJ / cm ² (in terms of 365 nm illuminance). After UV irradiation, 0.05% aqueous potassium hydroxide solution is sprinkled on the coating film with a spin developer to dissolve and remove the unexposed area, and the remaining exposed area is developed by washing with pure water for 10 seconds. Thus, a line and space pattern was formed. About the obtained pattern, the minimum contact | adherence pattern was observed using the laser microscope (brand name: VK-9700, product made by Keyence Corporation).
(2) Photosensitive resin composition Solvent-resistant photosensitive resin composition was spin-coated on a 5 cm square glass substrate, dried at 90 ° C. for 3 minutes, exposed to 100 mJ with a high-pressure mercury lamp, and at 230 ° C. A heat treatment was performed for 30 minutes to obtain a thin film having a thickness of 5 μm. Then, it was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 80 ° C. for 15 minutes, and the hue of NMP eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) to determine the absorbance at 430 nm. (In other words, the amount of the color material exuded from the glass substrate was evaluated by measuring the absorbance of the NMP immersion liquid after the test). The lower the measured value, the smaller the amount of the color material component oozed and the better. The solvent resistance evaluation results of the coating films prepared with the respective photosensitive resin compositions are shown in Table 2 as Examples 1 to 7 and Comparative Examples 1 to 6.

3. Preparation 1 of alkali-soluble resin
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 25 g of N-benzylmaleimide (BzMI), 100 g of acrylic acid (AA), 125 g of cyclohexyl acrylate (CHA), t-butylperoxy-2-ethylhexanoate (product) Name: Perbutyl (registered trademark) O, manufactured by NOF Corporation, hereinafter also referred to as PBO) 5 g, 17.5 g of propylene glycol monomethyl ether acetate (PGMEA), 7.5 g of diethylene glycol ethyl methyl ether (EMDG) were charged and mixed. . In addition, 10 g of n-dodecyl mercaptan (n-DM), 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 0.7 g of Antage W-400 (manufactured by Kawaguchi Chemical Co., Ltd.) and 194 g of 2- (vinyloxyethoxy) ethyl acrylate (VEEA: made by Nippon Shokubai Co., Ltd.) as a polymerization inhibitor were charged into the reaction vessel at 40 ° C. It was made to react for 3 hours and the copolymer solution (A-1) was obtained. The weight average molecular weight (Mw) and acid value of the copolymer solution (A-1) are shown together with the copolymer solutions (A-2) to (A-7) and (B-1) to (B-6). Write in 1.
Production Example 2
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, (α-allyloxymethyl) methyl acrylate (AMA-M) 25 g, AA 100 g, CHA 125 g, PBO 5 g, PGMEA 17.5 g, and EMDG 7.5 g were added as a monomer composition to the monomer dropping tank and mixed. . Further, 2.5 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, Antage W-4000.7 g and VEEA 194 g were charged as a polymerization inhibitor in the reaction vessel and reacted at 40 ° C. for 3 hours to obtain a copolymer solution (A-2).
Production Example 3
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (MD) 25 g, AA 100 g, CHA 125 g, PBO 5 g, PGMEA 17.5 g, and EMDG 7.5 g were added as monomer compositions to the monomer dropping tank. The mixture was stirred and mixed. Further, 6.0 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, Antage W-4000.7 g and VEEA 194 g were charged as a polymerization inhibitor in the reaction vessel and reacted at 40 ° C. for 3 hours to obtain a copolymer solution (A-3).
Production Example 4
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 25 g of BzMI, 55 g of MAA, 75 g of benzyl methacrylate (BzMA), 95 g of methyl methacrylate (MMA), 5 g of PBO, 17.5 g of PGMEA, and 7.5 g of EMDG were added to the monomer dropping tank and stirred and mixed. Moreover, 8.0 g of n-dodecyl mercaptan n-DM, 49 g of PGMEA, and 21 g of EMDG were added to the chain transfer agent dropping tank as a chain transfer agent solution, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, Antage W-4000.7 g and VEEA 55.4 g as a polymerization inhibitor were charged into the reaction vessel and reacted at 40 ° C. for 3 hours to obtain a copolymer solution (A-4).
Production Example 5
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, BzMI25g, AA163g, CHA62.5g, PBO5g, PGMEA17.5g, EMDG7.5g was thrown into the monomer dropping tank as a monomer composition and mixed. Further, 10 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Subsequently, Antage W-4000.7g and VEEA 194g were prepared as a polymerization inhibitor in the reaction vessel and reacted at 40 ° C for 3 hours to obtain a copolymer solution (A-5).
Production Example 6
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 25 g of BzMI, 100 g of AA, 125 g of CHA, and 2 g of PBO were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, n-DM7.0g, PGMEA49g, and EMDG21g were thrown into the chain transfer agent dripping tank as a chain transfer agent solution, and as a chain transfer agent solution in the chain transfer agent dripping tank, and it stirred and mixed.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Subsequently, Antage W-4000.7g and 194g of butyl vinyl ether (BVE) were prepared as a polymerization inhibitor in the reaction vessel, and reacted at 40 ° C for 3 hours to obtain a copolymer solution (A-6).

