JP2017160460A - Curable resin composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesiveness to a substrate (base material), heat resistance and transparency, is excellent in storage stability, and is useful for various applications such as a color filter; a cured product formed by the curable resin composition; and a color filter and a display device using the cured product.SOLUTION: There is provided a curable resin composition containing a (meth)acrylate-based polymer, a polymerizable compound and a photopolymerization initiator, where the (meth)acrylate-based polymer is a polymer having a structural unit derived from a tertiary carbon-containing (meth)acrylate-based monomer, and the curable resin composition is at least one embodiment selected from the group consisting of an embodiment in which the composition contains a polymer having a hydroxyl group and an embodiment in which the (meth)acrylate-based polymer further has a hydroxyl group.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition and its use. More specifically, it is useful for various applications such as various optical members and electrical / electronic devices 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. The present invention relates to a curable resin composition, its cured product, a color filter using the cured product, and a display device.

Curable resin compositions that can be cured by heat or active energy rays include, for example, color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices and solid-state imaging devices. Various applications for various uses such as optical members and electrical / electronic devices have been studied, and curable resin compositions having excellent characteristics required for each use have been developed. Among these applications, the color filter is a main member constituting a liquid crystal display device, a solid-state image sensor, and the like, and is generally a substrate and at least three primary colors (red (R), green (G), and blue (B)). And a protective film provided to cover and protect the pixel and the resin black matrix and to flatten the unevenness thereof, in addition to the pixel and the resin black matrix (BM) for separating them. .

In general, when forming a pixel of a color filter using a curable resin composition, (1) an application process for applying the curable resin composition to the entire surface of the substrate and (2) an application process for each pixel color. The resist film is subjected to pattern exposure through a photomask and the exposed portion is cured, and then the exposed portion is insolubilized, and (3) the unexposed portion is removed with a developer and then baked (baked). A developing and baking (baking) treatment process for further curing the exposed portion is performed, and the same process is repeated for each color. In consideration of application to such color filter applications, the curable resin composition has various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance and transparency. It is required to have. In recent years, optical members, electric devices, electronic devices, and the like are becoming smaller, thinner, and energy-saving, and accordingly, members such as color filters that are used are required to have high-quality performance.

With respect to conventional curable resin compositions, compositions suitable for color filter applications include, for example, structural units derived from monomers having an aliphatic polycyclic epoxy group and unsaturated carboxylic acid monomers. A colored photosensitive resin composition (see Patent Document 1) containing a binder resin having a structural unit to be released, a colorant, a photopolymerizable compound, a photopolymerization initiator, and a solvent, or a carboxyl group / phenolic hydroxyl group Comprising a structural unit having a residue protected by a thermally decomposable group, a structural unit having an epoxy group / oxetanyl group, and a structural unit having a carboxyl group / phenolic hydroxyl group, and radiation-sensitive radical polymerization A colored photosensitive resin composition (see Patent Document 2) containing an initiator, an ethylenically unsaturated compound, and a colorant is disclosed.

JP 2007-333847 A JP2012-22048

As described above, the curable resin composition is required to have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (also referred to as a base material), heat resistance, and transparency. ing. On the other hand, from the viewpoint of handling, the curable resin composition itself has storage stability (also referred to as storage stability), and the cured product stably exhibits transparency, solvent resistance, adhesion, heat resistance, and the like. It is also required to be able to demonstrate. In recent years, with the advancement of technologies for display devices and the like, there has been a strong demand for higher performance for each member used. For example, in color filter applications, high transparency is required after curing. Sex is required. However, in the current situation, conventional resin compositions cannot sufficiently meet these demands. For example, since the resin compositions described in Patent Documents 1 and 2 are not sufficiently curable, a cured product with high transparency cannot be obtained, and the storage stability is not sufficient. There was room for improvement in order to further enhance the curability of the product so that a high degree of transparency can be stably exhibited. In addition, there is room for improvement to improve the storage stability of the resin composition.

The present invention has been made in view of the above situation, and can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance and transparency. An object of the present invention is to provide a curable resin composition that is excellent in storage stability and useful for various uses such as a color filter. Another object of the present invention is to provide a cured product formed from such a curable resin composition, and a color filter and a display device using the cured product.

The present inventor has made various studies on curable resin compositions useful for various uses such as color filters. When the resin composition includes a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, the composition is cured. We paid attention to the fact that it would have sex. The (meth) acrylate-based polymer has a structural unit derived from a tertiary carbon-containing (meth) acrylate-based monomer, and the curable resin composition further includes a polymer having a hydroxyl group, And / or, if the (meth) acrylate polymer further has a hydroxyl group, the curable resin composition is excellent in storage stability, while the curability and solvent resistance after curing are dramatically improved. The present inventors have found that a cured product capable of stably expressing various physical properties such as high transparency, adhesion to a substrate (base material), heat resistance, and high hardness can be obtained. Such a curable resin composition is particularly useful for color filter applications, and is particularly suitable as a resin composition for forming a protective film or an insulating film for a color filter. Therefore, a cured product, a color filter and a display device formed from such a curable resin composition are extremely useful in the optical field, electrical machinery / electronics field, etc., as they 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.

Here, the (meth) acrylate polymer contained in the curable resin composition of the present invention has a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer, but the structural unit is decomposed by heat. Easy to be. Specifically, the O—C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent to the oxygen atom is easily cleaved, whereby (meth) acrylic acid and third It is decomposed into a stable compound generated on the secondary carbon atom side. Therefore, for example, when the curable resin composition of the present invention is used for forming a pixel of a color filter, the above-described tertiary carbon-containing (metathesis) is obtained by a heating process after development (also referred to as a baking process or a post-baking process). ) The structural unit derived from the acrylate monomer is decomposed to produce (meth) acrylic acid and a stable compound generated on the tertiary carbon atom side. And the hydroxyl group in the polymer which has the hydroxyl group which curable resin composition can have further, and / or the hydroxyl group which (meth) acrylate type polymer can have further, and the (meth) acrylic acid produced | generated. Due to the formation of an ester cross-linked structure, it is considered that the curability of the resin composition and the solvent resistance after curing are drastically improved.

The (meth) acrylate polymer and the polymer having a hydroxyl group are also preferably polymers having a polymerizable double bond in the side chain as described later. This can further improve the curability, but in the present invention, the storage stability as well as the curability of the curable resin composition is improved in comparison with the case where a polymer having a polymerizable double bond in the side chain is simply used. It becomes possible to improve. This is because in the present invention, as described above, a curing reaction due to an ester cross-linking structure can be expected between (meth) acrylic acid and a hydroxyl group generated by thermal decomposition. Since sufficient curability can be expressed even if the content of the bond is reduced, the possibility that the polymerizable double bond in the side chain reacts and gels during storage can be further reduced.

That is, the present invention is a curable resin composition comprising a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, wherein the (meth) acrylate polymer is a tertiary carbon-containing (meth) acrylate. A polymer having a structural unit derived from a monomer, and the curable resin composition further includes a polymer having a hydroxyl group, and a form in which the (meth) acrylate polymer further has a hydroxyl group. It is a curable resin composition that is at least one form selected from the group consisting of:

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 present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

[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.
The curable resin composition of the present invention includes the following three forms a) to c).
a) A curable resin composition containing at least four components of a (meth) acrylate polymer, a polymerizable compound, a photopolymerization initiator, and a polymer having a hydroxyl group, and the (meth) acrylate polymer is It is a polymer having a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer. Furthermore, you may have a hydroxyl group.
b) A curable resin composition containing at least three components of a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, and the (meth) acrylate polymer contains a tertiary carbon ( It is a polymer having a structural unit derived from a (meth) acrylate monomer and having a hydroxyl group.
c) A curable resin composition containing at least four components of a (meth) acrylate polymer, a polymerizable compound, a photopolymerization initiator, and a polymer having a hydroxyl group, and the (meth) acrylate polymer is It is a polymer having a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer and having a hydroxyl group.

