JP2018009059A - Curable resin composition and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that has a high level of development adhesion, also excels at curability, solvent resistance, transparency and the like, and is useful for various application including a color filter, and also provide a cured product of such a curable resin composition, and a color filter and a display device obtained using the cured product.SOLUTION: A curable resin composition contains a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator. The (meth) acrylate polymer contains a (meth) acrylate monomer unit having an alicyclic skeleton, a monomer unit having a hydroxy group, and a monomer unit having an active methylene group, but it is substantially free of a tertiary carbon-containing (meth) acrylate monomer unit.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition and its use.

Curable resin compositions that can be cured by heat or active energy rays are variously studied for various applications such as optical members, electrical machinery and electronic equipment, and are excellent in characteristics required for each application. Compositions are being developed. A color filter is an example of a specific application, and the color filter is a main member constituting a liquid crystal display device, a solid-state imaging device, etc., and is generally a substrate, which has at least three primary colors (red, green, and blue). In addition to a pixel and a resin black matrix that separates the pixel, the pixel includes a protective film and the like.

When performing pixel formation of a color filter using a curable resin composition, for each pixel color, (1) an application step of applying a curable resin composition to a substrate, and (2) a resist film formed by the application step In addition, after exposing the pattern through a photomask to cure the exposed portion, an exposure step for insolubilizing the cured portion, and (3) removing the unexposed portion with a developer, and then baking (baking) the exposed portion. Further, a developing and baking process step for curing is performed, and the same process is repeated for each color.

Considering application to such color filter applications, the curable resin composition has various physical properties such as curability, solvent resistance after curing, adhesion to the substrate, heat resistance and transparency. Is required. Therefore, a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, and the (meth) acrylate polymer is a tertiary carbon-containing (meth) acrylate monomer unit, a single unit having a hydroxyl group. A curable resin composition having a monomer unit and a monomer unit having an active methylene group has been developed (see Patent Document 1). In addition, resin compositions described in Patent Documents 2 and 3 have been developed as conventional curable resin compositions.

Japanese Patent Laid-Open No. 2006-29151 Japanese Patent No. 4645346 Japanese Patent Laid-Open No. 11-133600

The curable resin composition described in Patent Document 1 is excellent in various physical properties and extremely useful for color filter applications and the like, but can further exhibit adhesion after development (also referred to as development adhesion) as described later. There was room for ingenuity to do so. Further, the resin composition described in Patent Document 2 has problems in development adhesion, curability, transparency, and the like, and the resin composition described in Patent Document 3 has problems in curability, solvent resistance, and the like. It was.

The present invention has been made in view of the above situation, has a high development adhesion, is excellent in curability, solvent resistance, transparency, and the like, and is a curable resin useful for various applications such as a color filter. An object is to provide a composition. Another object of the present invention is to provide a cured product of such a curable resin composition, and a color filter and a display device using the cured product.

While this inventor examined the curable resin composition useful for various uses, such as a color filter, while the curable resin composition of patent document 1 is excellent in various physical properties, it is a cured film (coating film). It has been found that the development adhesiveness is not sufficient and there is a problem in this respect. This is probably due to the fact that the tertiary carbon-containing (meth) acrylate monomer constituting the polymer in the resin composition has high hydrophilicity, so that the developer can easily soak into the coating film. Therefore, a (meth) acrylate-based polymer (provided that a (meth) acrylate-based monomer unit having an alicyclic skeleton) is essential and includes a monomer unit having a hydroxyl group and a monomer unit having an active methylene group (however, When a resin composition containing this polymer, a polymerizable compound, and a photopolymerization initiator is used, the hydrophobicity of the polymer is probably It has been found that the adhesiveness can be remarkably improved and remarkably excellent development adhesiveness can be exhibited due to the fact that the developer is difficult to penetrate into the cured film (coating film) of the resin composition. Such a curable resin composition is excellent in curability, solvent resistance, transparency and the like, and thus is particularly useful for color filter applications, and is particularly suitable as a resin composition for forming color filter pixels. . Therefore, a cured product, a color filter, and a display device obtained by curing such a curable resin composition are extremely useful in the optical field, electrical machinery / electronic field, and can sufficiently meet the demand for higher performance in recent years. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a curable resin composition containing a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, and the (meth) acrylate polymer has an alicyclic skeleton (meth). A curable resin composition comprising an acrylate monomer unit, a monomer unit having a hydroxyl group and a monomer unit having an active methylene group, and substantially free of a tertiary carbon-containing (meth) acrylate monomer unit It is a thing.

The (meth) acrylate polymer preferably further contains a monomer unit having an acid group.

The (meth) acrylate polymer preferably has a ring structure in the main chain.

The (meth) acrylate polymer includes a (meth) acrylate monomer (a) having an alicyclic skeleton, a monomer (b) having a hydroxyl group, a monomer (c) having an active methylene group, an acid A monomer component comprising a monomer (d) having a group, a monomer (e) capable of forming a ring structure in the main chain, and another monomer (f) if necessary (however, 3 A polymer obtained by polymerizing a secondary carbon-containing (meth) acrylate-based monomer), the mass ratio of the monomer components (a / b / c / d / e / f) Is preferably 10 to 50/10 to 40/2 to 40/2 to 50/2 to 30/0 to 30 (provided that the total of a to f is 100% by mass).

The monomer having an active methylene group is preferably represented by the following formula (1).

In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom. X represents a divalent group represented by any of the following formulas (1-1) to (1-3). R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a divalent group represented by any of the following formulas (1-4) to (1-6). R ⁴ represents a cyano group (—CN), a nitro group (—NO ₂ ), or a group represented by the following formula (1-7) or (1-8). R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom.

The present invention is also a cured product obtained by curing the curable resin composition.
The present invention is also a color filter having the above cured product on a substrate.
The present invention is also a display device configured using the color filter.

The curable resin composition of the present invention has high development adhesion, is excellent in curability, solvent resistance, transparency and the like, and is useful for various applications such as a color filter. Therefore, the color filter and the display device having such a cured product (cured film) of the curable resin composition are very useful in the optical field, the electric machine / electronic field, and the like.

The present invention is described in detail below. A form in which two or three or more preferred forms of the present invention described below are combined is also a preferred form of the present invention.
In addition, in this specification, "the total amount of solid content of curable resin composition" is a component which forms hardened | cured material (The solvent etc. which volatilize at the time of formation of hardened | cured material are excluded) among the containing components of curable resin composition. ) Means the total amount.

[Curable resin composition]
Although the curable resin composition of this invention contains a (meth) acrylate type polymer, a polymeric compound, and a photoinitiator, these 1 type or 2 types or more can be used for these containing components, respectively. Further, if necessary, one or more other components may be further contained.
Hereinafter, each component will be described.

