KR102182764B1 - Curable resin composition and its use - Google Patents

Abstract

(Task) A curable resin composition that can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to substrate (substrate), heat resistance and transparency, has excellent storage stability, and is useful for various applications such as color filters. to provide. Further, a cured product formed from such a curable resin composition, and a color filter and a display device using the cured product are provided.
(Solution means) A curable resin composition comprising a (meth)acrylate-based polymer, a polymerizable compound, and a photoinitiator, wherein the (meth)acrylate-based polymer is a structural unit derived from a tertiary carbon-containing (meth)acrylate-based monomer As a polymer having, the curable resin composition is at least one type selected from the group consisting of a form containing a polymer further having a hydroxyl group, and a form wherein the (meth)acrylate-based polymer further has a hydroxyl group. Resin composition.

Description

Curable resin composition and its use {CURABLE RESIN COMPOSITION AND ITS USE}

The present invention relates to a curable resin composition and its use. More specifically, a curable resin composition useful for various applications such as color filters, ink, printing boards, printed wiring boards, semiconductor devices, photoresists, etc. used in liquid crystal displays or solid-state imaging devices, and various optical members and electric/electronic devices. , The cured product, and a color filter and a display device using the cured product.

Curable resin compositions that can be cured by heat or active energy rays include, for example, various optical devices such as color filters, ink, printing boards, printed wiring boards, semiconductor devices, photoresists, etc. used in liquid crystal displays or solid-state imaging devices. Application to various uses such as members and electric/electronic devices has been studied in various ways, and development of a curable resin composition having excellent properties required for each application has been made. Among these applications, a color filter is a main member constituting a liquid crystal display device or a solid-state imaging device, and generally, a substrate, a pixel of at least three primary colors (red (R), green (G), blue (B)), And in addition to the resin black matrix (BM) for shorting them, it is constituted by a protective film formed to cover and protect the pixels and the resin black matrix, and to flatten the irregularities thereof.

Typically, in the case of forming a pixel of a color filter using a curable resin composition, for one pixel, (1) a coating process of applying a curable resin composition to the entire surface of the substrate, and (2) a coating process. On the formed resist film, pattern exposure through a photomask to cure the exposed portion, an exposure step of insolubilizing the cured portion, and (3) removing the unexposed portion with a developer, and then firing (baking) the exposed portion. A method of performing a developing/baking (baking) treatment step of curing and repeating the same step with each color is employed. In consideration of application to such a color filter application, the curable resin composition is required to have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (substrate), heat resistance, and transparency. Further, in recent years, miniaturization, thinning, and energy saving of optical members, electric and electronic devices, and the like are in progress, and a high quality performance is desired for members such as color filters to be used.

With respect to the conventional curable resin composition, a composition suitable for use in a color filter includes, for example, a binder resin having a structural unit derived from a monomer having an aliphatic polycyclic epoxy group and a structural unit derived from an unsaturated carboxylic acid monomer, , A colorant, a photopolymerizable compound, a photopolymerization initiator, and a colored photosensitive resin composition containing a solvent (refer to Patent Document 1), or a structural unit having a residue protected by a carboxyl group/phenolic hydroxyl group by a thermally decomposable group, an epoxy group/oxeta A colored photosensitive resin composition comprising a structural unit having a nil group and a structural unit having a carboxyl group/phenolic hydroxyl group, a radiation-sensitive radical polymerization initiator, an ethylenically unsaturated compound, and a colorant (see Patent Document 2) ) Is disclosed.

Japanese Unexamined Patent Publication No. 2007-333847 Japanese Laid-Open Patent Publication No. 2012-22048

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 substrate), heat resistance, and transparency. On the other hand, from the viewpoint of handling, it is also required that the curable resin composition itself has storage stability (also referred to as storage stability), and that the cured product can stably exhibit transparency, solvent resistance, adhesion, heat resistance, and the like. And, in recent years, with the advancement of technology such as display devices, a higher level of performance has been strongly desired for each member to be used. For example, in a color filter application, a high degree of transparency is required after curing. . However, in the conventional resin composition, it is the present situation that cannot sufficiently respond to these demands. For example, the resin composition described in Patent Literature 1 or 2 has insufficient curability, so that a cured product having high transparency cannot be obtained, and storage stability is not sufficient, so that the curability of the resin composition is further increased, There was room for research in order to stably exhibit a high degree of transparency. In addition, there was room for research to improve the storage stability of the resin composition.

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

As a result of various studies on curable resin compositions useful for various applications such as color filters, the present inventors found that when a resin composition containing a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator is used, it becomes a curable resin composition. Noted. In addition, 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 contains a polymer having a hydroxyl group, and/ Alternatively, if the (meth)acrylate-based polymer is in a form having an additional hydroxyl group, the curable resin composition is excellent in storage stability, while curing properties and solvent resistance after curing are remarkably improved, high transparency, substrate (substrate (substrate) ) It was found that a cured product capable of stably expressing various physical properties such as adhesion, heat resistance, and high hardness can be obtained. Such a curable resin composition is particularly useful for color filter applications, and is particularly preferable as a resin composition for forming a protective film or insulating film for color filters. Therefore, it was found that a cured product, a color filter, and a display device formed from such a curable resin composition can sufficiently cope with the recent demand for high performance and become very useful in the optical field or the electric/electronic field. Considering what can be solved wonderfully, the present invention has been reached.