Production Example 7
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, MMA96g, MAA55g, BzMA100.5g, PBO5g, PGMEA17.5g, and EMDG7.5g were thrown into the monomer dropping tank as a monomer composition and mixed. Moreover, 8.5 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were put into the chain transfer agent dropping tank as a chain transfer agent solution, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 0.7 g of Antage W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 55 g of VEEA were charged into the reaction vessel as a polymerization inhibitor and reacted at 40 ° C. for 3 hours to obtain a copolymer solution (A-5).
Production Example 8
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 25 g of BzMI, 100 g of AA, 125 g of CHA, 5 g of PBO, 17.5 g of PGMEA, and 7.5 g of EMDG were added as a monomer composition to the monomer dropping tank and mixed with stirring. Further, 10 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 125 g of glycidyl methacrylate (GMA), Antage W-4000.7 g as a polymerization inhibitor, and 1.4 g of triethylamine (TEA) as a catalyst were charged in a reaction vessel and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. . Then, it cooled to room temperature and obtained the copolymer solution (B-1).
Production Example 9
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, AMA-M25g, AA100g, CHA125g, PBO5g, PGMEA17.5g, and EMDG7.5g were thrown into the monomer dropping tank as a monomer composition and mixed. Further, 2.5 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 125 g of GMA, Antage W-4000.7 g as a polymerization inhibitor, and 1.4 g of TEA as a catalyst were charged in a reaction vessel and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (B-2).
Production Example 10
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, MD25g, AA100g, CHA125g, PBO5g, PGMEA17.5g, and EMDG7.5g were thrown into the monomer dropping tank as a monomer composition, and mixed with stirring. Further, 7.0 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 125 g of GMA, Antage W-4000.7 g as a polymerization inhibitor, and 1.4 g of TEA as a catalyst were charged in a reaction vessel and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (B-3).
Production Example 11
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 25 g of BzMI, 55 g of MAA, 75 g of BzMA, 95 g of MMA, 5 g of PBO, 17.5 g of PGMEA, and 7.5 g of EMDG were added as a monomer composition to the monomer dropping tank and mixed with stirring. Further, 7.0 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 42.5 g of GMA, Antage W-4000.7 g as a polymerization inhibitor, and 1.4 g of TEA as a catalyst were charged in a reaction vessel and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (B-4).
Production Example 12
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 25 g of BzMI, 162.5 g of AA, 62.5 g of CHA, 5 g of PBO, 17.5 g of PGMEA, and 7.5 g of EMDG were added as a monomer composition into the monomer dropping tank and mixed with stirring. Further, 10 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 125 g of GMA, Antage W-4000.7 g as a polymerization inhibitor, and 1.4 g of TEA as a catalyst were charged in a reaction vessel and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (B-5).
Production Example 13
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 25 g of BzMI, 42.5 g of AA, 20 g of CHA, 162.5 g of butyl acrylate (BA), 5 g of PBO, 17.5 g of PGMEA, and 7.5 g of EMDG were added to the monomer dropping tank and mixed. Further, 10 g of n-DM, 49 g of PGMEA, and 21 g of EMDG were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
259 g of PGMEA and 111 g of EMDG were charged into the reaction tank, and after the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise over 180 minutes. After aging at 90 ° C. for 30 minutes, 1.25 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the mixture was cooled to room temperature to obtain a copolymer solution (B-6).

４、感光性樹脂組成物の調製及び評価
実施例１
バインダー樹脂として、共重合体溶液（Ａ−１）３．７５ｇ（固形分換算）、重合性単量体としてジペンタエリスリトールヘキサアクリレート（共栄社化学社製、以下ＤＰＨＡと表す）３．７５ｇ、染料としてＮｅｐｔｕｎｅ Ｇｅｌｂ０７５（ＢＡＳＦジャパン社製）１．７５ｇ及び、光ラジカル開始剤としてエタノン,１−[９−エチル６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル]−１，−(０−アセチルオキシム)（商品名：ＩＲＧＣＵＲＥ ＯＸＥ０２、ＢＡＳＦジャパン社製、以下ＯＸＥ０２と表す）１．０ｇを加え、不揮発分濃度が２０重量％となるようにＰＧＭＥＡで希釈し、感光性樹脂組成物（実施例１）を調製した。組成を表２に記す。
実施例２〜７、比較例１〜６
バインダー樹脂として共重合体溶液（Ａ−２〜Ａ−７、Ｂ−１〜Ｂ−６）をそれぞれ用いたこと以外は、調製例（実施例１）と同様にして感光性樹脂組成物（実施例２〜７、比較例１〜６）を各々調製した。組成を表２に記す。