<(Meth) acrylate polymer>
The (meth) acrylate polymer includes a (meth) acrylate monomer unit having an alicyclic skeleton, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group. If necessary, another monomer unit may be further contained, and each monomer unit may be one type or two or more types. However, the tertiary carbon-containing (meth) acrylate monomer unit is substantially not included.
The monomer unit means a structural unit derived from the monomer. Specifically, for example, the polymerizable carbon-carbon dioxygen in the monomer is obtained by a polymerization reaction or a crosslinking reaction of the monomer. This means a structural unit in which a double bond (C═C) is a single bond (C—C). Hereinafter, each monomer unit will be described.

(I) (Meth) acrylate monomer unit having an alicyclic skeleton (meth) acrylate monomer unit having an alicyclic skeleton refers to a (meth) acrylate monomer having an alicyclic skeleton (hereinafter referred to as “a”). It is a structural unit derived from the monomer (a).

The monomer (a) is a compound having one or more (meth) acryloyl groups and an alicyclic skeleton (also referred to as an alicyclic structure) in one molecule. Although carbon number of alicyclic skeleton is not specifically limited, For example, 3-30 are preferable. More preferably, it is 6-20. The alicyclic skeleton may be either a heterocyclic ring structure (for example, an epoxy ring) or a monocyclic ring structure in which the ring skeleton is composed only of carbon elements, but is a monocyclic ring structure composed of the latter carbon atoms. It is preferable. The alicyclic skeleton may be either a saturated ring skeleton or an unsaturated ring skeleton, but is preferably a saturated ring skeleton.

Specific examples of the monomer (a) include cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and (3,4-epoxycyclohexyl). Methyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, pentacyclopentadecane dimethanol (Meth) acrylate, cyclohexanedimethanol di (meth) acrylate, norbornane dimethanol di (meth) acrylate, p-menthane-1,8-diol di (meth) acrylate, p-menthane 2,8-diol di (meth) acrylate, p-menthane-3,8-diol di (meth) acrylate, bicyclo [2.2.2] -octane-1-methyl-4-isopropyl-5,6-dimethylol di (meta ) Acrylate and the like. Above all, from the viewpoint of further improvement in development adhesion, versatility, availability, etc., cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate and / or tricyclodecanyl (meth) acrylate Is preferred.

In the (meth) acrylate polymer, the content ratio of the (meth) acrylate monomer unit having an alicyclic skeleton is, for example, 10 to 50% by mass with respect to 100% by mass of the total amount of all monomer units. Preferably it is. Thereby, the curability becomes more sufficient and the solvent resistance is improved, and the development adhesion is further improved. More preferably, it is 15-48 mass%, More preferably, it is 20-45 mass%.

(Ii) Monomer unit having a hydroxyl group A monomer unit having a hydroxyl group is a structural unit derived from a monomer having a hydroxyl group (hereinafter also referred to as monomer (b)). By including such a monomer unit, the curability of the curable resin composition is improved, and a cured product having excellent solvent resistance and transparency can be provided.

The monomer (b) is a monomer having one or two or more hydroxyl groups in one molecule. For example, hydroxyalkyl (meth) acrylate is preferable. Although carbon number which comprises a hydroxyalkyl group is not specifically limited, For example, 1-20 are preferable, More preferably, it is 1-12, More preferably, it is 2-6.

Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, methyl α-hydroxymethylacrylate, α-hydroxymethylacrylic Examples include ethyl acrylate, t-butyl α-hydroxymethyl acrylate, and t-amyl α-hydroxymethyl acrylate.

In the (meth) acrylate polymer, the content ratio of the monomer unit having a hydroxyl group is preferably, for example, 10 to 40% by mass with respect to 100% by mass of the total amount of all monomer units. Thereby, curability becomes more sufficient and solvent resistance improves. In addition, since the hydrophilicity is appropriate, it is possible to more sufficiently reduce the occurrence of defects during development (for example, peeling during development or roughening and whitening of the surface). More preferably, it is 10-35 mass%, More preferably, it is 15-30 mass%.

(Iii) Monomer unit having an active methylene group The monomer unit having an active methylene group is a structural unit derived from a monomer having an active methylene group (hereinafter also referred to as monomer (c)). is there. By including such a monomer unit, the solvent resistance and developability of the curable resin composition are improved.

The monomer (c) is a monomer having one or more active methylene groups in one molecule. For example, a compound represented by the above formula (1) is suitable. Thereby, it becomes possible to improve the sensitivity of the curable resin composition.

The formula (1), R ¹ and R ⁵ are the same or different and each represents a hydrogen atom, or represents a hydrocarbon group which may 1 to 24 carbon atoms which may contain heteroatoms. Among these, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, a hexoxy group, a cyclohexoxy group, or the following formula (1-9) To (1-11), more preferably a hydrogen atom or a methyl group.

R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. Among them, a single bond, a methylene group, an ethylene group, a propylene group, a butylene group, a propylene group, a hexylene group, a cyclohexylene group, an octylene group, a decylene group, or a dodecylene group is preferable, and a single bond, a methylene group is more preferable. Group or ethylene group.

Specifically, as the compound represented by the above formula (1), for example, compounds represented by the following formulas (2-1) to (2-16) are preferable.

In the above formulas (2-1) to (2-7) and (2-16), R ⁶ is the same or different and represents a hydrogen atom or a methyl group. That is, a compound that derives a structural unit composed of a methacryl group or a compound that derives a structural unit composed of an acryl group may be used. Among these compounds represented by the formulas (2-1) to (2-16), 2- (methacryloyloxy) ethyl acetoacetate (that is, a compound represented by the above formula (2-1), and R ⁶ Are particularly preferred. Moreover, you may use together the unsaturated compound which has an active methine group illustrated by Unexamined-Japanese-Patent No. 2007-34134.

In the (meth) acrylate polymer, the content ratio of the monomer unit having an active methylene group is preferably 2 to 40% by mass with respect to 100% by mass of the total amount of all monomer units, for example. is there. Thereby, the effect of solvent resistance is particularly exhibited, and the developability is also improved. In addition, when the content ratio is excessively large, when used in combination with a coloring material or a polyfunctional polymerizable monomer, it tends to be whitened when it is incompatible with these to form a cured film, and heat resistance coloring property Is not sufficiently exhibited, and the brightness when formed into a panel does not tend to be sufficient. More preferably, it is 3-30 mass%, More preferably, it is 4-20 mass%.

(Iv) Monomer unit having an acid group The (meth) acrylate polymer preferably further has a monomer unit having an acid group. The monomer unit having an acid group is a structural unit derived from a monomer having an acid group (hereinafter also referred to as monomer (d)). For example, an acrylic acid unit means a structural unit derived from acrylic acid when acrylic acid is copolymerized or graft polymerized.

The monomer (d) is a monomer having one or two or more acid groups in one 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. Of these, a carboxyl group or a carboxylic anhydride group is preferable, a carboxyl group is more preferable, and a (meth) acrylic acid group is still more preferable.