<(Meth) acrylate polymer>
In the curable resin composition, the (meth) acrylate polymer is a polymer having a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer. A structural unit derived from a tertiary carbon-containing (meth) acrylate monomer is a structure in which a polymerizable carbon-carbon double bond (C═C) in the monomer is a single bond (C—C). Although it means a unit, the monomer preferably has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. That is, the tertiary carbon-containing (meth) acrylate-based monomer preferably has a structure in which an oxygen atom adjacent to the (meth) acryloyl group is bonded to a tertiary carbon atom. The tertiary carbon atom means a carbon atom having three other carbon atoms bonded to the carbon atom.

The tertiary carbon-containing (meth) acrylate monomer is a compound having one polymerizable carbon-carbon double bond in the molecule, that is, a (meth) acryloyl group (CH ₂ = C (R) in the molecule. A compound having one -C (= O)-) is preferable, and for example, the following general formula (1):
_{CH 2 = C (R) -C} (= O) -O-A (1)
(R represents a hydrogen atom or a methyl group. A represents a monovalent organic group containing a structure having a tertiary carbon atom on the oxygen atom side).

In the general formula (1), the organic group represented by A can be represented by, for example, —C (R ¹ ) (R ² ) (R ³ ). In this case, R ¹ , R ² and R ³ are the same or different and are preferably a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group may be a saturated hydrocarbon group. And may be an unsaturated hydrocarbon group. Moreover, it may have a cyclic structure and may further have a substituent. R ¹ , R ^2, and R ³ may be linked to each other at a terminal site to form a cyclic structure.
In the present invention, as will be described later, a new O-C bond formed between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom in A adjacent thereto is cleaved. The number of carbon atoms of the organic group represented by A is preferably 12 or less in that the compound is easily volatilized. Among them, the organic group represented by A is preferably a group derived from t-butyl (meth) acrylate and / or t-amyl (meth) acrylate. The organic group represented by A may have a branched structure.

Here, in the tertiary carbon-containing (meth) acrylate monomer, the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group is bonded to a hydrogen atom at least one of the adjacent carbon atoms. It is preferred that For example, a tertiary carbon-containing (meth) acrylate monomer is a compound represented by the above general formula (1), and A is represented by -C (R ¹ ) (R ² ) (R ³ ). It is preferable that at least one of R ¹ , R ² and R ³ contains a carbon atom having one or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom. In such a form, by heating, the O—C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto is cut, and (meth) acrylic acid is generated at the same time. Then, a double bond (C═C) is formed between the tertiary carbon atom and the carbon atom adjacent to the tertiary carbon atom, and a new compound is generated more stably.

The new compound produced as described above is preferably volatile. In this case, the film thickness of the cured product (cured film) is reduced due to volatilization of the new compound from the cured product, and at the same time, for example, the curable resin composition further includes a color material. In some cases, the colorant concentration increases after heating. Therefore, it is possible to realize a further thinner film, and to achieve higher color purity and higher light blocking ratio of the black matrix. In view of this point, R ¹ , R ² and R ³ are preferably the same or different and are each a saturated hydrocarbon group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 saturated hydrocarbon group, More preferably, it is a C1-C5 saturated hydrocarbon group, Most preferably, it is a C1-C3 saturated hydrocarbon group.

From the viewpoint of developability, the (meth) acrylate polymer is preferably an alkali-soluble polymer, and is preferably a polymer having 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. Or two or more of them may be present. Among these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.

When the (meth) acrylate polymer is a polymer having an acid group in the molecule, the acid value (AV) of the polymer is not particularly limited. For example, it is 20 mgKOH / g or more and less than 300 mgKOH / g. Preferably it is. Thereby, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having better developability. The lower limit of the acid value is more preferably 30 mgKOH / g or more, and still more preferably 40 mgKOH / g or more. Moreover, 200 mgKOH / g or less is more preferable, More preferably, it is 150 mgKOH / g or less.
The acid value of the polymer can be determined, for example, as described later.

The (meth) acrylate-based polymer may also be a polymer having a hydroxyl group (hydroxyl group) in the molecule. That is, the (meth) acrylate polymer may be a polymer further having a hydroxyl group, and such a form is also a preferred form of the present invention. Thereby, the sclerosis | hardenability of curable resin composition is improved more and the hardened | cured material which is more excellent by transparency can be given.

The (meth) acrylate polymer can be obtained, for example, by polymerizing a monomer component containing a tertiary carbon-containing (meth) acrylate monomer. Preferably, the monomer component further includes a monomer having an acid group and a polymerizable double bond. Moreover, when the said (meth) acrylate type polymer has a hydroxyl group, it is suitable that the said monomer component further contains the monomer which has a hydroxyl group and a polymerizable double bond.
In addition, each monomer used can use 1 type (s) or 2 or more types, respectively.

The (meth) acrylate-based polymer may be a polymer (also referred to as a base polymer) obtained by polymerizing such a monomer component, and, as will be described later, an acid is added to the base polymer. A polymer obtained by reacting a compound having a functional group capable of bonding to a group and a polymerizable double bond (also referred to as a polymer having a polymerizable double bond in the side chain or a polymer containing a side chain double bond) These may be suitable. More preferably, it is a polymer containing a side chain double bond, whereby a curability can be further improved, and a cured product that is further excellent in transparency, adhesion, and the like can be obtained. The side chain polymerizable double bond is preferably a radical polymerizable double bond.

In the monomer component, the tertiary carbon-containing (meth) acrylate monomer is as described above, but the content of the monomer is 5% with respect to 100% by mass of the total amount of the monomer component. It is suitable that it is at least mass%. Thereby, the effect of this invention resulting from the structural unit derived from a tertiary carbon containing (meth) acrylate type monomer will be expressed further. More preferably, it is 15 mass% or more, Most preferably, it is 20 mass% or more. Further, the upper limit of the content ratio may be appropriately set in consideration of the content ratio of other monomers, for example, when used for color filter applications, from the viewpoint of further improving the pattern characteristics and developability, It is suitable that it is 90 mass% or less. More preferably, it is 75 mass% or less, More preferably, it is 60 mass% or less.

Examples of the monomer having an acid group and a polymerizable double bond include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; maleic acid, fumaric acid, and itacon. Unsaturated polyvalent carboxylic acids such as acid, citraconic acid, and mesaconic acid; a chain between unsaturated groups such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate and carboxyl groups Unsaturated monocarboxylic acids extended; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; phosphate 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 from the viewpoint of reactivity, alkali solubility, etc., more preferable is (meth) acrylic acid, and among these, methacrylic acid is particularly preferable.
In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The content ratio of the monomer having an acid group and a polymerizable double bond is preferably set so that the acid value of the (meth) acrylate polymer is within the preferable range described above. For example, the content of the monomer having an acid group and a polymerizable double bond is preferably 5% by mass or more, more preferably 10% by mass or more, with respect to 100% by mass of the total amount of the monomer components. More preferably, it is 20 mass% or more. Moreover, it is preferable that it is 85 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less.

The monomer component also preferably contains a monomer having a hydroxyl group and a polymerizable double bond as described above. Such a monomer is preferably a monomer having a hydroxyl group in the side chain, and is preferably a monomer having a hydroxyl group and a (meth) acryloyl group from the viewpoint of reactivity. is there. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy (meth) acrylate Preferred examples include hydroxyalkyl (meth) acrylates such as butyl, 4-hydroxybutyl (meth) acrylate, and 2,3-hydroxypropyl (meth) acrylate.
The (meth) acryloyl group means a methacryloyl group and / or an acryloyl group.

When the monomer component includes a monomer having a hydroxyl group and a polymerizable double bond, the content of the monomer is, for example, 1% by mass or more with respect to 100% by mass of the total amount of the monomer component. It is preferable that More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more. Further, considering the content ratio of the tertiary carbon-containing (meth) acrylate monomer and the monomer having an acid group and a polymerizable double bond, it is preferably 70% by mass or less, more preferably 50% by mass. % Or less.

The (meth) acrylate polymer contained in the curable resin composition of the present invention is a polymer having a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer, but further has a ring structure in the main chain. It is preferable to have. Examples of the ring structure include an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, and a lactone ring. In order to have these ring structures, the monomer component may further contain other copolymerizable monomers (also referred to as other monomers) in addition to the monomers described above.
Examples of the other monomer include N-substituted maleimide monomers, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers, α- (non It is preferable to use a saturated alkoxyalkyl) acrylate monomer (preferably an alkyl- (α-allyloxymethyl) acrylate monomer). Thus, the monomer component further comprises an N-substituted maleimide monomer, a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, and an α- (unsaturated alkoxyalkyl) acrylate monomer. A form containing at least one monomer selected from the group consisting of monomers is one of the preferred forms of the present invention. In addition, 1 type (s) or 2 or more types, such as a (meth) acrylic acid ester-type monomer and an aromatic vinyl-type monomer, are used suitably according to a required physical property.