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, and the structural unit is easily decomposed by heat. Specifically, the OC bond between the oxygen atom adjacent to the (meth)acryloyl group and the tertiary carbon atom adjacent thereto is liable to be cleaved, thereby generating the (meth)acrylic acid and the tertiary carbon atom side. Decomposes into stable compounds. Therefore, for example, in the case where the curable resin composition of the present invention is used for pixel formation of a color filter, the above-described tertiary carbon content (meta) is carried out by a heating step after development (also referred to as a firing step or a post-baking step). ) Constituent units derived from acrylate-based monomers are decomposed to produce a stable compound generated on the side of (meth)acrylic acid and tertiary carbon atoms. In addition, an ester crosslinked structure between the hydroxyl group in the polymer having a hydroxyl group that the curable resin composition may additionally have, and/or the hydroxyl group that the (meth)acrylate-based polymer may further have, and the resulting (meth)acrylic acid Due to the occurrence, it is thought that the curing properties of the resin composition and the solvent resistance after curing are drastically improved.

It is preferable that the (meth)acrylate-based polymer or the polymer having a hydroxyl group is a polymer having a polymerizable double bond in the side chain as described later. Thereby, although the curability can be further improved, in the present invention, it becomes possible to improve the curability and storage stability of the curable resin composition, rather than simply using a polymer having a polymerizable double bond in the side chain. Even so, in the present invention, as described above, a curing reaction due to an ester crosslinked structure between (meth)acrylic acid and a hydroxyl group generated by thermal decomposition can be expected, so that the content of the polymerizable double bond in the polymer is Even if it is small, since sufficient curability can be expressed, the possibility of gelation due to reaction of the side chain polymerizable double bond during storage can be further reduced.

That is, the present invention is a curable resin composition comprising a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator, and the (meth)acrylate-based polymer is a structural unit derived from a tertiary carbon-containing (meth)acrylate-based monomer It is a polymer having, and the curable resin composition is at least one type selected from the group consisting of a form including a polymer further having a hydroxyl group, and the (meth)acrylate-based polymer further comprising a form having a hydroxyl group. It is a curable resin composition.

The present invention is also a cured product obtained by curing the curable resin composition.

The present invention is furthermore a color filter having the 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, a combination of two or three or more individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[Curable resin composition]

The curable resin composition of the present invention contains a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator, but each of these components may be used alone or in combination of two or more. Moreover, you may further contain 1 type or 2 or more types of other components as needed.

<(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. The structural unit derived from a tertiary carbon-containing (meth)acrylate monomer refers to a structural unit in which a polymerizable carbon-carbon double bond (C=C) in the monomer becomes a single bond (CC), but the monomer is ( It is preferable that the oxygen atom adjacent to the meth)acryloyl group has a structure in which it is bonded to a tertiary carbon atom. That is, it is preferable that the tertiary carbon-containing (meth)acrylate-based monomer has a structure in which an oxygen atom adjacent to a (meth)acryloyl group is bonded to a tertiary carbon atom. In addition, a tertiary carbon atom means a carbon atom having 3 other carbon atoms bonded to the carbon atom.

As the tertiary carbon-containing (meth)acrylate-based monomer, a compound having one polymerizable carbon-carbon double bond in the molecule, that is, a (meth)acryloyl group (CH ₂ =C(R)-C( It is preferably a compound having one =O)-), and, for example, the following general formula (1):

CH ₂ =C(R)-C(=O)-OA (1)

(R represents a hydrogen atom or a methyl group. A represents a monovalent organic group including a structure having a tertiary carbon atom on the oxygen atom side.) It is preferably a compound represented by.

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 or an unsaturated hydrocarbon group. Moreover, what has a cyclic structure may be sufficient and may have a substituent further. Further, R ¹ , R ² and R ³ may be linked to each other at terminal sites to form a cyclic structure.

In addition, in the present invention, as will be described later, the OC bond between the oxygen atom adjacent to the (meth)acryloyl group and the tertiary carbon atom in A adjacent thereto is cleaved, and the resulting new compound is liable to volatilize. In, it is preferable that carbon number of the organic group represented by A is 12 or less. Among these, the organic group represented by A is preferably a group derived from t-butyl (meth)acrylate and/or t-amyl (meth)acrylate. In addition, the organic group represented by A may have a branched structure.

Here, in the tertiary carbon-containing (meth)acrylate-based monomer, in the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth)acryloyl group, at least one of the adjacent carbon atoms is bonded to a hydrogen atom. It is desirable to have. For example, when the tertiary carbon-containing (meth)acrylate monomer is a compound represented by the general formula (1), and A is a group represented by -C(R ¹ )(R ² )(R ³ ), R ¹ It is preferable that at least one of R ² and R ³ has one or more hydrogen atoms. In such a form, by heating, the OC bond between the oxygen atom adjacent to the (meth)acryloyl group and the tertiary carbon atom adjacent thereto is cleaved, and (meth)acrylic acid is produced, and the third A double bond (C=C) is formed between the class carbon atom and the carbon atom adjacent thereto, resulting in more stable formation of a new compound.

It is preferable that the new compound produced as described above is volatilized. In this case, due to the fact that the new compound evaporates from the cured product, the film thickness of the cured product (cured film) is reduced, and, for example, when the curable resin composition further contains a color material, a color material The concentration increases after heating. Therefore, it becomes possible to achieve a further thinning, and to achieve higher color purity and higher light-shielding ratio of the black matrix. In consideration of this point, R ¹ , R ² and R ³ are the same or different, and are preferably saturated hydrocarbon groups having 1 to 15 carbon atoms. More preferably, they are 1 to 10 saturated hydrocarbon groups, still more preferably 1 to 5 saturated hydrocarbon groups, and particularly preferably 1 to 3 saturated hydrocarbon groups.