Particularly preferred as the monomer (d) is (meth) acrylic acid. That is, the monomer unit having an acid group is preferably a (meth) acrylic acid unit. Thus, the form in which the said (meth) acrylate type polymer further contains a (meth) acrylic acid unit is one of the suitable forms of this invention. (Meth) acrylic acid means acrylic acid and / or methacrylic acid. Among them, acrylic acid is preferable to methacrylic acid in terms of solvent resistance.

Here, the acid value (AV) of the (meth) acrylate polymer is preferably 20 to 300 mgKOH / g. Thereby, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having better developability. In particular, when the acid value is in this range, the solvent resistance is further improved, the development speed is moderate, the adhesion is further improved, and the possibility of surface roughness during development is further suppressed. Can do. Moreover, solvent resistance further improves by setting content of the monomer unit (preferably (meth) acrylic acid unit) which has an acid group so that an acid value may become this range. The acid value is more preferably 60 to 160 mgKOH / g.

In the (meth) acrylate polymer, the content ratio of the monomer unit having an acid group (preferably a (meth) acrylic acid unit) is within the preferable range described above for the acid value of the (meth) acrylate polymer. It is preferable to set so as to be. For example, it is preferable that it is 2-50 mass% with respect to 100 mass% of total amounts of all the monomer units. More preferably, it is 5-40 mass%, More preferably, it is 8-30 mass%.

(V) Main chain ring structure The (meth) acrylate polymer preferably has a ring structure in the main chain. As a result, it is possible to obtain a cured product that is superior in heat resistance, surface hardness, and adhesiveness, and that, for example, changes with time after exposure to high temperatures are further suppressed and various physical properties can be expressed more stably. In recent display devices, tempered glass may be used for the substrate in order to give various members strength to withstand external impacts, but the main chain has a ring structure as the (meth) acrylate polymer. Use of the polymer having a polymer is very suitable because a cured product capable of exhibiting excellent adhesion to tempered glass even after high temperature exposure is obtained.

Suitable examples of the ring structure include an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, and a lactone ring. In addition, you may have 1 or 2 or more ring structures in a principal chain.

When the (meth) acrylate-based polymer has a ring structure in the main chain, the polymer is, for example, a single monomer that can form a ring structure in the main chain as a polymerization component (that is, a monomer component used for polymerization). It can be obtained by using at least one kind of body (also referred to as a monomer or a monomer (e) capable of introducing a ring structure into the main chain).

Examples of the monomer (e) include a monomer having a double bond-containing ring structure in the molecule, and a monomer that forms a polymer having a ring structure in the main chain by cyclopolymerization. Can be mentioned. Specifically, at least one selected from the group consisting of N-substituted maleimide monomers, acrylic ether dimers, and α- (unsaturated alkoxyalkyl) acrylate monomers is preferred. In this case, the (meth) acrylate polymer is a polymer having an N-substituted maleimide monomer unit, an acrylic ether dimer unit, and / or an α- (unsaturated alkoxyalkyl) acrylate monomer unit. It becomes. Among these, for example, when having an N-substituted maleimide monomer unit and / or an acrylic ether dimer unit, a cured film having improved heat resistance, hardness, dispersibility (for example, colorant dispersibility) and the like can be provided. Is possible. When it has an acrylic ether dimer unit, the heat resistant colorability of the cured product (cured film) is improved. In addition, having an α- (unsaturated alkoxyalkyl) acrylate monomer unit contributes to plate-making properties such as adhesion, curability, and dry redissolvability, colorant dispersibility, heat resistance, and transparency. It becomes possible to give a cured film with improved and the like.

(V-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 the 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;

(V-2) Acrylic ether dimer As the acrylic ether dimer, for example, a compound represented by the following general formula (3) is preferable.

In said formula, R < ⁷ > and R <^8> are the same or different, and represent the C1-C25 organic group which may have a hydrogen atom or a substituent. The organic group having 1 to 25 carbon atoms is preferably a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. For example, linear or branched alkyl groups exemplified in JP2013-61599A [0037]; aryl groups; alicyclic groups; alkyl groups substituted with alkoxy; alkyl substituted with aryl groups 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.
R ⁷ and R ⁸ may be the same 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 viewpoints of little coloring, dispersibility, industrial availability, and the like, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate is more preferable.

(V-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.

As the α- (allyloxymethyl) acrylate, for example, a compound represented by the following general formula (4) is suitable.

In the above formula, R ⁹ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms which may have a substituent. In the present specification, “α- (allyloxymethyl) acrylate” includes a compound in which R ⁹ represents a hydrogen atom (that is, α-allyloxymethylacrylic acid).

The R ⁹ may be appropriately selected according to the purpose and application, but as the organic group having 1 to 30 carbon atoms that can be represented by R ⁹ , carbon atoms having 1 to 30 carbon atoms which may have a substituent. A hydrogen group is preferred. 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 monomer can be produced, for example, by the production method described in International Publication No. 2010/114077 pamphlet.

In the (meth) acrylate polymer, the content ratio of monomer units capable of forming a ring structure in the main chain is preferably 2 to 30% by mass in 100% by mass of the total amount of all monomer units. . Thereby, the development adhesiveness is further improved, and the light-resistant adhesiveness and hardness are further improved. More preferably, it is 5-25 mass%, More preferably, it is 5-20 mass%.

(Vi) Other monomer units The above (meth) acrylate polymer may also contain one or more structural units derived from other monomers (hereinafter also referred to as monomer (f)), if necessary. Two or more kinds may be included.

The monomer (f) is not particularly limited. For example, other (meth) acrylic acid ester monomers that do not correspond to the monomers (a) to (e) described above, and aromatic vinyl monomers. Monomers and other copolymerizable monomers. Of these, (meth) acrylic acid ester monomers are preferred.

The (meth) acrylic acid ester monomer is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth) N-butyl acrylate, s-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylic acid phenyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, 1,4-Dioxaspiro [4,5] dec-2-yl (meth) acrylic in addition to phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate Acid, (meth) acryloylmorpholine, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1, Examples include 3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, and the like. It is done. Among them, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate are easy to balance heat resistance, colorant dispersibility, and solvent resolubility. And / or aralkyl (meth) acrylates such as benzyl (meth) acrylate are preferred.

Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, methoxy styrene, and the like. Of these, styrene and vinyltoluene are preferable from the viewpoint of heat resistance coloring property and heat decomposition property of the resin.

Although it does not specifically limit as said other copolymerizable monomer, For example, (meth) acrylamides, such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; Polystyrene, polymethyl (meth) acrylate , Macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain such as polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone and polycaprolactam; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl Nyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and other vinyl ethers; N-vinylpyrrolidone, N-vinyl N-vinyl compounds such as caprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate; and the like.