Here, for example, N-substituted maleimide monomers and / or dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers and / or alkyl- (α-allyloxymethyl) acrylate monomers When is used, it becomes possible to give a cured product having further improved heat resistance, hardness, dispersibility of colorant and the like. In particular, when a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer and / or an alkyl- (α-allyloxymethyl) acrylate monomer is used, curing that is superior in terms of heat-resistant coloration Things are obtained.
The content ratio of the other monomer is preferably 60% by mass or less, and more preferably 50% by mass or less, in 100% by mass of the total amount of the monomer components. In particular, when an N-substituted maleimide monomer, a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer and / or an α- (unsaturated alkoxyalkyl) acrylate monomer are included, the content ratio Is preferably 2 to 60% by mass, more preferably 2 to 50% by mass, and still more preferably 3 to 40% by mass from the viewpoints of heat resistance, hardness, colorant dispersibility, development speed, transparency, and the like. It is.

Examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like can be mentioned, and one or more of these can be used. Among these, 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;

Examples of the dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer include 2,2 ′-[oxybis (methylene)] bisacrylic acid, dialkyl-2,2 ′-[oxybis (methylene). )] Bis-2-propenoate, dialkyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, etc., compounds in which at least one of the ester moieties contains a tertiary carbon. Among these, it is preferable to use, for example, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate from the viewpoints of transparency, dispersibility, industrial availability, and the like.

Examples of the α- (unsaturated alkoxyalkyl) acrylate monomer include α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl. N-propyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, Examples include α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate neopentyl, and the like. Of these, alkyl- (α-allyloxymethyl) acrylate monomers are preferred. As the alkyl- (α-allyloxymethyl) acrylate monomer, for example, methyl- (α-allyloxymethyl) acrylate is used from the viewpoint of transparency, dispersibility, industrial availability, and the like. Is preferred.
The α- (unsaturated alkoxyalkyl) acrylate can be produced, for example, by a production method disclosed in International Publication No. 2010/114077.

As the (meth) acrylic acid ester monomer, for example, a monomer having an alicyclic skeleton is preferable in consideration of the surface hardness of the cured product. Specifically, for example, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, pentacyclopentadecanedimethanol rudi (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 ( ) Acrylate, p-menthane-3,8-diol di (meth) acrylate, bicyclo [2.2.2] -octane-1-methyl-4-isopropyl-5,6-dimethylol di (meth) acrylate, and the like. . Among these, it is preferable to use cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate from the viewpoints of versatility and availability. It is also preferable to use an alicyclic epoxy compound such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, or ethyl glycidyl (meth) acrylate.

Examples of the (meth) acrylic acid ester monomer include, 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- (meth) acrylic acid 2- Ethylhexyl, 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 , Phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, α-hydroxy 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, in addition to t-butyl methyl acrylate, t-amyl α-hydroxymethyl acrylate, etc. 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) ) Acrylyloxymethyl-2-methyl-2-cyclohexyl-1 , 3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, and the like. Among them, (meth) methyl acrylate, (meth) ethyl acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, etc., because it is easy to balance heat resistance, colorant dispersibility, and solvent resolubility Of these, alkyl (meth) acrylates are preferred.

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

The other monomer may be, for example, one or more of the following compounds.
(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; heavy materials such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone and polycaprolactam Macromonomers having a (meth) acryloyl group at one end of the combined molecular chain; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Class: methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl 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-vinylcaprolactam, N-vinylimidazole N-vinyl compounds such as N-vinylmorpholine and N-vinylacetamide; Unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate;

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.

The polymerization initiation method in the above polymerization reaction may be performed by supplying energy necessary for initiation of polymerization to the monomer component from an active energy source such as heat, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and the like. If an initiator is used in combination, the energy required for initiating polymerization can be greatly reduced, and reaction control is facilitated, which is preferable.
The molecular weight of the polymer obtained by polymerizing the monomer components can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.

When the monomer component is polymerized by the solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction. For example, it may be appropriately set according to the polymerization conditions such as the polymerization mechanism, the type and amount of the monomer to be used, the polymerization temperature, the polymerization concentration and the like. When is used, it is efficient and preferable to use a solvent containing the solvent for solution polymerization of the monomer component.

As said solvent, the following compound etc. are mentioned suitably, for example, These 1 type (s) or 2 or more types can be used.
Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethers such as glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol Jie Glycol ethers such as ether ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl 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, Esters of glycol monoethers such as propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate; methyl acetate, ethyl acetate, propyl acetate , Isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Alkyl esters such as ethyl ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl isobutyrate Ketones such as ruketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone ;etc.

Among these solvents, propylene glycol monomethyl ether, propylene are used because of the solubility of the resulting polymer, surface smoothness when forming a coating film, little influence on the human body and the environment, and industrial availability. It is more preferable to use glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, or ethyl lactate.

As the usage-amount of the said solvent, it is suitable that it is 50-1000 mass parts with respect to 100 mass parts of said monomer components. More preferably, it is 100-500 mass parts.

When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy. Depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. And may be selected as appropriate. Moreover, you may use together reducing agents, such as transition metal salt and amines, with a polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxy- 2-ethylhexanoate, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis ( 2-methylpropionate), hydrogen peroxide, persulfate, etc., which are usually used as polymerization initiators, such as peroxides and azo compounds, may be used alone or in combination of two or more. May be.

The amount of the polymerization initiator used may be appropriately set according to the type and amount of the monomer used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, the molecular weight of the target polymer, etc., and is particularly limited. It is not a thing. For example, in order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer component. More preferably, it is 0.5-15 mass parts.

In the above polymerization, a chain transfer agent usually used may be used as necessary. Preferably, a polymerization initiator and a chain transfer agent are used in combination. In addition, when a chain transfer agent is used at the time of superposition | polymerization, it exists in the tendency which can suppress the increase in molecular weight distribution or gelatinization.

Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and n-mercaptopropionic acid n- Octyl, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3- Mercaptocarboxylic esters such as mercaptopropionate); alkyl mercapts such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane Mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; Aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; Tris [(3- Mercaptopropionyloxy) -ethyl] isocyanurate and other mercaptoisocyanurates; 2-hydroxyethyl disulfide and diethyl sulfides such as tetraethyl thiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; α-methylstyrene dimer and the like Body dimers; alkyl halides such as carbon tetrabromide. These may be used alone or in combination of two or more.

Among these, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercaptoisocyanurates, in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. It is preferable to use a compound having a mercapto group such as More preferred are alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, and still more preferred are n-dodecyl mercaptan and mercaptopropionic acid.

The amount of the chain transfer agent used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, the molecular weight of the target polymer, and the like. For example, in order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer component. More preferably, it is 0.5-15 mass parts.

Regarding the polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomer to be used, the type and amount of the polymerization initiator, and is preferably 50 to 150 ° C, for example, 70 to 120 ° C. is more preferable. Further, the polymerization time can be appropriately set similarly, but for example, 1 to 6 hours is preferable, and 2 to 5 hours is more preferable.

A polymer obtained by reacting a compound having a functional group capable of binding to an acid group and a polymerizable double bond with a base polymer obtained by polymerizing the monomer component, the (meth) acrylate polymer. In the case of (also referred to as a side chain double bond-containing polymer), one or more kinds of compounds having a functional group capable of binding to an acid group and a polymerizable double bond can be used. In such a compound, examples of the polymerizable double bond include (meth) acryloyl group, vinyl group, allyl group, methallyl group, etc., and the compound has one or more of these. Is preferred. Of these, a (meth) acryloyl group is preferable in terms of reactivity. In addition, examples of the functional group capable of binding to an acid group include a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, and the like, and those having one or more of these as the compound are 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.