4. Preparation and evaluation of photosensitive resin composition Example 1
As binder resin, 3.75 g (converted to solid content) of copolymer solution (A-1), 3.75 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter referred to as DPHA) as a polymerizable monomer, and dye 1.75 g of Neptune Gelb075 (BASF Japan) and etanone, 1- [9-ethyl 6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1,-(0- Acetyl oxime) (trade name: IRGCURE OXE02, manufactured by BASF Japan Ltd., hereinafter referred to as OXE02) 1.0 g was added, diluted with PGMEA so that the nonvolatile content concentration was 20% by weight, and a photosensitive resin composition (Example) 1) was prepared. The composition is shown in Table 2.
Examples 2-7, Comparative Examples 1-6
A photosensitive resin composition (implemented in the same manner as in Preparation Example (Example 1)) except that the copolymer solutions (A-2 to A-7, B-1 to B-6) were used as binder resins, respectively. Examples 2-7 and Comparative Examples 1-6) were prepared respectively. The composition is shown in Table 2.

The photosensitive resin composition prepared above was transferred to a Duran bottle, the sealed sample was stored at 40 ° C. for 1 month, and a storage stability test was performed. The viscosity before and after the test was measured and the rate of change was calculated. The evaluation criteria are shown below.
○: Change rate is 100% ± 20%
Δ: Change rate is 100% ± 20-50%
X: The following was confirmed from the Examples and Comparative Examples in which the rate of change was 100% ± 50% or more.
Examples 1 to 5 and Comparative Examples 1 to 5 are mainly different depending on whether an addition monomer for introducing a side chain double bond into an alkali-soluble resin is derived from a vinyl ether compound or derived from a glycidyl compound. Under these differences, the results of evaluating the absorbance at a wavelength close to the maximum absorption wavelength of the color material used, the minimum adhesion pattern after development, and the solvent resistance of the coating film were compared. Examples 1 to 5 using an alkali-soluble resin into which a bond has been introduced have remarkably good results in both adhesion and solvent resistance. This is presumably because the glass transition temperature of the resin was lowered and the photosensitive group was located at a position farther from the main chain, which promoted cross-linking between molecules during post-baking.

The difference between Example 6 and Comparative Example 6 is the method of introducing a side chain butyl group, either by adding a vinyl ether compound or by copolymerizing acrylate. Since Example 6 has better adhesion and solvent resistance, it is more suitable to introduce a side chain butyl group by addition of a vinyl ether compound. This is presumably because the carboxyl group is regenerated by elimination of the vinyl ether compound during post-baking, and a cross-linking is formed by reaction with other carboxyl groups, hydroxyl groups, etc. in the composition.
Example 4 and Example 7 are comparisons regarding the presence or absence of the main chain ring structure of the alkali-soluble resin. Like Example 4, it can confirm that adhesiveness and solvent resistance are favorable by introduce | transducing a main chain ring structure. This is considered that the heterocyclic structure assists the adhesion to the substrate. In addition, it is considered that the heterocycle itself is combined with oxygen to reduce the inhibition of curing by oxygen, and as a result, the curing is promoted and the solvent resistance is improved.
Although not specified above, the cured film of the photosensitive resin composition obtained in the examples was excellent in transparency and heat resistance.

  The photosensitive resin composition of the present invention is excellent in curability, alkali developability and adhesion, and is suitable for resists for forming members in the field of electronic information, such as plating resists and color filter resists, and is solvent resistant. In particular, it is suitable for forming a color filter pixel (colored layer).

Claims (10)

Alkali-soluble resin (A) having a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2) as essential structural units, a polymerizable monomer A photosensitive resin composition comprising a body (B), a dye (C), and a photoradical initiator (D).

(R ₁ in the formula represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group.)

(R ₁ in the formula is the same as R ₁ in the (1), R ₂ represents .Y represents a hydrogen atom or an organic residue represents an organic residue.) 2. The photosensitive resin composition according to claim 1, wherein Y in the formula (2) is an organic residue having a (meth) acryloyl group. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) has a glass transition temperature of 0 ° C. or lower. The said alkali-soluble resin (A) has a ring structure in a principal chain, The photosensitive resin composition as described in any one of Claims 1-3 characterized by the above-mentioned. It is the photosensitive resin composition for color filters, The photosensitive resin composition as described in any one of Claims 1-4 characterized by the above-mentioned. A cured film obtained by curing the photosensitive resin composition according to claim 1. A member for a display device, comprising the cured film according to claim 6. A display device comprising the cured film according to claim 6. Alkali-soluble resin (A) having a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2) as essential structural units, a polymerizable monomer A method for producing a photosensitive resin composition, comprising mixing a body (B), a dye (C), and a photo radical initiator (D).

(R ₁ in the formula represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic anhydride group, or a phosphoric acid group.)

(R ₁ in the formula is the same as R ₁ in the (1), R ₂ represents .Y represents a hydrogen atom or an organic residue represents an organic residue.) 10. The photosensitive resin composition according to claim 9, wherein the alkali-soluble resin (A) is an alkali-soluble resin obtained by reacting a carboxyl group-containing polymer with a compound having a vinyl ether group. Method.