In the (meth) acrylate polymer, the content ratio of other monomer units is preferably 0 to 30% by mass with respect to 100% by mass of all monomer units, for example. More preferably, it is 0-20 mass%, More preferably, it is 0-10 mass%, Most preferably, it is 0-5 mass%.

Here, the (meth) acrylate polymer does not substantially contain a tertiary carbon-containing (meth) acrylate monomer unit. The term “substantially free of tertiary carbon-containing (meth) acrylate-based monomer units” as used herein means that the tertiary carbon-containing (meth) acrylate-based monomer units are not sufficiently effective. Meaning that it may contain (for example, the case where the monomer unit is included as an impurity-derived component), specifically, the total monomer component contained in the (meth) acrylate-based polymer is 100% by mass. On the other hand, the content of the tertiary carbon-containing (meth) acrylate monomer unit is less than 5% by mass. This content is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. While the (meth) acrylate polymer does not substantially contain a tertiary carbon-containing (meth) acrylate monomer unit, it essentially contains a (meth) acrylate monomer unit having an alicyclic skeleton. Therefore, remarkably high development adhesion can be exhibited with respect to the developer.

In order to obtain a (meth) acrylate polymer that does not substantially contain a tertiary carbon-containing (meth) acrylate monomer unit, a single substance that does not substantially contain a tertiary carbon-containing (meth) acrylate monomer. It is preferred to polymerize the monomer component. The term “substantially free of a tertiary carbon-containing (meth) acrylate monomer” as used herein means that a tertiary carbon-containing (meth) acrylate-based monomer is used with respect to 100% by mass of all monomer components used for polymerization. It means that the content of the monomer is less than 5% by mass. This content is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less.

In this specification, a tertiary carbon-containing (meth) acrylate monomer unit means a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer, and a tertiary carbon-containing (meth) acrylate. The system monomer is a compound having one or more (meth) acryloyl groups and tertiary carbon atoms in one molecule. The tertiary carbon atom means a carbon atom having three other carbon atoms bonded to the carbon atom. The details of the tertiary carbon-containing (meth) acrylate monomer are as described in JP-A-2006-29151 [0015] to [0020].

The (meth) acrylate polymer in the present invention is preferably a monomer containing the monomers (a), (b) and (c) and substantially free of a tertiary carbon-containing (meth) acrylate monomer. A polymer obtained by polymerizing a monomer component. In addition, a polymer obtained by reacting this polymer (also referred to as a base polymer) with a compound having a functional group capable of bonding to an acid group and a polymerizable double bond (also referred to as a side chain double bond-containing polymer). This side chain double bond-containing polymer is also included in the (meth) acrylate polymer of the present invention. In addition, the monomer and compound of a raw material can use 1 type (s) or 2 or more types, respectively.

The monomer component contains the monomers (a), (b) and (c), but preferably further contains the monomer (d) and / or (e), and the monomer (d) And (e) are more preferable. That is, the (meth) acrylate polymer is a monomer component (provided that the tertiary carbon-containing (meth) is composed of the monomers (a) to (e) and, if necessary, the monomer (f). A polymer obtained by polymerizing (substantially free of an acrylate monomer) is particularly preferable. In this case, the mass ratio of monomer components (a / b / c / d / e / f) is 10 to 50/10 to 40/2 to 40/2 to 50/2 to 30/0 to 30. It is preferable (however, the sum of a to f is 100% by mass). More preferably 15 to 48/10 to 35/2 to 30/5 to 40/5 to 25/0 to 20, still more preferably 20 to 45/15 to 30/4 to 20/8 to 30/5 to 20 / 0-10.

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 preferred because it is industrially advantageous and structural adjustments such as molecular weight are 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 industrial. Is also preferable. A preferable form of the polymerization reaction is as described in JP-A-2006-29151 [0062] to [0072].

As described above, when the (meth) acrylate polymer is a side chain double bond-containing polymer, it is preferable because development adhesion and solvent resistance are further improved as the number of crosslinking points increases. Such a (meth) acrylate polymer can be obtained by reacting the base polymer with a compound having a functional group capable of bonding to an acid group and a polymerizable double bond.

Examples of the polymerizable double bond in the compound having a functional group capable of binding to the acid group and a polymerizable double bond include (meth) acryloyl group, vinyl group, allyl group, methallyl group, and the like. Those having one or more of these are preferred. Of these, a (meth) acryloyl group is preferable in terms of reactivity. Moreover, as a functional group which can couple | bond with an acid group, a hydroxyl group, an epoxy group, oxetanyl group, an isocyanate group etc. are mentioned, for example, What has these 1 type (s) or 2 or more types as the said compound is suitable. Of these, epoxy groups (including glycidyl groups) are preferred from the viewpoint of the speed of the modification treatment reaction, heat resistance, and dispersibility.

Examples of the compound having a functional group capable of binding to the acid group and a polymerizable double bond include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, Examples thereof include vinyl benzyl glycidyl ether, allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide, and the like, and one or more of these can be used. Among these, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group. In particular, glycidyl (meth) acrylate and / or (and) having high reactivity and being easy to control, easily available, and capable of introducing not only radical polymerizable double bonds but also hydroxyl groups at the same time. More preferred is (meth) acrylic acid 3,4-epoxycyclohexylmethyl.

The addition amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond is preferably 2 to 60 mass with respect to 100 mass parts of the total amount of the monomer component (base polymer component) giving the base polymer. Part. When the added amount of the compound is within this range, the curability is further increased, and the strength after curing is more sufficient. More preferably, it is 10 parts by mass or more. The upper limit is more preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less.

The method of reacting a compound having a functional group capable of bonding to an acid group and a polymerizable double bond with (a part of) the acid group in the base polymer is not particularly limited as long as a known addition method or the like is employed. . The reaction temperature is preferably, for example, 60 ° C to 140 ° C. It is also preferable to use a known catalyst such as an amine compound such as triethylamine or dimethylbenzylamine; an ammonium salt such as tetraethylammonium chloride; a phosphonium salt such as tetraphenylphosphonium bromide; an amide compound such as dimethylformamide;

In the present invention, the (meth) acrylate polymer preferably has a polystyrene-equivalent weight average molecular weight of 3000 to 100,000. Thereby, there exists a tendency for the applicability | paintability at the time of apply | coating curable resin composition to become favorable, and it becomes difficult to produce a film reduction at the time of image development. More preferably, it is 3000-50,000. As a result, better developability can be exhibited, solvent resistance is improved, and development speed is further increased. More preferably, it is 5000 to 40,000, and particularly preferably 10,000 to 30,000.

The (meth) acrylate polymer also preferably has a molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.1 to 6.0. When the molecular weight distribution is in this range, the developability tends to be excellent. More preferably, it is 1.2-4.0.
In the present specification, the weight average molecular weight and the number average molecular weight of the polymer can be determined according to the measurement method (GPC method) described in Examples described later.