As a method for obtaining the side chain double bond-containing polymer, for example, when reacting the base polymer with a compound having a functional group capable of binding to an acid group and a polymerizable double bond, the base polymer A method in which the amount of an acid group (preferably a carboxyl group) exceeds the amount of a functional group capable of binding to the acid group and a compound having a polymerizable double bond; the base polymer and a function capable of binding to the acid group And a method of reacting a compound having a polybasic acid anhydride group after reacting with a compound having a group and a polymerizable double bond.

The step of reacting the base polymer (preferably a polymer having a carboxyl group as an acid group) with a compound having a functional group capable of binding to an acid group and a polymerizable double bond ensures a good reaction rate, And in order to prevent gelatinization, it is preferable to carry out in the temperature range of 50-160 degreeC. More preferably, it is 70-140 degreeC, More preferably, it is 90-130 degreeC. Moreover, in order to improve reaction rate, the basic catalyst and acidic catalyst for esterification or transesterification normally used can be used as a catalyst. Among them, it is preferable to use a basic catalyst because side reactions are reduced.

Examples of the basic catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tri-n-octylamine, and tetramethylethylenediamine; tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, and n-dodecyltrimethyl. Quaternary ammonium salts such as ammonium chloride; urea compounds such as tetramethylurea; alkylguanidines such as tetramethylguanidine; amide compounds such as dimethylformamide and dimethylacetamide; tertiary phosphines such as triphenylphosphine and tributylphosphine; tetraphenylphosphonium Quaternary phosphonium salts such as bromide and benzyltriphenylphosphonium bromide; It is possible to have. Of these, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable in terms of reactivity, handling properties, and halogen-free properties.

The amount of the catalyst used is 0.01 with respect to 100 parts by mass of the total amount of the monomer component, a functional group capable of binding to an acid group (for example, an epoxy group) and a compound having a polymerizable double bond. It is preferable to set it to -5.0 mass parts. More preferably, it is 0.1-3.0 mass parts.

The step of reacting the above base polymer with a compound having a functional group capable of bonding to an acid group and a polymerizable double bond is also possible to add a polymerization inhibitor and prevent the presence of a molecular oxygen-containing gas in order to prevent gelation. It is preferable to carry out below. As the molecular oxygen-containing gas, air or oxygen gas diluted with an inert gas such as nitrogen is usually used and blown into the reaction vessel.

As the polymerization inhibitor, a commonly used polymerization inhibitor for radically polymerizable monomers can be used. For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl. -2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), etc. Phenolic inhibitors, organic acid copper salts, phenothiazines and the like, and one or more of these can be used. Among them, a phenol-based inhibitor is preferable in terms of low coloration and ability to prevent polymerization, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), methoquinone, 6-t- Butyl-2,4-xylenol and 2,6-di-t-butylphenol are more preferable.

The amount of the polymerization inhibitor used is a function capable of binding to the monomer component and the acid group from the viewpoint of ensuring a sufficient polymerization preventing effect and curability when a curable resin composition is obtained. It is preferable that it is 0.001-1.0 mass part with respect to 100 mass parts of total amounts with the group and the compound which has a polymerizable double bond. More preferably, it is 0.01-0.5 mass part.

Examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride. Acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, anhydrous Examples include pyromellitic acid, and one or more of these can be used.

The (meth) acrylate polymer preferably has a weight average molecular weight of 2000 to 250,000. By being in such a range, it becomes possible to exhibit better developability. More preferably, it is 3000-100000, More preferably, it is 4000-50000. In addition, when the said (meth) acrylate type polymer is high molecular weight (for example, 10000-50000), there exists a tendency which can obtain hardened | cured material of higher hardness, and the one where acid value is higher (preferably 150 mgKOH / g or more) , 200 mgKOH / g or less), it tends to be easily developed.
The weight average molecular weight of the polymer can be determined, for example, as described later.

When the (meth) acrylate polymer is a polymer having a double bond in the side chain (that is, a side chain double bond-containing polymer), the double bond equivalent is preferably 200 to 10,000. By being in such a range, the storage stability of the polymer becomes better. More preferably, it is 200-5000, More preferably, it is 250-4000, Most preferably, it is 300-4000.
The double bond equivalent is the mass of the solid content of the polymer solution (also referred to as a resin solution) per 1 mol of the double bond of the polymer. The mass of the solid content of the polymer solution referred to here is the sum of the mass of the constituent components of the monomer component and the mass of the polymerization inhibitor. 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.

The curable resin composition of the present invention also has at least one form selected from the group consisting of a form further comprising a polymer having a hydroxyl group and a form wherein the (meth) acrylate polymer further has a hydroxyl group. Is. Thus, by having a hydroxyl group in the system, an ester cross-linked structure is formed with (meth) acrylic acid generated by the decomposition of the structural unit derived from the tertiary carbon-containing (meth) acrylate monomer described above. As a result, the curability is remarkably increased, and it is possible to give a cured product that is particularly excellent in transparency. In addition, at the same time that the curable resin composition further includes a polymer having a hydroxyl group, the (meth) acrylate polymer may further have a hydroxyl group.

As described above, the (meth) acrylate polymer further has a hydroxyl group, as described above, a tertiary carbon-containing (meth) acrylate monomer, and a monomer having a hydroxyl group and a polymerizable double bond. A base polymer obtained by polymerizing a monomer component containing a monomer having an acid group and a polymerizable double bond, preferably a functional group capable of binding to an acid group and Preferred is a side chain double bond-containing polymer obtained by reacting a compound having a heavy bond. Among these, the latter side chain double bond-containing polymer is preferable.

<Polymer having hydroxyl group>
When the curable resin composition further contains a polymer having a hydroxyl group in addition to the (meth) acrylate polymer, the polymer having a hydroxyl group is particularly limited as long as it has a hydroxyl group in the molecule. Is not to be done. Among these, from the viewpoint of further improving developability, a polymer exhibiting alkali solubility is preferable, and a polymer having an acid group in the molecule is preferable. The acid group is as described above in the (meth) acrylate polymer, and the acid value of the hydroxyl group-containing polymer is also within the preferred range described above in the (meth) acrylate polymer. Is preferred.

Examples of the polymer having a hydroxyl group include a monomer having a hydroxyl group and a polymerizable double bond, and preferably a monomer component further containing a monomer having an acid group and a polymerizable double bond. Preferred examples include a base polymer obtained by reacting a compound having a functional group capable of bonding with an acid group and a polymerizable double bond with the base polymer. Among these, the latter side chain double bond-containing polymer is preferable.
Thus, the form in which the (meth) acrylate polymer and / or the polymer having a hydroxyl group is a polymer having a polymerizable double bond in the side chain is included in a preferred form of the present invention.

In the monomer component forming the polymer having a hydroxyl group, a monomer having a hydroxyl group and a polymerizable double bond, and preferred forms and specific examples of a monomer having an acid group and a polymerizable double bond, etc. Is as described above, and each monomer may be used alone or in combination of two or more.

The content ratio of the monomer having a hydroxyl group and a polymerizable double bond is preferably 1% by mass or more with respect to 100% by mass of the total amount of monomer components forming the polymer having the hydroxyl group, for example. . More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more. Moreover, it is preferable that it is 90 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 25 mass% or less.

The content ratio of the monomer having an acid group and a polymerizable double bond is preferably set so that the acid value is within the above-described preferred range, for example, forming a polymer having the hydroxyl group. The content ratio of the monomer having an acid group and a polymerizable double bond is preferably 5% by mass or more with respect to 100% by mass of the total amount of the monomer components. More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. Moreover, it is preferable that it is 99 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 60 mass% or less, Most preferably, it is 50 mass% or less.

The monomer component that forms the polymer having a hydroxyl group may also contain other copolymerizable monomers in addition to the monomers described above. Examples of other monomers include N-substituted maleimide monomers, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers, and alkyl- (α- (α-) other than the monomers described above. One or more of allyloxymethyl) acrylate monomer, (meth) acrylic acid ester monomer, aromatic vinyl monomer and the like are preferably used. These preferred forms and specific examples are as described above.
The content of other monomers is preferably 60% by mass or less, and preferably 50% by mass or less, in 100% by mass of the total amount of monomer components forming the polymer having a hydroxyl group. More preferred. In particular, when an N-substituted maleimide monomer is included, the content is preferably 2 to 60% by mass, more preferably from the viewpoints of heat resistance, hardness, colorant dispersibility, development speed, transparency, and the like. Is 2-50 mass%, More preferably, it is 3-40 mass%.