From the viewpoint of developability, the (meth)acrylate polymer is preferably a polymer exhibiting alkali solubility, and is preferably a polymer having an acid group in its molecule.

Examples of the acid group include a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, a sulfonic acid group, and other functional groups that react with alkaline water for neutralization, and may have only one of these, and two or more You may have it. Especially, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.

When the (meth)acrylate-based polymer is a polymer having an acid group in its molecule, the acid value (AV) of the polymer is not particularly limited, but, for example, it is preferably 20 mgKOH/g or more and less than 300 mgKOH/g. Do. Thereby, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having more excellent developability. As the lower limit of the acid value, it is more preferably 30 mgKOH/g or more, still more preferably 40 mgKOH/g or more. Further, it is more preferably 200 mgKOH/g or less, and still more preferably 150 mgKOH/g or less.

The acid value of the polymer can be obtained, 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-based polymer may further be a polymer having a hydroxyl group, and such a form is also one of the preferred embodiments of the present invention. Thereby, the curability of the curable resin composition is further improved, and a cured product having more excellent transparency can be provided.

The (meth)acrylate polymer can be obtained, for example, by polymerizing a monomer component containing a tertiary carbon-containing (meth)acrylate monomer. Preferably, this monomer component further contains a monomer having an acid group and a polymerizable double bond. In addition, when the (meth)acrylate-based polymer has a hydroxyl group, it is preferable that the monomer component further contains a monomer having a hydroxyl group and a polymerizable double bond.

In addition, each of the monomers used may be one or two or more.

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 described later, a functional group capable of bonding with an acid group and a polymerizable double bond are added to the base polymer. It may be a polymer obtained by reacting the possessed compound (also referred to as a polymer having a polymerizable double bond in the side chain or a side chain double bond-containing polymer), and any of these is preferable. More preferably, it is a side-chain double bond-containing polymer, whereby the curing property is further improved, and a cured product having further excellent transparency and adhesion can be obtained. In addition, it is preferable that the polymerizable double bond of the side chain is a radical polymerizable double bond.

In the above monomer component, the tertiary carbon-containing (meth)acrylate-based monomer is as described above, but the content ratio of the monomer is preferably 5% by mass or more with respect to 100% by mass of the total amount of the monomer component. Thereby, the effect of the present invention resulting from the constituent units derived from the tertiary carbon-containing (meth)acrylate-based monomer is further expressed. It is more preferably 15% by mass or more, particularly preferably 20% by mass or more. In addition, the upper limit of the content ratio may be appropriately set in consideration of the content ratio of other monomers. For example, in the case of use for color filter applications, from the viewpoint of further improving pattern characteristics and developability, it is 90% by mass or less. desirable. 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 vinylbenzoic acid; Unsaturated polyhydric carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; Unsaturated monocarboxylic acids in which a chain extends between an unsaturated group and a carboxyl group, such as succinate mono (2-acryloyloxyethyl) and succinate mono (2-methacryloyloxyethyl); Unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Phosphoric acid group-containing unsaturated compounds, such as light ester P-1M (made by Kyoeisha Chemical), etc. are mentioned. Among these, it is preferable to use a carboxylic acid monomer (unsaturated monocarboxylic acids, unsaturated polyhydric carboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferably, from the viewpoint of reactivity and alkali solubility, it is preferable to use unsaturated monocarboxylic acids, more preferably (meth)acrylic acid, and among them, methacrylic acid is particularly preferable.

In addition, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

It is preferable to set the content ratio of the said acidic group and the monomer which has a polymerizable double bond so that the acid value of a (meth)acrylate type polymer may fall within the preferable range mentioned above. For example, it is preferable that the content ratio of the monomer having an acid group and a polymerizable double bond is 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% with respect to 100% by mass of the total amount of the monomer components. It is not less than mass%. 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.

It is also preferable that the monomer component also 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 further, from the viewpoint of reactivity, it is preferably a monomer having a hydroxyl group and a (meth)acryloyl group. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-(meth)acrylic acid Hydroxyalkyl (meth)acrylates, such as hydroxybutyl, 4-hydroxybutyl (meth)acrylate, and 2,3-hydroxypropyl (meth)acrylate, are mentioned preferably.

In addition, a (meth)acryloyl group means a methacryloyl group and/or an acryloyl group.

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

The (meth)acrylate-based 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-based monomer, but it is preferable to further have a cyclic structure in the main chain. Examples of the ring structure include an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, and a lactone ring. In order to have these cyclic structures, the monomer component may further contain other copolymerizable monomers (also referred to as other monomers) in addition to the above-described monomers.

Examples of the other monomers include N-substituted maleimide-based monomers other than the above-described monomers, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers, α-(unsaturated alkoxyalkyl) It is preferable to use an acrylate monomer (preferably an alkyl-(α-allyloxymethyl) acrylate monomer) or the like. As described above, the monomer component further comprises an N-substituted maleimide-based monomer, a dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer, and an α-(unsaturated alkoxyalkyl) acrylate-based monomer. The form containing at least one monomer selected from the group is one of the preferred forms of the present invention. In addition, one or two or more types, such as a (meth)acrylic acid ester-based monomer or an aromatic vinyl-based monomer, are preferably used depending on the required physical properties.

Here, for example, an N-substituted maleimide-based monomer and/or a dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer and/or an alkyl-(α-allyloxymethyl)acrylate-based monomer When used, it becomes possible to impart a cured product having more improved heat resistance, hardness, color material dispersibility, and the like. In particular, when a dialkyl-2,2'-(oxydimethylene) diacrylate monomer and/or an alkyl-(α-allyloxymethyl) acrylate monomer is used, a cured product more excellent in terms of heat coloring property is Is obtained.