In the curable resin composition of the present invention, the content ratio of the (meth) acrylate polymer may be appropriately set according to the use and the blending of other components. For example, the solid content of the (meth) acrylate polymer The content is preferably 5% by mass or more with respect to 100% by mass of the total solid content of the curable resin composition. Moreover, it is suitable that it is 80 mass% or less. By being in such a range, it becomes possible to show the effect of the present invention more remarkably. More preferably, it is 7-70 mass%, More preferably, it is 10-60 mass%.
In the present invention, an acrylic polymer usually used in this field may be used in combination with the (meth) acrylate polymer as long as the effects of the present invention are not impaired.

<Polymerizable compound>
The curable resin composition of the present invention also contains a polymerizable compound. The polymerizable compound is also referred to as a polymerizable monomer, and can be polymerized by irradiation with active radicals such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays), electron beams, etc. A low molecular compound having a polymerizable unsaturated group). For example, the monofunctional compound which has one polymerizable unsaturated group in a molecule | numerator, and the polyfunctional compound which has 2 or more are mentioned.

As the monofunctional polymerizable monomer, for example, among the compounds exemplified as other monomers preferably contained in the monomer component of the (meth) acrylate polymer, an N-substituted maleimide monomer Or (meth) acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended; Saturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; A monomer having an active methylene group or an active methine group can also be used.

Examples of the polyfunctional polymerizable monomer include 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 (meth) acrylate compounds such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate;

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 higher polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrile Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, polyfunctional vinyl ethers such as ethylene oxide adduct of dipentaerythritol hexavinyl ether;

(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, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, ( Vinyl ether group-containing (meth) acrylic such as p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, and 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate Acid esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethyl Lumpur propane tetra allyl ether, ethylene oxide adduct of pentaerythritol tetra-allyl ether, polyfunctional allyl ethers such as ethylene oxide adduct of dipentaerythritol hexa-allyl ether;

Allyl group-containing (meth) acrylic esters such as allyl (meth) acrylate; tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene Polyfunctional (meth) acryloyl group-containing isocyanurates such as oxide-added tri (methacryloyloxyethyl) isocyanurate; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. Polyfunctional isocyanate and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and other hydroxyl-containing (meth) acrylate esters Multifunctional urethane (meth) acrylates obtained by reaction of a; polyfunctional aromatic vinyl compounds such as divinylbenzene; and the like.

Among the polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further improving the curability of the curable resin composition. When a polyfunctional polymerizable compound is used as the polymerizable compound, the functional number is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less.
The molecular weight of the polymerizable compound is not particularly limited, but is preferably 2000 or less from the viewpoint of handling.

When a polyfunctional polymerizable compound is used as the polymerizable compound, among the polymerizable compounds, from the viewpoint of reactivity, economy, availability, etc., a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate It is preferable to use a compound having a (meth) acryloyl group such as a compound or a (meth) acryloyl group-containing isocyanurate compound. More preferably, it is a polyfunctional (meth) acrylate compound, whereby the curable resin composition becomes more excellent in photosensitivity and curability, and it becomes possible to obtain a cured product having higher hardness and transparency. . More preferably, a trifunctional or higher polyfunctional (meth) acrylate compound is used.

In the curable resin composition of the present invention, the content ratio of the polymerizable compound may be appropriately set according to the purpose and application in addition to the type of the polymerizable compound and (meth) acrylate polymer to be used. From the viewpoint of being more excellent in properties and plate making properties, it is preferably 2% by mass or more, and more preferably 80% by mass or less with respect to 100% by mass of the total solid content of the curable resin composition. The lower limit is more preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 10% by mass or more, and the upper limit is more preferably 70% by mass or less, still more preferably 60% by mass or less, particularly preferably. Is 50% by mass or less, and most preferably 40% by mass or less.

<Photopolymerization initiator>
The curable resin composition of the present invention further contains a photopolymerization initiator. The photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator.

The radical polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or more commonly used ones may be used. it can. Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. A photosensitizer and / or photoradical polymerization accelerator may be used together with the photopolymerization initiator, or may not be used. Even if a photosensitizer and / or a radical photopolymerization accelerator are not used in combination, the effects of the present invention can be sufficiently exerted, but when used together, sensitivity and curability are further improved.

Specific examples of the photopolymerization initiator include the following compounds.
2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-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-methylphenyl) methyl] -1- [4- (4-morpholinyl) fur Nyl] -1-butanone and other alkylphenone compounds; benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzophenone compounds such as 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Benzoin compounds such as isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone;

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- ( Oxime ester compounds such as 2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); oxime ether compounds; bis (η5-2,4-cyclopentadien-1-yl ) -Bis (2 Titanocene compounds such as 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium; benzoate compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; 9-phenylacridine and the like An acridine compound;

Among the photopolymerization initiators, it is preferable to use an alkylphenone compound, an oxime ester compound, and / or an oxime ether compound. The oxime ester compound and the oxime ether compound are collectively referred to as “oxime compound”. However, when the oxime compound is used, the curability of the curable resin composition is remarkably improved and the solvent resistance of the resulting cured product is improved. Sexually improves. The effect obtained by using such an oxime compound is a unique effect when used in combination with a (meth) acrylate polymer having a monomer unit having an active methylene group. Thus, the form in which the said photoinitiator contains an oxime type compound at least is one of the suitable forms of this invention. Among oxime compounds, oxime ester compounds are particularly suitable.

In the curable resin composition of the present invention, the content of the photopolymerization initiator is not particularly limited as long as it is appropriately set depending on the purpose, application, etc., but the solid content of the curable resin composition excluding the photopolymerization initiator The total amount is preferably 0.1 parts by mass or more with respect to 100 parts by mass. Thereby, the hardened | cured material excellent by adhesiveness can be obtained, and peeling is suppressed more fully even after high temperature exposure. In consideration of the balance between the influence of the decomposition product of the photopolymerization initiator, economy, and the like, the amount is preferably 30 parts by mass or less. The lower limit is more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, and the upper limit is more preferably 25 parts by mass or less, and still more preferably 20 parts by mass or less. is there.

Examples of the photosensitizer and photoradical polymerization accelerator that may be used in combination with the photopolymerization initiator include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; 4-dimethylamino And dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole; .

The photosensitizer and the radical photopolymerization accelerator do not have to be used as described above. However, in the case of using the photosensitizer and the photoradical polymerization accelerator, a curable resin is used from the viewpoint of balance between curability, influence of decomposition products, and economy. It is preferable that it is 0.001-20 mass% with respect to 100 mass% of solid content total amount of a composition. More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

<Other ingredients>
-Solvent-
The curable resin composition of the present invention preferably also contains a solvent. A solvent is preferably used as a diluent or the like. Specifically, the viscosity is lowered to improve the handleability; the coating film is formed by drying; the coloring material is used as a dispersion medium; and each of the components contained in the curable resin composition is suitably used. Is a low-viscosity organic solvent or water capable of dissolving or dispersing.