Regarding the method of polymerizing the monomer component and the method of reacting the base polymer obtained by polymerizing the monomer component with a compound having a functional group capable of binding to an acid group and a polymerizable double bond , As described above.

In the curable resin composition, the content ratio of the (meth) acrylate polymer and the polymer having a hydroxyl group may be appropriately set according to the use, the blending of other components, and the like. The content of the component (when the polymer having a hydroxyl group is not included, the solid content of only the (meth) acrylate polymer) is 5% with respect to 100% by mass of the total solid content of the curable resin composition. % Or more is preferable. 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%.
The “total amount of solids” means the total amount of components that form a cured product (excluding solvents that volatilize during the formation of the cured product).

Here, when both the (meth) acrylate polymer and the polymer having a hydroxyl group are included, the blending ratio is determined by thermal decomposition of a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer. What is necessary is just to set a compounding ratio so that the produced (meth) acrylic acid and the hydroxyl group in a system may carry out ester bridge | crosslinking easily, and it does not specifically limit. For example, the mass ratio ((meth) acrylate polymer / polymer having a hydroxyl group) = 1 to 99/99 to 1 is preferable. More preferably, it is 10-90 / 90-10.

<Polymerizable compound>
The curable resin composition 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.

Examples of the monofunctional polymerizable monomer include, for example, N-substituted maleimide and (meta) among the compounds exemplified as other monomers preferably contained in the monomer component of the (meth) acrylate polymer. ) Acrylic 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; Unsaturated acid anhydride Aromatic vinyls, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, unsaturated isocyanates, and the like.

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 acid esters such as (meth) acrylic acid allyl;
Multifunctional (meth) acryloyl groups such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate Containing isocyanurates;
Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate;
Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Polyfunctional urethane (meth) acrylates obtained;
Polyfunctional aromatic vinyls such as divinylbenzene;

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 of the present invention. 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.

The content ratio of the polymerizable compound may be appropriately set according to the purpose and use in addition to the type of the polymerizable compound to be used and the type of the (meth) acrylate-based polymer. Therefore, 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 50% by mass or less, particularly preferably. Is 30% by mass or less, and most preferably 20% by mass or less.

<Photopolymerization initiator>
The curable resin composition further contains a photopolymerization initiator. The photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator. A 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 can be used. . 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); bis (η5-2,4-cyclopentadien-1-yl) -bis (2 , 6-Difluoro-3- (1 - pyrrol-1-yl) - phenyl) titanocene compounds such as titanium; p-dimethylaminobenzoic acid, p- benzoic acid ester compounds such as diethyl benzoate; acridine compounds such as 9-phenyl acridine or the like.

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 Examples thereof include dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

The content of the photopolymerization initiator may be appropriately set according to the purpose, use, etc., and is not particularly limited, but is 0 with respect to 100 parts by mass of the total solid content of the curable resin composition excluding the photopolymerization initiator. It is suitable that it is 1 part by mass or more. 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.

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 preferably also contains a solvent. A solvent is preferably used as a diluent or the like. That is, specifically, the viscosity is lowered and the handling property is improved; the coating film is formed by drying; the coloring material is used as a dispersion medium; and the like. It is a low-viscosity organic solvent or water that can dissolve or disperse each of the components.

As the solvent, those usually used can be used, and may be appropriately selected according to the purpose and application, and are not particularly limited, and examples thereof include the following compounds. These may be used alone or in combination of two or more.

Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethers such as glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol Jie Ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, glycol ethers such as propylene glycol diethyl ether;

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 Esters of glycol monoethers such as monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Alkyl esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons; Aliphatic hydrocarbons such as hexane, cyclohexane, and octane; Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Water;

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 further includes, for example, a coloring material (also referred to as a colorant); a dispersant; a heat resistance improver; a leveling agent; a development aid; Inorganic fine particles such as silane, aluminum and titanium coupling agents; thermosetting resins such as fillers, epoxy resins, phenolic resins and polyvinylphenol; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization Inhibitors; UV absorbers; antioxidants; matting agents; antifoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic agents; quinonediazide compounds; 1 type (s) or 2 or more types, such as an acidic 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. Hereinafter, these contained components will be described.

-Color material-
As the color material, for example, a pigment or a dye is 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 the above 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. These may be selected or used in combination. Of the pigments, organic pigments are more preferable.

Examples of the pigment include azo pigments, phthalocyanine pigments, polycyclic pigments (for example, quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone). , Metal complex, diketopyrrolopyrrole, etc.), organic pigments such as dye lake pigments; white and extender pigments (eg, titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) Chromatic pigment (for example, chrome lead, cadmium, chromium vermilion, nickel titanium, chromium titanium, yellow iron oxide, bengara, zinc chromate, red lead, ultramarine, bitumen, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.) , Black pigments (eg carbon black, bone black, graphs) Ito, iron black, titanium black, etc.), the luminous material pigments (e.g. pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (such as zinc sulfide, strontium sulfide, and inorganic pigments strontium aluminate, etc.) and the like. Examples of pigment colors that can be used include yellow, red, purple, blue, green, brown, black, and white.

The pigment may also be subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc. depending on the purpose and application.

Specific examples of the pigments are shown below by color index (CI; issued by The Society of Dyers and Colorists) by color, but the color material of the present invention is not limited to these. Moreover, these may be used independently and may be used in combination of 2 or more types. The following “CI” means a color index, and a number means a color index number.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 49, 53, 55, 60, 61, 61: 1, 62, 62: 1, 63, 65, 71, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 127: 1, 128, 129, 130, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170.172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 209, 209: 1, 212, 213, 214, 215, 219 and the like.

Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 31, 34, 36, 38, 39, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, 81, and the like.
Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5,5: 1, 13, 14, 15, 16, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 39, 42, 44, 47, 49, 50 and the like.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 37, 38, 40, 41, 42, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 49: 1, 49: 2, 50: 1, 52, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 54, 57, 57: 1, 57: 2, 58, 58: 2, 58: 4, 60, 60: 1, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 89, 90: 1, 95, 97, 101, 101: 1, 102, 104, 105, 106, 108, 108: 1, 109, 112, 113, 114, 122, 123, 136, 14 146, 147, 149, 150, 151, 164, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 215, 216, 220, 221, 224, 226, 230, 231, 232, 233 235, 236, 237, 238, 239, 242, 243, 245, 247, 248, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265 266, 267, 268, 269, 270, 271, 272, 273 274,275,276,279, and the like.

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17, 17: 1, 19, 24, 24: 1, 25, 26, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80 and the like.
Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like.

Examples of the brown pigment include C.I. I. Pigment brown 5, 6, 23, 24, 25, 32, 41, 42, and the like.
Examples of the black pigment include aniline black, carbon black, lamp black, bone black, black iron, titanium black, C.I. I. Pigment black 1, 6, 7, 9, 10, 11, 12, 13, 20, 31, 32, 34, and the like. Examples of white pigments include C.I. I. Pigment white 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28, and the like.

As the dye, for example, organic dyes described in JP 2010-9033 A, JP 2010-211198 A, JP 2009-51896 A, and JP 2008-50599 A may be used. it can. Of these, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like are preferable.

The content ratio of the color material (that is, the total ratio of the pigment and the dye) can be appropriately set according to the purpose and application, but the preferable range of the content ratio of the color material is a solid content of the curable resin composition. It is 3-70 mass% with respect to the total amount of 100 mass%. More preferably, it is 5-60 mass%, More preferably, it is 10-50 mass%.

-Dispersant-
The above-mentioned dispersant has an interaction site with a color material and an interaction site with a dispersion medium (for example, a solvent or a binder resin), and has a function of stabilizing the dispersion of the color material into the dispersion medium. In general, it is classified into a resin-type dispersant (for example, a polymer dispersant), a surfactant (for example, a low-molecular dispersant), and a pigment derivative. The curable resin composition of the present invention preferably contains a dispersant together with the color material. In addition, as a dispersant (that is, a resin-type dispersant, a surfactant and / or a pigment derivative), a commonly used dispersant can be used. Moreover, one type of dispersant may be used alone, or two or more types may be used in combination.