In addition, the content ratio of the other monomers 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-based monomer, a dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer and/or an α-(unsaturated alkoxyalkyl) acrylate-based monomer is included, the content ratio is, From the viewpoints of heat resistance, hardness, color material dispersibility, development speed, transparency, and the like, it is preferable to set it as 2 to 60 mass%, more preferably 2 to 50 mass%, still more preferably 3 to 40 mass%.

As the N-substituted maleimide-based monomer, for example, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide Mid, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, and the like, and one or two or more of these can be used. Among them, from the viewpoint of transparency, N-phenylmaleimide and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable.

Examples of the N-benzyl maleimide include benzyl maleimide; alkyl substituted benzyl maleimide such as p-methylbenzyl maleimide and p-butylbenzyl maleimide; phenolic hydroxyl group-substituted benzyl maleimide such as p-hydroxybenzyl maleimide; Halogen-substituted benzyl maleimide, such as o-chlorobenzyl maleimide, o-dichlorobenzyl maleimide, and p-dichlorobenzyl maleimide, etc. are mentioned.

As the dialkyl-2,2'-(oxydimethylene)diacrylate-based monomer, for example, 2,2'-[oxybis(methylene)]bisacrylic acid, dialkyl-2,2'-[ At least one of the ester moieties, such as oxybis(methylene)]bis-2-propenoate and dialkyl-2,2'-[oxybis(methylene)]bis-2-propenoate, contains tertiary carbon. The compound etc. which are doing are mentioned. Among these, it is preferable to use, for example, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. from the viewpoint of transparency, dispersibility, and ease of industrial availability. .

Examples of the α-(unsaturated alkoxyalkyl)acrylate-based monomer include α-allyloxymethylacrylic acid, α-allyloxymethyl acrylate, α-allyloxymethyl acrylate, α-allyloxymethylacrylic acid n- Propyl, α-allyloxymethylacrylate i-propyl, α-allyloxymethylacrylate n-butyl, α-allyloxymethylacrylate s-butyl, α-allyloxymethylacrylate t-butyl, α-allyloxymethylacrylate n- Amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate neopentyl, and the like. Among them, alkyl-(?-allyloxymethyl) acrylate monomers are preferred. As the alkyl-(α-allyloxymethyl)acrylate monomer, from the viewpoint of transparency, dispersibility, and ease of industrial availability, for example, methyl-(α-allyloxymethyl)acrylate, etc. are used. It is desirable.

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

As the (meth)acrylic acid ester-based monomer, for example, considering the surface hardness of the cured product, a monomer having an alicyclic skeleton is preferable. Specifically, for example, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (3,4- Epoxycyclohexyl)methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylol-tricyclodecanedi (Meth)acrylate, pentacyclopentadecandimethanoldi(meth)acrylate, cyclohexanedimethanoldi(meth)acrylate, norbornanedimethanoldi(meth)acrylate, p-mentane-1,8-diol Di(meth)acrylate, p-mentane-2,8-dioldi(meth)acrylate, p-mentane-3,8-dioldi(meth)acrylate, bicyclo[2.2.2]-octane-1 -Methyl-4-isopropyl-5,6-dimethyloldi(meth)acrylate, etc. are mentioned. Among these, from the viewpoint of versatility and availability, use of cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanyl (meth)acrylate It is desirable. In addition, it is also preferable to use an alicyclic epoxy compound such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and ethyl glycidyl (meth) acrylate.

The (meth)acrylic acid ester monomer is also, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate , S-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, ( Tridecyl meth)acrylate, octyl (meth)acrylate, isoctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid2 -Methoxyethyl, (meth)acrylate 2-ethoxyethyl, (meth)acrylate phenoxyethyl, (meth)acrylate tetrahydrofurfuryl, (meth)acrylate N,N-dimethylaminoethyl, α-hydroxymethylacrylic acid In addition to methyl, α-hydroxymethyl ethyl acrylate, α-hydroxymethyl acrylate t-butyl, α-hydroxymethyl acrylate t-amyl, etc., 1,4-dioxaspiro[4,5]dec-2-yl Methacrylic acid, (meth)acryloylmorpholine, tetrahydrofurfurylacrylate, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-( Meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-di Oxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, etc. are also mentioned. Among them, alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and benzyl (meth)acrylate, are easily balanced in terms of heat resistance, dispersibility of colorant, and solvent resolubility. This is desirable.

Examples of the aromatic vinyl-based monomer include styrene, vinyl toluene, α-methylstyrene, and methoxystyrene. Among them, styrene and/or vinyl toluene are preferred from the viewpoint of heat-resistant coloring and heat decomposition resistance of the resin.

The other monomers may also be one or two or more of the following compounds, for example.

(Meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; Macromonomers having a (meth)acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; Conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether , Vinyl ethers such as methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether; N-vinyl compounds, such as N-vinylpyrrolidone, N-vinyl caprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinyl acetamide; Unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate.

As a method of polymerizing the monomer component, commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization may be used, and may be appropriately selected according to the purpose and use. Among them, solution polymerization is industrially advantageous, and structural adjustment such as molecular weight is also easy, so it is preferable. In addition, the polymerization mechanism of the monomer component can be a polymerization method based on mechanisms such as radical polymerization, anionic polymerization, cation polymerization, and coordination polymerization, but a polymerization method based on a radical polymerization mechanism is also advantageous industrially. Do.