As the solvent, one or two commonly used solvents can be used, and the solvent is not particularly limited as long as it is appropriately selected according to the purpose and application. For example, monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; esters of glycol monoethers; alkyl esters; ketones; aromatic hydrocarbons; Water; etc. are preferred. Specific examples of these solvents include compounds described in JP-A-2015-42697 [0042]. For example, glycol monoether esters include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl Le acetate and the like.

The amount of the solvent used may be appropriately set according to the purpose and application, and is not particularly limited, but is 10 to 90% by mass in the total amount of 100% by mass of the curable resin composition of the present invention. It is preferable to do. More preferably, it is 20-80 mass%.

The curable resin composition of the present invention further has, for example, a colorant (also referred to as a colorant); a dispersant; a heat resistance improver; a leveling agent; a development aid; Inorganic fine particles such as silica fine particles; Coupling agents such as silane, aluminum and titanium; Thermosetting resins such as fillers, epoxy resins, phenol resins and polyvinylphenols; Curing aids such as polyfunctional thiol compounds; Plasticizers Polymerization inhibitor, ultraviolet absorber, antioxidant, matting agent, antifoaming agent, antistatic agent, slip agent, surface modifier, thixotropic agent, thixotropic agent, quinonediazide compound, polyhydric phenol compound; 1 type, or 2 or more types, such as a cationically polymerizable compound; acid generator; For example, when using the said curable resin composition for a color filter use, it is preferable that a coloring material is included. Thus, the form in which the curable resin composition further contains a color material is also one of the preferred forms of the present invention. A form containing at least one selected from the group consisting of a colorant, a dispersant, a heat resistance improver, a leveling agent, a coupling agent, and a development aid is also suitable.

As the color material, for example, pigments and dyes are preferably used. These may be used alone or in combination of two or more. Moreover, you may combine a pigment and dye. For example, when forming red, blue, and green pixels of a color filter, a technique that exhibits color characteristics obtained by combining color materials, such as blue and purple, green and yellow, is preferably used. Further, when forming a black matrix, it can be formed using a black color material. Among pigments and dyes, for example, pigments (for example, organic pigments or inorganic pigments) are excellent in terms of durability, and, for example, dyes are excellent in terms of improving luminance of panels and the like. May be selected or used in combination. Among the pigments, an organic pigment is more preferable.

Preferred examples of the pigments and dyes and the content ratio of the coloring material are as described in JP-A-2016-29151 [0101] to [0105]. The dispersants are classified into resin-type dispersants (for example, polymer dispersants), surfactants (for example, low-molecular dispersants), and pigment derivatives. These preferable examples, content ratios, and other Preferred examples of the additive are as described in JP-A-2006-29151 [0106] to [0116].

<Manufacturing method>
It does not specifically limit as a manufacturing method of the curable resin composition of this invention, For example, it can prepare by mixing and disperse | distributing the containing component mentioned above using various mixers and dispersers. The mixing / dispersing step is not particularly limited, and may be performed by a normal method. Further, it may further include other steps that are normally performed. In addition, when the said curable resin composition contains a color material, it is suitable to manufacture through the dispersion | distribution process process of a color material.

Examples of the color material dispersion treatment step include, first, weighing each of a predetermined amount of a color material (preferably an organic pigment), a dispersant, and a solvent, and then paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender. And the like, and using a dispersing machine such as a method, a color material is dispersed in fine particles to form a liquid color material dispersion (also referred to as a mill base). Preferably, after kneading and dispersing with a roll mill, kneader, blender or the like, fine dispersion is performed with a media mill such as a bead mill filled with 0.01 to 1 mm beads. A (meth) acrylate polymer, a polymerizable compound (polymerizable monomer), a photopolymerization initiator, and a solvent and a leveling agent as necessary, which were separately stirred and mixed with the obtained mill base. A curable resin composition can be obtained by adding a composition (preferably a transparent liquid) containing, etc., and mixing to obtain a uniform dispersion solution.
The obtained curable resin composition is preferably filtered with a filter or the like to remove fine dust.

[Cured product]
The curable resin composition of the present invention has high development adhesion, and is excellent in various physical properties such as photosensitivity, curability, developability, solvent resistance, adhesion to a substrate, heat resistance and transparency. It gives things. Such a cured product is also excellent in image formability and surface smoothness, and has, for example, no unexposed residue or background stains after development. A cured product obtained by curing such a curable resin composition is one aspect of the present invention.

The cured product (cured film) preferably has a film thickness (thickness) of 0.1 to 20 μm. Thereby, it can fully respond to the request | requirement of low profile, such as a member using the said hardened | cured material, a display apparatus, etc. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

The cured product is used for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used in liquid crystal display devices, solid-state imaging devices, etc., and electrical / electronic devices. Are preferably used. Especially, it is preferable to use for a color filter. A color filter using the curable resin composition as described above, specifically, a color filter having the cured product on a substrate is also one aspect of the present invention. Hereinafter, the color filter will be further described.

〔Color filter〕
The color filter of this invention consists of a form which has the said hardened | cured material on a board | substrate.
In the above color filter, the cured product formed from the curable resin composition of the present invention is particularly suitable as a segment that needs to be colored, such as a black matrix or pixels such as red, green, blue, and yellow. However, it is also suitable as a segment that does not necessarily require coloring such as a photospacer, a protective layer, and an orientation control rib.

Examples of the substrate used in the color filter include glass substrates such as white plate glass, blue plate glass, alkali tempered glass, and silica-coated blue plate glass; ring-opened polymers of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin, and hydrogen thereof. Sheet, film or substrate made of thermoplastic resin such as additive; sheet, film or substrate made of thermosetting resin such as epoxy resin or unsaturated polyester resin; metal substrate such as aluminum plate, copper plate, nickel plate, stainless steel plate A ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member made of various materials such as a glass substrate (for example, a color filter for LCD) having a color material layer on the surface; Among these, from the viewpoint of heat resistance, a glass substrate or a sheet, film or substrate made of a heat resistant resin is preferable. The substrate is preferably a transparent substrate.
Moreover, you may perform the chemical | medical treatment etc. by a corona discharge process, an ozone process, a silane coupling agent, etc. to the said base material as needed.

[Production method of color filter]
In order to obtain the color filter, for example, for each pixel (that is, for each pixel of one color), a step of placing the curable resin composition on the substrate (also referred to as a placement step) and a placement on the substrate A step of irradiating light to the cured curable resin composition (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a development step), and a step of performing a heat treatment (also referred to as a heating step). It is preferable to adopt a manufacturing method that employs a method and repeats the same method for each color. Note that the order of forming the pixels of each color is not particularly limited.