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.
The resin-type dispersant has 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. In addition, a resin in which an anchor chain and a compatible chain have a block structure is particularly preferably used.

Examples of the trade name of the resin-type dispersant include the following. However, it is not limited to these.
EFKA-46, 47, 48, 745, 1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4540, 4550, 6750, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 1525070, 5207 (above, manufactured by EFKA ADDITIVES); Anti-Ter ra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, 160, 161, 162, 163, 164, 166, 182, P-104, P-104S, P105, 220S, 203, 204, 205, 2000, 2001, 9075, 9076, 9077 (above, manufactured by Big Chemie); SOLPERSE 3000 5000, 9000, 12000, 13240, 13940, 17000, 20000, 22000, 24000, 24000GR, 26000, 28000 (manufactured by Nihon Lubrizol); Disperlon 7301, 32 374, 234, 1220, 2100, 2200, KS260, KS273N, 152MS (above, manufactured by Enomoto Kasei Co., Ltd.); Ajisper PB-711, 821, 822, 880, PN-411, PA-111 (above, Ajinomoto Fine Techno Co., Ltd.) KP series (manufactured by Shin-Etsu Chemical Co., Ltd.); Polyflow series (manufactured by Kyoeisha Chemical Co., Ltd.); Megafuck series (manufactured by DIC (DIC)); Disperseid series (manufactured by San Nopco);

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, and an amide group. And phthalimide groups. Examples of the structure of the base dye include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, diketopyrrolopyrrole. And the like.

The content of the dispersant (that is, the resin-type dispersant, the surfactant and / or the pigment derivative) may be appropriately set according to the purpose and application, but the dispersion stability and durability (heat resistance, light resistance) From the viewpoint of balance between weather resistance and the like) and transparency, for example, it is preferably 0.01 to 60% by mass with respect to 100% by mass of the total solid content of the curable resin composition. More preferably, it is 0.1-50 mass%, More preferably, it is 0.3-40 mass%.

-Heat resistance improver-
The heat resistance improver is preferably used for improving heat resistance and strength. As the heat resistance improver, for example, an N- (alkoxymethyl) melamine compound, a compound having two or more epoxy groups or oxetanyl groups, and the like are suitable. In particular, when the curable resin composition is used as a resist for a photospacer, a transparent resist for a protective film, or a resist for an interlayer insulating film, these uses are preferable.

-Leveling agent-
The leveling agent is preferably used for improving leveling properties. As the leveling agent, a fluorine-based or silicon-based surfactant is preferable.

-Coupling agent-
The coupling agent is preferably used for improving adhesion. The coupling agent is preferably a silane coupling agent, and examples thereof include epoxy, methacrylic, and amino silane coupling agents. Among these, an epoxy silane coupling agent is preferable.

-Development aid-
The development aid is preferably used for improving developability. Examples of the development aid include monocarboxylic acids such as (meth) acrylic acid, acetic acid and propionic acid; polyvalent carboxylic acids such as maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid and trimellitic acid; maleic anhydride And carboxylic acid anhydrides such as succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride;

It does not specifically limit as a manufacturing method of the said curable resin composition, 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 coloring material, it is suitable to manufacture through the dispersion processing process of a coloring 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 composition containing a (meth) acrylate polymer, a polymerizable monomer, a photopolymerization initiator, and, if necessary, a solvent, a leveling agent, and the like, which are separately stirred and mixed with the obtained mill base. A curable resin composition can be obtained by adding (preferably a transparent liquid) and mixing to obtain a uniform dispersion solution.
In addition, it is preferable that the obtained curable resin composition is filtered with a filter or the like to remove fine dust.

[Cured product]
As described above, the curable resin composition of the present invention is particularly excellent in photosensitivity and curability, and has basic performance such as developability, solvent resistance, adhesion to a substrate (base material), heat resistance, and transparency. It gives a cured product that is excellent in. 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 also 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. Thus, a color filter using the curable resin composition, 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.

<Color filter manufacturing method>
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.

-Placement step (preferably coating step)-
The arrangement step is preferably performed by coating. Examples of the method of applying the curable resin composition on the substrate include spin coating, slit coating, roll coating, and cast coating, and any method can be preferably used.
In the arranging step, it is preferable that the coating film is dried after the curable resin composition is applied onto the substrate. The coating film can be dried using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but it is usually performed at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. Is preferred.

-Light irradiation process-
In the light irradiation step, the active light source used is, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, etc. Lamp light sources, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, semiconductor lasers, and the like are used. Further, examples of the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.
In the irradiation process of the active energy beam, the active energy beam may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insolubilized or hardly soluble in the developer.

-Development process-
The development step is a step of developing with a developer after the light irradiation step described above to remove unexposed portions and form a pattern. Thereby, the patterned cured film can be obtained. The development treatment can be usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.

The developer used in the development step is not particularly limited as long as it dissolves the curable resin composition of the present invention. Usually, an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may be used. . In addition, when using alkaline aqueous solution as a developing solution, it is preferable to wash | clean with water after image development.

Examples of the organic solvent suitable as the developer include an ether solvent and an alcohol solvent. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkyl phenyl ethers, aralkyl phenyl ethers, diaromatic ethers , Isopropanol, benzyl alcohol and the like.

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Examples of the organic solvent in this case include organic solvents suitable as the developer described above.
Examples of the alkali agent include inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. Alkali agents: Examples include amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and these may be used alone or in combination of two or more. May be combined.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates, alkylnaphthalene sulfonic acids, and the like. Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids, and the like. These may be used alone or in combination of two or more. Also good.

-Heating process-
The heating step is a step of further curing the exposed portion (cured portion) by baking after the developing step described above (also referred to as a post-curing step). For example, using a light source such as a high-pressure mercury lamp, for example, a step of post-exposure with a light amount of 0.5 to ⁵ J / cm ² , a step of post-heating at a temperature of 60 to 260 ° C. for 10 seconds to 120 minutes, etc. Can be mentioned. By performing such a post-curing step, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film. Further, by this heating step, a part of the structural unit of the (meth) acrylate polymer contained in the curable resin composition (that is, a part of the tertiary carbon-containing (meth) acrylate monomer). Since the (part) is decomposed, curability and solvent resistance can be improved.

The film thickness of the cured film obtained by the heating step (that is, the cured film obtained by thermosetting the curable resin composition) is preferably 0.1 to 20 μm. By using the curable resin composition of the present invention, a cured film having a sufficiently reduced film thickness can be provided. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.
In addition, it is suitable for the film thickness of the coating film (namely, cured film) obtained by the said heating process that it is 90% or less, when the film thickness of the coating film before a heating is 100%. More preferably, it is 80% or less, More preferably, it is 70% or less.

In the heating step, the heating temperature is preferably 150 ° C. or higher. Thereby, since the part originating in a part of said tertiary carbon containing (meth) acrylate type monomer is decomposed more effectively, it becomes possible to realize improvement of curability and solvent resistance more. . More preferably, it is 160 degreeC or more, More preferably, it is 170 degreeC or more, Most preferably, it is 180 degreeC or more. Moreover, it is preferable to set it as 260 degrees C or less, More preferably, it is 250 degrees C or less.

Although the heating time in the said heating process is not specifically limited, For example, it is suitable to set it as 5 to 60 minutes. Also, the heating method is not particularly limited, and for example, it can be performed using a heating device such as a hot plate, a convection oven, or a high-frequency heater.

[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.

Since the curable resin composition of the present invention is configured as described above, various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance and transparency are stable. It is excellent in storage stability and useful for various applications such as a color filter. Therefore, a color filter and a display device having a cured product (cured film) formed from such a curable resin composition are very useful in the optical field, the electric machine / electronic field, and the like.

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”.
In the following synthesis examples and the like, various physical properties and the like were measured as follows.

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

<Solid content>
About 1 g of a 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 hot air dryer (trade name: PHH-101, manufactured by Espec Corp.), after drying at 140 ° C. for 1.5 hours under vacuum, the mixture was 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.

<Acid value>
3 g of the resin solution is precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an automatic titration apparatus (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555) using a 0.1 N aqueous KOH solution as a titrant. ), 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.