In the polymerization initiation method in the polymerization reaction, energy required for polymerization initiation may be supplied as a monomer component from an active energy source such as heat, electromagnetic waves (e.g., infrared, ultraviolet, X-ray, etc.), and electron beams. When used together, the energy required for polymerization initiation can be greatly reduced, and the reaction control becomes easy, which is preferable.

Further, the molecular weight of the polymer obtained by polymerizing the monomer component can be controlled by adjusting the amount or type of the polymerization initiator, the polymerization temperature, and the type or amount of the chain transfer agent.

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

As the solvent, for example, the following compounds and the like are preferably mentioned, and one or two or more of these can be used.

Mono alcohols, such as methanol, ethanol, isopropanol, n-butanol, and 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 monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol monoethers such as propylene glycol monobutyl ether and 3-methoxybutanol; Glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether Ethers; 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 Glycol mono such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, and 3-methoxybutyl acetate Ether esters; Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3- Alkyl esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 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;

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

The amount of the solvent used is preferably 50 to 1000 parts by mass based on 100 parts by mass of the monomer component. More preferably, it is 100 to 500 parts by mass.

In the case of polymerizing the monomer component 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 heat energy, and may be appropriately selected according to polymerization conditions such as polymerization temperature, solvent, and type of monomer to be polymerized. Moreover, you may use together reducing agents, such as a transition metal salt and amines, together with a polymerization initiator.

As the polymerization initiator, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t -Butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) , Dimethyl 2,2'-azobis(2-methylpropionate), hydrogen peroxide, persulfate, and the like, peroxides and azo compounds commonly used as polymerization initiators, and these may be used alone, or two types You may use the above together.

The amount of the polymerization initiator used may be appropriately set depending on the type or amount of the monomer to be used, polymerization conditions such as polymerization temperature, polymerization concentration, and the molecular weight of the target polymer, and is not particularly limited. For example, in obtaining a polymer having a weight average molecular weight of several thousands to tens of thousands, it is preferably 0.1 to 20 parts by mass per 100 parts by mass of the monomer component. More preferably, it is 0.5 to 15 parts by mass.

In the polymerization, a chain transfer agent commonly used may also be used if necessary. Preferably, a polymerization initiator and a chain transfer agent are used in combination. In addition, when a chain transfer agent is used during polymerization, there is a tendency that an increase in molecular weight distribution or gelation can be suppressed.

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, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylol Mercaptocarboxylic acid esters such as propanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercaptopropionate) Ryu; Alkyl mercaptans such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, and 1,2-dimercaptoethane; Mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; Aromatic mercaptans such as benzene thiol, m-toluene thiol, p-toluene thiol, and 2-naphthalene thiol; Mercaptoisocyanurates such as tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate; Disulfides such as 2-hydroxyethyl disulfide and tetraethyl thiuram disulfide; Dithiocarbamates such as benzyl diethyldithiocarbamate; monomer dimers such as α-methylstyrene dimer; And halogenated alkyls such as carbon tetrabromide. These may be used alone or in combination of two or more.

Among these, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, from the viewpoint of availability, crosslinking preventing ability, and the degree of reduction in polymerization rate are small. It is preferable to use a compound having a mercapto group, such as mercapto isocyanurates. More preferably, they are alkyl mercaptans, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, and still more preferably n-dodecylmercaptan and mercaptopropionic acid.

The amount of the chain transfer agent to be used may be appropriately set depending on the type or amount of the monomer to be used, polymerization conditions such as polymerization temperature, polymerization concentration, and the molecular weight of the target polymer, and is not particularly limited. For example, in obtaining a polymer having a weight average molecular weight of several thousands to tens of thousands, it is preferably 0.1 to 20 parts by mass per 100 parts by mass of the monomer component. More preferably, it is 0.5 to 15 mass %.

Regarding the above polymerization conditions, the polymerization temperature may be appropriately set according to the type or amount of the monomer to be used, the type or amount of the polymerization initiator, etc. For example, 50 to 150°C is preferable, and 70 to 120°C is More preferable. Moreover, although the polymerization time can be similarly set appropriately, for example, 1 to 6 hours are preferable, and 2 to 5 hours are more preferable.

The (meth)acrylate-based polymer is a polymer obtained by reacting a compound having a functional group capable of bonding with an acid group and a polymerizable double bond with a base polymer obtained by polymerizing the monomer component (also referred to as a side-chain double bond-containing polymer) ), as a compound having a functional group capable of bonding with an acid group and a polymerizable double bond, one type or two or more types may be used. In such a compound, examples of the polymerizable double bond include a (meth)acryloyl group, a vinyl group, an allyl group, and a metalyl group, and one or two or more of these may be used as the compound. It is desirable to have. Especially, a (meth)acryloyl group is preferable from a reactive point. In addition, as a functional group capable of bonding with an acid group, for example, a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, etc. can be mentioned, and it is preferable to have one or two or more of these as the compound. . Among them, an epoxy group (including a glycidyl group) is preferable from the viewpoint of speed of the modification treatment reaction, heat resistance, and dispersibility.

As a compound having a functional group capable of bonding with the acid group and a polymerizable double bond, for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate Cidyl, vinylbenzyl glycidyl ether, allyl glycidyl ether, (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, vinylcyclohexene oxide, etc., and one or two or more of these Can be used. Among them, it is preferable to use a compound (monomer) having an epoxy group and a (meth)acryloyl group.