The preferable form of each said process is as Unexamined-Japanese-Patent No. 2006-29151 [0125]-[0137]. In the development step, an ether solvent, an alcohol solvent or an alkaline aqueous solution is preferably used as the developer, and the alkaline aqueous solution preferably contains an inorganic alkaline agent or amine as an alkaline agent. When an alkaline aqueous solution is used, it is preferable to wash with water after development.

[Display device]
The present invention is also a display device configured using the color filter.
In addition, the display apparatus member and display apparatus which have the hardened | cured material formed with the said curable resin composition are also contained in suitable embodiment of this invention. The cured product (cured film) formed by the curable resin composition is stable, excellent in adhesion to a substrate, etc., and has high hardness, high smoothness, and high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or insulating film in various display devices.

As the display device, for example, a liquid crystal display device, a solid-state imaging device, a touch panel display device, and the like are suitable.
In addition, when using the said hardened | cured material (cured film) as a member for display apparatuses, the said member may be a film-form single layer or multilayer member comprised from the said cured film, or this single layer or multilayer It may be a member in which another layer is further combined with the above member, or may be a member including the above-mentioned cured film in its constitution.

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 mass” and “%” means “% by mass”. Various physical properties were measured as follows.

1. Weight average molecular weight polystyrene as a standard substance, tetrahydrofuran as an eluent, HLC-8220GPC (manufactured by Tosoh Corporation), column: weight average by GPC (gel permeation chromatography) method using TSKgel SuperHZM-M (manufactured by Tosoh Corporation) The molecular weight was measured.

2. About 1 g of a solid polymer solution (also referred to as a resin solution or a polymer solution) was weighed into an aluminum cup, dissolved by adding about 3 g of acetone, and then naturally dried at room temperature. Then, using a vacuum dryer (trade name: VOS-301SD type, manufactured by Tokyo Rika Kikai Co., Ltd.), it was dried at 120 ° C. under vacuum for 1.5 hours, then allowed to cool in a desiccator, and the mass was measured. From the mass reduction amount, the solid content (% by mass) of the polymer solution was calculated.

3. 3 g of acid value resin solution was precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an auto titrator (trade name, manufactured by Hiranuma Sangyo Co., Ltd.) using 0.1 N KOH aqueous solution as the titrant. : COM-555), the acid value of the polymer solution was measured, and the acid value (AV) per gram of the solid content was determined from the acid value of the solution and the solid content of the solution.

4. Development adhesiveness curable resin composition was applied onto a 10 cm square glass substrate with a spin coater, dried at 100 ° C. for 3 minutes, and then 2 to 100 μm of various lines and spaces at a distance of 100 μm from the coating film. A UV photo aligner (TME-150RNS, manufactured by TOPCON) equipped with a 2.0 kW ultra high pressure mercury lamp and a pattern photomask arranged with a UV light was irradiated at an intensity of 50 mJ / cm ² (converted to 365 nm illuminance). After UV irradiation, a 0.05% potassium hydroxide aqueous solution is sprayed on the coating film with a spin developing machine for 30 seconds and 60 seconds to dissolve and remove the unexposed area, and the remaining exposed area is 10% with pure water. Development was carried out by washing with water for 2 seconds. Various line and space films with a thickness of 2 μm formed after development were confirmed with a laser microscope (VK-9700, manufactured by Keyence Corporation), and the development adhesion was evaluated by the size of the line in which the line and space was completely formed.

5. The light-absorbing curable resin composition was spin-coated on a 5 cm square glass substrate, dried at 100 ° C. for 3 minutes, exposed to 100 mJ with a high-pressure mercury lamp, and heat-treated at 230 ° C. for 30 minutes to obtain a film thickness. A 2 μm thin film was obtained. Then, it was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 85 ° C. for 10 minutes, and the hue of 1-methyl-2-pyrrolidone eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The absorbance at 450 nm was determined.

Synthesis example 1
Propylene glycol monomethyl ether in a reaction vessel equipped with a synthesis thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping vessel introduction port for resin solution 1 (BzMI-CHMA-MMA-HEMA-AAEM-AA copolymer solution 1) After charging 155.7 parts of acetate and replacing with nitrogen, the mixture was heated to 90 ° C. On the other hand, as a dropping tank (A), 10 parts of N-benzylmaleimide, 43.5 parts of cyclohexyl methacrylate, 1 part of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of 2-acetoacetoxyethyl methacrylate are placed in a beaker. , 15.5 parts of acrylic acid and 2 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) were prepared and mixed in a dropping tank (B) with n- A mixture obtained by stirring and mixing 0.6 parts of dodecyl mercaptan and 20 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction vessel reached 90 ° C., dropping was started over 3 hours from the dropping vessel while maintaining the same temperature, and polymerization was performed. After maintaining the temperature at 90 ° C. for 30 minutes after completion of the dropping, the temperature was raised to 105 ° C. and aging was performed for 180 minutes. The obtained polymer solution (resin solution 1) was analyzed according to the above measurement method. The results are shown in Table 1.

Synthesis example 2
The amount of synthetic monomer charged in resin solution 2 (BzMI-CHMA-MMA-HEMA-AAEM-MAA copolymer solution 2) was changed to 10 parts N-benzylmaleimide, 36 parts cyclohexyl methacrylate, 1 part methyl methacrylate, The polymer solution (resin solution 2) was analyzed in the same manner as in Synthesis Example 1 except that 20 parts of 2-hydroxyethyl methacrylate, 10 parts of 2-acetoacetoxyethyl methacrylate, and 23 parts of methacrylic acid were used. . The results are shown in Table 1.

Synthesis example 3
Synthesis of Resin Solution 3 (MD-CHMA-MMA-HEMA-AAEM-AA Copolymer Solution 3) Instead of N-benzylmaleimide, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate ( The same operation as in Synthesis Example 1 was performed except that MD) was used, and the obtained polymer solution (resin solution 3) was analyzed. The results are shown in Table 1.

Synthesis example 4
Synthesis of Resin Solution 4 (AMA-CHMA-MMA-HEMA-AAEM-AA Copolymer Solution 4) Synthesis was performed except that methyl- (α-allyloxymethyl) acrylate (AMA) was used instead of N-benzylmaleimide. The same operation as in Example 1 was performed, and the resulting polymer solution (resin solution 4) was analyzed. The results are shown in Table 1.

Synthesis example 5
The amount of synthetic monomer charged in the resin solution 5 (BzMI-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 5) is 10 parts of N-benzylmaleimide, 43.5 parts of t-butyl methacrylate, The same polymer solution as obtained in Synthesis Example 1 except that 1 part of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of 2-acetoacetoxyethyl methacrylate, and 15.5 parts of acrylic acid were used. (Resin solution 5) was analyzed. The results are shown in Table 1.