<Absorbance of curable resin composition>
A curable resin composition is spin-coated on a 5 cm square glass substrate, dried at 80 ° C. for 3 minutes, exposed to 100 mJ with a high-pressure mercury lamp, and heat-treated at 220 ° C. for 30 minutes to form a thin film having a thickness of 5 μm. Got. Then, it was immersed in 20 g of 1-methyl-2-pyrrolidone at 25 ° C. for 2 hours, and the hue of 1-methyl-2-pyrrolidone eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation), and 450 nm. The absorbance was determined.

Synthesis example 1
Synthetic thermometer of resin solution 1 (BzMI-CHMA-t-BMA-MAA copolymer solution), a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank introduction port, a propylene glycol monomethyl ether acetate 844. After charging 57 g and purging with nitrogen, the mixture was heated to 90 ° C. On the other hand, 50 g of N-benzylmaleimide, 125 g of cyclohexyl methacrylate, 225 g of tert-butyl methacrylate, 100 g of methacrylic acid and t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation) as a dropping tank (A) "Perbutyl O") was prepared by stirring and mixing 10 g, and 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed in the dropping tank (B). 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 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 7800, the acid value was 129 mgKOH / g, and the resin solid content was 35.0% by mass.

Synthesis example 2
Synthetic thermometer of resin solution 2 (BzMI-CHMA-HEMA-MAA copolymer solution), stirrer, gas introduction pipe, cooling pipe and dropping tank introduction port were charged with 844.57 g of propylene glycol monomethyl ether acetate. After charging and replacing with nitrogen, the mixture was heated to 90 ° C. On the other hand, as a dropping tank (A), 50 g of N-benzylmaleimide, 250 g of cyclohexyl methacrylate, 100 g of 2-hydroxyethyl methacrylate, 100 g of methacrylic acid and t-butylperoxy-2-ethylhexanoate (Nippon Yushi Co., Ltd.) A product obtained by stirring and mixing 10 g of “Perbutyl O” (manufactured by “Perbutyl O”) was prepared, and 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed in a dropping tank (B). 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 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 7700, the acid value was 129 mgKOH / g, and the resin solid content was 35.0% by mass.

Synthesis example 3
A synthesis thermometer of a resin solution 3 (side chain double bond-containing copolymer; BzMI-t-BA-AA // GMA copolymer solution), a stirrer, a gas introduction pipe, a cooling pipe, and a dripping tank introduction port were provided. A reaction vessel was charged with 1006.67 g of propylene glycol monomethyl ether, purged with nitrogen, and then heated to 90 ° C. On the other hand, as a dropping tank (A), 20 g of N-benzylmaleimide, 250 g of t-butyl acrylate, 230 g of acrylic acid, and t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) were placed in a beaker. A mixture prepared by stirring and mixing 10 g was prepared, and a dropping tank (B) prepared by stirring and mixing 40 g of n-dodecyl mercaptan and 160 g of propylene glycol monomethyl ether was prepared. After the temperature of the reaction vessel reached 90 ° C., dropping was started from the dropping vessel while maintaining the same temperature, and polymerization was carried out over 3 hours. After maintaining the temperature at 90 ° C. for 30 minutes after completion of the dropping, the temperature was raised to 115 ° C. and aging was performed for 90 minutes.
Thereafter, the nitrogen in the gas introduction tube was changed to an oxygen / nitrogen mixed gas (oxygen / nitrogen = 5/95 vol%), and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (Kawaguchi Chemical Co., Ltd.) was used as an inhibitor. 1.34 g of “Antage w-400”) and 2.68 g of triethylamine as a catalyst were added and mixed with stirring. Then, 393.74 g of glycidyl methacrylate was added as an additional compound, and the mixture was heated to 115 ° C. and added. After 8 hours, the reaction was terminated when the residual GMA amount by GC (gas chromatography) analysis was 0.5% by mass or less, and the acid group-containing copolymer having a radically polymerizable double bond in the side chain. A polymer solution of the polymer was obtained.
When the obtained polymer solution was analyzed, the weight average molecular weight was 6800, the acid value was 58 mgKOH / g, and the resin solid content was 39.0% by mass.
“BzMI-t-BA-AA // GMA copolymer solution” means a solution of a copolymer obtained by reacting a base polymer obtained by using BzMI, t-BA and AA with GMA. "Means.

Synthesis example 4
A synthesis thermometer of a resin solution 4 (side chain double bond-containing copolymer; BzMI-CHA-HEA-AA / GMA copolymer solution), a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank introduction port were provided. A reaction vessel was charged with 1006.67 g of propylene glycol monomethyl ether, purged with nitrogen, and then heated to 90 ° C. On the other hand, as a dropping tank (A), 20 g of N-benzylmaleimide, 150 g of cyclohexyl acrylate, 100 g of 2-hydroxyethyl acrylate, 230 g of acrylic acid and t-butylperoxy-2-ethylhexanoate (Nippon Yushi Co., Ltd.) A product obtained by stirring and mixing 10 g of “Perbutyl O” (manufactured “Perbutyl O”) was prepared, and a dropping tank (B) prepared by stirring and mixing 40 g of n-dodecyl mercaptan and 160 g of propylene glycol monomethyl ether 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 115 ° C. and aging was performed for 90 minutes.
Thereafter, the nitrogen in the gas introduction tube was changed to an oxygen / nitrogen mixed gas (oxygen / nitrogen = 5/95 vol%), and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (Kawaguchi Chemical Co., Ltd.) was used as an inhibitor. 1.34 g of “Antage w-400”) and 2.68 g of triethylamine as a catalyst were added and mixed with stirring. Then, 393.74 g of glycidyl methacrylate was added as an additional compound, and the mixture was heated to 115 ° C. and added. After 8 hours, the reaction was terminated when the residual GMA amount by GC (gas chromatography) analysis was 0.5% by mass or less, and the acid group-containing copolymer having a radically polymerizable double bond in the side chain. A polymer solution of the polymer was obtained.
When the obtained polymer solution was analyzed, the weight average molecular weight was 6800, the acid value was 58 mgKOH / g, and the resin solid content was 39.0% by mass.
The “BzMI-CHA-HEA-AA // GMA copolymer solution” means a solution of a copolymer obtained by reacting GMA with a base polymer obtained using BzMI, CHA, HEA and AA. "Means.

Synthesis example 5
Propylene glycol monomethyl ether acetate in a reaction vessel equipped with a synthetic thermometer, stirrer, gas introduction tube, cooling tube, and dropping vessel introduction port for resin solution 5 (BzMI-CHMA-t-BMA-HEMA-MAA copolymer solution) -After charging 844.57g and substituting with nitrogen, it heated and heated up to 90 degreeC. On the other hand, 50 g of N-benzylmaleimide, 125 g of cyclohexyl methacrylate, 125 g of t-butyl methacrylate, 100 g of 2-hydroxyethyl methacrylate, 100 g of methallylic acid, and t-butylperoxy-2-ethyl as a dropping tank (A) A mixture prepared by stirring and mixing 10 g of hexanoate (Nippon Yushi Co., Ltd. “Perbutyl O”) was prepared, and a dropping tank (B) prepared by mixing 21 g of n-dodecyl mercaptan and 84 g 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 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 7700, the acid value was 133 mgKOH / g, and the resin solid content was 35.0 mass%.

Synthesis Example 6
Synthesis thermometer, stirrer, gas introduction pipe, cooling pipe and dropping tank introduction port of resin solution 6 (side chain double bond-containing copolymer; BzMI-t-BA-HEA-AA // GMA copolymer solution) The reaction vessel equipped was charged with 1006.67 g of propylene glycol monomethyl ether, purged with nitrogen, and then heated to 90 ° C. On the other hand, as a dropping tank (A), 20 g of N-benzylmaleimide, 150 g of t-butyl acrylate, 100 g of 2-hydroxyethyl acrylate, 230 g of acrylic acid, and t-butylperoxy-2-ethylhexanoate (Japan) A product obtained by stirring and mixing 10 g of “Perbutyl O” manufactured by Yushi Co., Ltd. was prepared, and a dropping tank (B) prepared by stirring and mixing 40 g of n-dodecyl mercaptan and 160 g of propylene glycol monomethyl ether 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 115 ° C. and aging was performed for 90 minutes.
Thereafter, the nitrogen in the gas introduction tube was changed to an oxygen / nitrogen mixed gas (oxygen / nitrogen = 5/95 vol%), and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (Kawaguchi Chemical Co., Ltd.) was used as an inhibitor. 1.34 g of “Antage w-400”) and 2.68 g of triethylamine as a catalyst were added and mixed with stirring. Then, 393.74 g of glycidyl methacrylate was added as an additional compound, and the mixture was heated to 115 ° C. and added. After 8 hours, the reaction was terminated when the residual GMA amount by GC (gas chromatography) analysis was 0.5% by mass or less, and the acid group-containing copolymer having a radically polymerizable double bond in the side chain. A polymer solution of the polymer was obtained.
When the obtained polymer solution was analyzed, the weight average molecular weight was 6800, the acid value was 58 mgKOH / g, and the resin solid content was 39.0% by mass.
The “BzMI-t-BA-HEA-AA // GMA copolymer solution” means a copolymer obtained by reacting GMA with a base polymer obtained using BzMI, t-BA, HEA and AA. It means “polymer solution”.