As a method of obtaining the side chain double bond-containing polymer, for example, when reacting the base polymer with a compound having a functional group capable of bonding with an acid group and a polymerizable double bond, the acid group of the base polymer (preferably Is a method of making the amount of carboxyl group) excessive than the amount of the compound having a functional group capable of bonding to the acid group and a polymerizable double bond; After reacting the base polymer with a compound having a functional group capable of bonding with an acid group and a polymerizable double bond, a method of further reacting a compound having a polybasic acid anhydride group may be mentioned.

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

Examples of the basic catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tri-n-octylamine, and tetramethylethylenediamine; Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, and n-dodecyltrimethylammonium chloride; Urea compounds such as tetramethylurea; Alkyl guanidines such as tetramethylguanidine; Amide compounds such as dimethylformamide and dimethylacetamide; Tertiary phosphine such as triphenylphosphine and tributylphosphine; And quaternary phosphonium salts such as tetraphenylphosphonium bromide and benzyltriphenylphosphonium bromide, and one or two or more of these may be used. Among them, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable from the viewpoints of reactivity, handling properties, and halogen-free.

The amount of the catalyst to be used is preferably 0.01 to 5.0 parts by mass based on 100 parts by mass of the total amount of the monomer component, the functional group capable of bonding with an acid group (for example, an epoxy group, etc.) and a compound having a polymerizable double bond. . More preferably, it is 0.1 to 3.0 mass parts.

The step of reacting the base polymer with a compound having a functional group capable of bonding with an acid group and a polymerizable double bond is further carried out in the presence of a molecular oxygen-containing gas by adding a polymerization inhibitor in order to prevent gelation. desirable. As the molecular oxygen-containing gas, usually, air or oxygen gas diluted with an inert gas such as nitrogen is used, and is absorbed in the reaction vessel.

As the polymerization inhibitor, a polymerization inhibitor for radically polymerizable monomers that are commonly used may be used, for example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, metoquinone, 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), and other phenolic inhibitors, organic acid copper salts, phenothiazine, and the like, and one or two or more of these can be used. Among them, phenolic inhibitors are preferred from the viewpoints of low coloration and polymerization preventing ability, and from the viewpoint of availability and economy, 2,2'-methylenebis(4-methyl-6-t-butylphenol), metoquinone , 6-t-butyl-2,4-xylenol and 2,6-di-t-butylphenol are more preferable.

The amount of the polymerization inhibitor used is a compound having a functional group capable of bonding with the monomer component and an acidic group and a polymerizable double bond from the viewpoint of securing a sufficient polymerization preventing effect and curing properties when used as a curable resin composition. It is preferable that it is 0.001 to 1.0 mass parts with respect to 100 mass parts of the total amount of. More preferably, it is 0.01 to 0.5 mass parts.

Examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methylhexa Hydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. And one or two or more of these may be used.

It is preferable that the said (meth)acrylate-type polymer has a weight average molecular weight of 2000-250000. By being in such a range, it becomes possible to exhibit more favorable developability. More preferably, it is 3000 to 100000, More preferably, it is 4000 to 50000. In addition, when the (meth)acrylate polymer has a high molecular weight (for example, 10000 to 50000), a cured product having a higher hardness tends to be obtained, and the higher the acid value (preferably 150 mgKOH/g As described above, there is a tendency to be easily developed by controlling at 200 mgKOH/g or less).

The weight average molecular weight of the polymer can be determined, for example, as described later.

When the (meth)acrylate-based polymer is a polymer having a double bond in a side chain (ie, a side chain double bond-containing polymer), the double bond equivalent is preferably 200 to 10000. By being in such a range, the storage stability of a polymer becomes more favorable. It is more preferably 200 to 5000, still more preferably 250 to 4000, and particularly preferably 300 to 4000.

The double bond equivalent is the mass of the solid content of the polymer solution (also referred to as a resin solution) per mol of double bonds in the polymer. The mass of the solid content of the polymer solution referred to herein is the sum of the mass of the constituent components of the monomer component and the mass of the polymerization inhibitor. It is possible to obtain by dividing the mass of the solid content of the polymer solution by the amount of double bonds in the polymer. The amount of double bonds of the polymer can be determined from the amount of the compound having an added acid group, a functional group capable of bonding and a polymerizable double bond.

The curable resin composition of the present invention is also of at least one type selected from the group consisting of a form containing a polymer further having a hydroxyl group, and a form wherein the (meth)acrylate-based polymer further has a hydroxyl group. In this way, by having a hydroxyl group in the system, the ester crosslinked structure is generated between the (meth)acrylic acid caused by decomposition of the structural unit derived from the tertiary carbon-containing (meth)acrylate monomer described above. And curing properties are remarkably high, and it becomes possible to provide a cured product particularly excellent in transparency. Further, the curable resin composition may further contain a polymer having a hydroxyl group, and the (meth)acrylate polymer may further have a hydroxyl group.

As the form in which the (meth)acrylate-based polymer further has a hydroxyl group, as described above, a tertiary carbon-containing (meth)acrylate-based monomer and a monomer having a hydroxyl group and a polymerizable double bond are included, A base polymer preferably obtained by polymerizing a monomer component further containing a monomer having an acid group and a polymerizable double bond; A side chain double bond-containing polymer obtained by reacting a compound having a functional group capable of bonding with an acid group and a polymerizable double bond to the base polymer is preferably mentioned. Among them, the latter side chain double bond-containing polymer is preferred.

<Polymer having a hydroxyl group>

When the curable resin composition further includes a polymer having a hydroxyl group in addition to the (meth)acrylate-based polymer, the polymer having a hydroxyl group is not particularly limited as long as it has a hydroxyl group in the molecule. Among them, from the viewpoint of further enhancing developability, it is preferably a polymer exhibiting alkali solubility, and a polymer having an acid group in the molecule is preferred. The acid group is as described above in the (meth)acrylate polymer, and the acid value of the polymer having a hydroxyl group is preferably within the above-described preferred range in the (meth)acrylate polymer. .