Synthesis Example 6
Synthetic monomer charge amount of resin solution 6 (BzMI-t-BMA-MMA-HEMA-AAEM-MAA copolymer solution 6) is 10 parts of N-benzylmaleimide, 36 parts of t-butyl methacrylate, methacrylic acid. A polymer solution (resin solution 6) was obtained in the same manner as in Synthesis Example 1 except that 1 part of methyl, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of 2-acetoacetoxyethyl methacrylate, and 23 parts of methacrylic acid were used. ) Was analyzed. The results are shown in Table 1.

Synthesis example 7
The amount of the synthetic monomer of resin solution 7 (BzMI-CHMA-MMA-HEMA-AA copolymer solution 7) is 10 parts of N-benzylmaleimide, 53.5 parts of cyclohexyl methacrylate, 1 part of methyl methacrylate, The same polymer solution (resin solution 7) was analyzed as in Synthesis Example 1 except that 20 parts of 2-hydroxyethyl methacrylate and 15.5 parts of acrylic acid were used. The results are shown in Table 1.

Synthesis Example 8
Synthetic monomer charge amount of resin solution 8 (BzMI-t-BMA-MMA-HEMA-AA copolymer solution 8) is 10 parts of N-benzylmaleimide, 53.5 parts of t-butyl methacrylate, methacrylic acid. The same polymer solution (resin solution 8) was analyzed as in Synthesis Example 1 except that 1 part of methyl, 20 parts of 2-hydroxyethyl methacrylate, and 15.5 parts of acrylic acid were used. The results are shown in Table 1.

The symbols in Table 1 are as follows.
BzMI: N-benzylmaleimide MD: dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate AMA: methyl- (α-allyloxymethyl) acrylate CHMA: cyclohexyl methacrylate t-BMA: methacrylic acid t -Butyl MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate AAEM: 2-acetoacetoxyethyl methacrylate AA: acrylic acid MAA: methacrylic acid

Production Example 1
Preparation of Pigment Dispersion 1 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparon DA-7301 as a dispersant, and C.I. I. Pigment Green 58 (2.25 parts) and C.I. I. Pigment Yellow 138 (1.5 parts) was mixed and dispersed with a paint shaker for 3 hours to obtain Pigment Dispersion 1.

Example 1
2.0 parts resin solution 1, 0.70 parts dipentaerythritol hexaacrylate as a polymerizable compound, 0.35 parts Irgacure 369 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, pigment dispersion 1 Was mixed with 6.5 parts of propylene glycol monomethyl ether acetate as a solvent to obtain a curable resin composition 1.
The development adhesion of this curable resin composition and the absorbance of NMP after the NMP dissolution test were measured under the above conditions. The development adhesion was 12 μm for a completely formed line and space in 30 seconds of development, and 10 μm in 60 seconds of development. Absorbance was 5 × 10 ⁻² .

Examples 2-4, Comparative Examples 1-4
Except having set it as the mixing | blending shown in Table 2, it carried out similarly to Example 1, and obtained curable resin composition 2-8, respectively, Then, the light absorbency of NMP after a development adhesiveness and a NMP elution test was evaluated, respectively. The results are shown in Table 2.

From the results in Table 2, the following was confirmed.
Examples 1 to 4 include (meth) acrylate monomer units having an alicyclic skeleton, monomer units having a hydroxyl group, and monomer units having an active methylene group as the resin solutions 1 to 4 (meta ) An acrylate polymer (however, a tertiary carbon-containing (meth) acrylate monomer unit is not substantially contained) is used, whereas Comparative Examples 1 and 2 are resin solutions 5 and 6 As an implementation, it does not contain (meth) acrylate monomer units having an alicyclic skeleton, while using a (meth) acrylate polymer containing tertiary carbon-containing (meth) acrylate monomer units Different from Examples 1-4. Comparative Example 3 is different from Examples 1 to 4 in that a (meth) acrylate polymer not containing a monomer unit having an active methylene group was used as the resin solution 7. Comparative Example 4 does not include a (meth) acrylate monomer unit having an alicyclic skeleton and a monomer unit having an active methylene group as the resin solution 8, while a tertiary carbon-containing (meth) acrylate monomer It differs from Examples 1-4 by the point which used the (meth) acrylate type polymer containing a body unit.

Under these differences, a cured product was obtained under the same conditions, and the results of evaluation of development adhesion and absorbance were compared. In Comparative Examples 1, 2, and 4, in Examples 1 to 4, adhesion for 30 seconds was developed. It can be seen that the film line width was significantly narrowed and no film peeling occurred even after 60 seconds of development, despite the narrow line line width (see Table 2). The better the development adhesion, the wider the development margin (allowable width). From this result, the curable resin composition of the present invention containing the (meth) acrylate polymer having the above configuration has a wide development margin and is easy to handle. It turned out to be a thing. Moreover, in the comparative example 3, it turns out that the light absorbency of hardened | cured material is remarkably large and the coloring material has eluted from hardened | cured material (refer Table 2). If the curability and solvent resistance of the curable composition are insufficient, the absorbance of the eluate increases due to the elution of the coloring material. From this result, the monomer unit having an active methylene group It has been found that the use of a (meth) acrylate-based polymer that does not contain bismuth results in insufficient curability and solvent resistance.
In addition, all the hardened | cured material of the resin composition obtained in Examples 1-4 was a thing with high transparency.

Claims (8)

A curable resin composition comprising a (meth) acrylate polymer, a polymerizable compound and a photopolymerization initiator,
The (meth) acrylate polymer includes a (meth) acrylate monomer unit having an alicyclic skeleton, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group. A curable resin composition containing substantially no (meth) acrylate monomer unit. The curable resin composition according to claim 1, wherein the (meth) acrylate polymer further includes a monomer unit having an acid group. The curable resin composition according to claim 1, wherein the (meth) acrylate polymer has a ring structure in the main chain. The (meth) acrylate polymer includes a (meth) acrylate monomer (a) having an alicyclic skeleton, a monomer (b) having a hydroxyl group, a monomer (c) having an active methylene group, and an acid. A monomer component comprising a monomer (d) having a group, a monomer (e) capable of forming a ring structure in the main chain, and another monomer (f) if necessary (however, 3 A polymer obtained by polymerizing a secondary carbon-containing (meth) acrylate monomer),
The mass ratio (a / b / c / d / e / f) of the monomer components is 10-50 / 10-40 / 2-40 / 2-50 / 2-30 / 0-30 (provided that a The total of ˜f is 100% by mass.) The curable resin composition according to claim 3. The curable resin composition according to claim 1, wherein the monomer having an active methylene group is represented by the following formula (1).

In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom. X represents a divalent group represented by any of the following formulas (1-1) to (1-3). R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a divalent group represented by any of the following formulas (1-4) to (1-6). R ⁴ represents a cyano group (—CN), a nitro group (—NO ₂ ), or a group represented by the following formula (1-7) or (1-8). R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom.

Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-5. A color filter comprising the cured product according to claim 6 on a substrate. A display device comprising the color filter according to claim 7.