Synthesis example 7
Synthetic thermometer of resin solution 7 (MMA-MAA copolymer solution), stirrer, gas introduction pipe, cooling pipe and dropping tank introduction port were charged with 844.57 g of propylene glycol monomethyl ether acetate, After replacing with nitrogen, the mixture was heated to 90 ° C. On the other hand, a dripping tank (A) prepared by stirring and mixing 400 g of methyl methacrylate, 100 g of methallylic acid and 10 g of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) in a beaker is prepared. Then, in a dropping tank (B), 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed. 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 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 7700, the acid value was 133 mgKOH / g, and the resin solid content was 35.0 mass%.

Synthesis Example 8
Propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping vessel introduction port for a resin solution 8 (BzMI-t-BMA-HEMA-MAA copolymer solution) 874.57 g was charged and purged with nitrogen, and then heated to 90 ° C. On the other hand, as a dripping tank (A), 50 g of N-benzylmaleimide, 235 g of t-butyl methacrylate, 100 g of 2-hydroxyethyl methacrylate, 115 g of methallylic acid and t-butylperoxy-2-ethylhexanoate (Japan) A product obtained by stirring and mixing 10 g of “Perbutyl O” manufactured by Yushi Co., Ltd. was prepared, and a dropping tank (B) prepared by stirring and mixing 6 g of n-dodecyl mercaptan and 54 g 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 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 15500, the acid value was 150 mgKOH / g, and the resin solid content was 35.0% by mass.

Synthesis Example 9
Propylene glycol monomethyl ether acetate in a reaction tank equipped with a synthetic thermometer, stirrer, gas introduction pipe, cooling pipe and dropping tank introduction port for resin solution 9 (MD-t-BMA-HEMA-MAA copolymer solution) After 844.57 g was charged and purged with nitrogen, it was heated to 90 ° C. On the other hand, as a dropping tank (A), 50 g of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (MD), 250 g of t-butyl methacrylate, 100 g of 2-hydroxyethyl methacrylate, methallyl A mixture prepared by stirring and mixing 100 g of acid and 10 g of t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) was added to a dropping tank (B), 15 g of n-dodecyl mercaptan, propylene glycol. A mixture prepared by stirring and mixing 84 g of 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 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 12000, the acid value was 133 mgKOH / g, and the resin solid content was 35.0 mass%.

Synthesis Example 10
Synthetic thermometer of resin solution 10 (AMA-t-BMA-HEMA-MAA copolymer solution), stirrer, gas introduction pipe, cooling pipe and dropping tank introduction port in a reaction tank, propylene glycol monomethyl ether acetate After 844.57 g was charged and purged with nitrogen, it was heated to 90 ° C. On the other hand, as a dropping tank (A), 50 g of methyl- (α-allyloxymethyl) acrylate (AMA), 250 g of t-butyl methacrylate, 100 g of 2-hydroxyethyl methacrylate, 100 g of methallylic acid and t-butylperoxy were added to a beaker. A mixture prepared by stirring and mixing 10 g of 2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation) was mixed in a dropping tank (B) with 15 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate. I prepared something. 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 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 12,300, the acid value was 132 mgKOH / g, and the resin solid content was 35.2% by mass.

Table 1 shows details of the resin solutions 1 to 10.
In addition, regarding the compounding quantity of the monomer which comprises resin in Table 1, the numerical value of each monomer which comprises a base polymer is each compounding ratio (mass%) when these total quantity is 100 mass%. Was described. In Synthesis Examples 4 and 6, the numerical value of GMA (a compound having a functional group capable of binding to an acid group and a polymerizable double bond) added to the base polymer has an acid group and a polymerizable double bond. The GMA ratio added to the carboxylic acid content of the monomer (in this case, AA) is described as “GMA blend ratio (AA blend ratio with GMA added (mass%)) = {GMA The molar amount of (mol) / the molar amount of AA (mol)} × AA mixing ratio (mass%) ”. For example, in Synthesis Example 4, AA in the base polymer (100% by mass) is composed of 46% by mass, and 2769 mmol of GMA is added to 46% by mass (3191 mmol) of AA. The ratio (mass%) was defined as “40”.

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 MMA: methyl methacrylate CHMA: cyclohexyl methacrylate CHA: Cyclohexyl acrylate t-BMA: t-butyl methacrylate t-BA: t-butyl acrylate HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate MAA: methacrylic acid AA: acrylic acid GMA: glycidyl methacrylate

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 36 (Monastral Green 6Y-CL, manufactured by Heubach) 2.25 parts, and C.I. I. Pigment Yellow 150 (Yellow Pigment E4GN-GT, manufactured by Lanxess) (1.5 parts) was mixed and dispersed in a paint shaker for 3 hours to obtain Pigment Dispersion 1.

Example 1
1.0 part of resin solution 1, 1.0 part of resin solution 2, 0.70 part of dipentaerythritol hexaacrylate as a radical polymerizable compound, Irgacure 369 (Ciba Specialty Chemicals) as a radical polymerizable photopolymerization initiator Co., Ltd.) 0.35 parts, Pigment Dispersion 1 7.88 parts, and propylene glycol monomethyl ether acetate 6.57 parts as a solvent were mixed to obtain a curable resin composition 1. When the absorbance of this curable resin composition 1 was measured, it was 1.6 × 10 ⁻² .

Examples 2-8, Comparative Examples 1-7
Except having set it as the mixing | blending shown in Table 2 and 3, it carried out similarly to Example 1, and obtained the curable resin composition 2-15, respectively, Then, the light absorbency was measured, respectively. The results are shown in Tables 2 and 3.

From the results in Tables 2 and 3, the following was confirmed.
Example 1 and Comparative Examples 1, 2, 5 and 6; Example 2 and Comparative Examples 3 and 4; Examples 3, 6, 7 and 8 and Comparative Example 7; Example 4 and Comparative Examples 3 and 4; In each of these examples, the cured product was obtained under the same conditions, and the absorbance was measured. When these were compared, the absorbance was significantly higher in the comparative example than in the examples, and the transparency of the cured product was inferior. I understand. Here, if the curability and solvent resistance of the curable resin composition are insufficient, the absorbance of the cured product increases due to the elution of the coloring material. It turns out that curable resin composition of a comparative example was inadequate in sclerosis | hardenability and solvent resistance compared with the example. Further, although not shown in the table, all of the cured products obtained in the examples were excellent in various physical properties such as developability, adhesion to the substrate, and heat resistance.

Claims (6)

A curable resin composition comprising a (meth) acrylate polymer, a polymerizable compound and a photopolymerization initiator,
The (meth) acrylate polymer is a polymer having a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer, and has a weight average molecular weight of 2000 to 15500,
The curable resin composition is in a form further including a polymer having a hydroxyl group, and at least one form selected from the group consisting of a form in which the (meth) acrylate polymer further has a hydroxyl group. A curable resin composition. 2. The curability according to claim 1, wherein the tertiary carbon-containing (meth) acrylate monomer has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. Resin composition. The curable resin composition according to claim 1 or 2, wherein the (meth) acrylate polymer and / or the polymer having a hydroxyl group is a polymer having a polymerizable double bond in a side chain. . Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-3. A color filter comprising the cured product according to claim 4 on a substrate. A display device comprising the color filter according to claim 5.