The polymer having a hydroxyl group includes, for example, a monomer having a hydroxyl group and a polymerizable double bond, and preferably a base polymer obtained by polymerizing a monomer component further comprising a monomer having an acid group and a polymerizable double bond ; A side chain double bond-containing polymer obtained by reacting a compound having a functional group capable of bonding with an acid group and a polymerizable double bond to the base polymer is preferably mentioned. Among them, the latter side chain double bond-containing polymer is preferred.

As described above, the form in which the (meth)acrylate-based polymer and/or the polymer having a hydroxyl group is a polymer having a polymerizable double bond in the side chain is included in the 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 a preferred form or specific example of the monomer having an acid group and a polymerizable double bond are as described above, and each monomer Each of 1 type or 2 or more types may be used.

The content ratio of the hydroxyl group and the monomer having a polymerizable double bond is preferably 1% by mass or more with respect to, for example, 100% by mass of the total amount of the monomer components forming the polymer having the hydroxyl group. 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 acid group and the monomer having a polymerizable double bond is preferably set so that the acid value is within the above-described preferred range, for example, based on 100% by mass of the total amount of the monomer components forming the polymer having the hydroxyl group. It is preferable that the content ratio of the monomer having an acid group and a polymerizable double bond is 5% by mass or more. More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. Further, it is preferably 99% by mass or less, more preferably 85% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

The monomer component that forms the polymer having a hydroxyl group may further contain other copolymerizable monomers in addition to the above-described monomers. Other monomers include, for example, N-substituted maleimide-based monomers other than the above-described monomers, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers, and alkyl-(α-allyloxymethyl). ) One or two or more types such as an acrylate monomer, a (meth)acrylic acid ester monomer, and an aromatic vinyl monomer are preferably used. These preferred forms and specific examples are as described above.

In addition, the content ratio of the other monomers 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 forming the polymer having a hydroxyl group. In particular, when an N-substituted maleimide-based monomer is included, the content ratio is preferably 2 to 60% by mass, more preferably 2 from the viewpoints of heat resistance, hardness, colorant dispersibility, development speed, and transparency. It is -50 mass%, More preferably, it is 3-40 mass%.

A method of polymerizing the monomer component or a method of reacting a compound having a functional group capable of bonding with an acid group and a polymerizable double bond to the base polymer obtained by polymerizing the monomer component is as described above.

In the curable resin composition, the content ratio of the (meth)acrylate-based polymer and the polymer having a hydroxyl group may be appropriately set according to the use or blending of other components, for example, their total solid content (polymer having a hydroxyl group) When not included, it means the solid content of only a (meth)acrylate polymer) It is preferable that it is 5 mass% or more with respect to 100 mass% of the total solid content of a curable resin composition. Moreover, it is preferable that it is 80 mass% or less. By being in such a range, it becomes possible to show the effect of this invention more remarkably. More preferably, it is 7 to 70 mass%, More preferably, it is 10 to 60 mass%.

In addition, the "total amount of solid content" means the total amount of components that form a cured product (excluding a solvent that volatilizes when forming a cured product).

Here, in the case of including both the (meth)acrylate-based polymer and the polymer having a hydroxyl group, the blending ratio thereof is (meth)acrylate generated by thermal decomposition of the constituent units derived from the tertiary carbon-containing (meth)acrylate-based monomer. ) The mixing ratio may be set so that the acrylic acid and the hydroxyl group in the system are easily ester crosslinked, and there is no particular limitation. For example, it is preferable to set these mass ratio ((meth)acrylate type polymer/polymer which has a hydroxyl group)=1 to 99/99 to 1. More preferably, it is 10 to 90/90 to 10.

<Polymerizable compound>

The curable resin composition also contains a polymerizable compound. The polymerizable compound is also referred to as a polymerizable monomer, and a polymerizable unsaturated bond (polymerizable unsaturated bond) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (e.g., infrared, ultraviolet, X-ray, etc.), and electron beams. It is a low-molecular compound having a group). For example, a monofunctional compound having one polymerizable unsaturated group in a molecule and a polyfunctional compound having two or more are mentioned.

Examples of the monofunctional polymerizable monomer include N-substituted maleimide and (meth)acrylic acid esters among compounds exemplified as other monomers preferably contained in the monomer component of the (meth)acrylate-based polymer; (Meth)acrylamides; Unsaturated monocarboxylic acids; Unsaturated polyhydric carboxylic acids; Unsaturated monocarboxylic acids in which a chain extends between an unsaturated group and a carboxyl group; Unsaturated acid anhydride logistics; Aromatic vinyls; Conjugated dienes; Vinyl esters; Vinyl ethers; N-vinyl compounds; Unsaturated isocyanates, etc. are mentioned.

As said polyfunctional polymerizable monomer, the following compounds etc. are mentioned, for example.

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 Bifunctional (meth)acrylate compounds such as (meth)acrylate, cyclohexanedimethanoldi(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F alkylene oxide di(meth)acrylate ;

Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritolhepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide added trimethylolpropanetri (Meth)acrylate, ethylene oxide addition ditrimethylolpropane tetra(meth)acrylate, ethylene oxide addition pentaerythritol tetra(meth)acrylate, ethylene oxide addition dipentaerythritol hexa(meth)acrylate, propylene oxide addition 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-capro Trifunctional or higher polyfunctional (meth)acrylate compounds such as lactone-added dipentaerythritol 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 alkyl Renoxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene Polyfunctional vinyl ethers such as oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether;

2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4- (meth)acrylic acid Vinyloxybutyl, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, (meth)acrylate )(Meth)acrylic acid containing vinyl ether groups such as p-vinyloxymethylphenylmethyl acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)ethyl (meth)acrylate 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 alkyl Renoxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene Polyfunctional allyl ethers such as oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether;

Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate;

Tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide addition tri(acryloyloxyethyl)isocyanurate, alkylene oxide addition tri( Polyfunctional (meth)acryloyl group-containing isocyanurates such as methacryloyloxyethyl) isocyanurate;

Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate;

Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate Polyfunctional urethane (meth)acrylates obtained by using;

Polyfunctional aromatic vinyls such as divinylbenzene, etc.

Among the polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further enhancing the curability of the curable resin composition of the present invention. When a polyfunctional polymerizable compound is used as the polymerizable compound, the number of functionalities is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. In addition, from the viewpoint of further suppressing cure shrinkage, the functional number is preferably 10 or less, and more preferably 8 or less.

Further, the molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, for example, 2000 or less is preferable.

In the case of using a polyfunctional polymerizable compound 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 and 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 a higher hardness and higher transparency. More preferably, a trifunctional or higher polyfunctional (meth)acrylate compound is used.

As the content ratio of the polymerizable compound, in addition to the type of the polymerizable compound or the (meth)acrylate-based polymer to be used, it may be appropriately set according to the purpose or use, but from the viewpoint of more excellent developability and plateability, curability It is preferable that it is 2 mass% or more with respect to 100 mass% of total solid content of a resin composition, and it is preferable that it is 80 mass% or less. As a lower limit, it is more preferably 5% by mass or more, still more preferably 8% by mass or more, particularly preferably 10% by mass or more, and as an upper limit, more preferably 70% by mass or less, still more preferably 50% by mass or less, It is particularly preferably 30% by mass or less, and most preferably 20% by mass or less.

<Photopolymerization initiator>

The curable resin composition further includes a photoinitiator. As a photoinitiator, Preferably, it is a radical polymerizable photoinitiator. The radical polymerizable photopolymerization initiator generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or two or more commonly used ones can be used. Further, if necessary, a photosensitizer, a photoradical polymerization accelerator, or the like may be used alone or in combination of two or more. Together with the photoinitiator, a photosensitizer and/or a photoradical polymerization accelerator may or may not be used. Even if the photosensitizer and/or the photo-radical polymerization accelerator are not used together, the effect of the present invention is sufficiently exhibited, but when used together, the 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-hydroxycyclohexylphenylketone, 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 ) Alkylphenone compounds such as phenyl]-1-butanone; Benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Thioxanthone type such as thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, and 2,4-diethyl thioxanthone Compound;

2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloro Halomethylated triazine compounds such as romethyl)-s-triazine; 2-Trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3 Halomethylated oxadiazole compounds such as ,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2'-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'- Biimidazole compounds, such as tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-car Oxime ester compounds such as bazol-3-yl]- and 1-(O-acetyloxime); Titanocene-based compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; Acridine compounds such as 9-phenylacridine;

Examples of the photosensitizers and photo-radical polymerization accelerators that may be used in combination with the photoinitiator include dye-based compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin-based compounds, and pyromethene dyes; Dialkylaminobenzene-based compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; And mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, and 2-mercaptobenzoimidazole.

The content of the photopolymerization initiator may be appropriately set depending on the purpose, use, etc., and is not particularly limited, but is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total solid content of the curable resin composition excluding the photopolymerization initiator. Thereby, a cured product having more excellent adhesion can be obtained, and peeling is more sufficiently suppressed even after exposure to a high temperature. Further, in consideration of the balance of the effect of the decomposition product of the photopolymerization initiator and economic efficiency, it is preferably 30 parts by mass or less. As a lower limit, it is more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, and as an upper limit, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less. .

The photosensitizer and the photo-radical polymerization accelerator do not need to be used as described above, but in the case of use, from the viewpoint of the balance of curability, the influence of the decomposition product, and the economy, the total solid content of the curable resin composition is 100% by mass. On the other hand, it is preferably 0.001 to 20 mass%. It is more preferably 0.01 to 15% by mass, and still more preferably 0.05 to 10% by mass.

<other ingredients>

-solvent-

It is preferable that the said curable resin composition further contains a solvent. The solvent is preferably used as a diluent or the like. Specifically, the viscosity is lowered and the handling property is improved; Forming a coating film by drying; It is a low-viscosity organic solvent or water which is preferably used for setting as a dispersion medium for a coloring material or the like and capable of dissolving or dispersing each of the components contained in the curable resin composition.

As the solvent, a commonly used one can be used, and it is not particularly limited as long as it is appropriately selected according to the purpose and use, 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, and 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 monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol monoethers such as propylene glycol monobutyl ether and 3-methoxybutanol; Glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether Ethers;

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 Glycol mono such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, and 3-methoxybutyl acetate Ether esters; Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3- Alkyl esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 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; Water, etc.

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

The curable resin composition may further include, for example, a colorant (also referred to as a colorant) according to the required characteristics of each application to which it is applied; Dispersant; Heat resistance improver; Leveling agent; Developing aid; Inorganic fine particles such as silica fine particles; Coupling agents such as silane-based, aluminum-based, and titanium-based; Thermosetting resins, such as a filler, an epoxy resin, a phenol resin, and polyvinylphenol; Curing aids such as polyfunctional thiol compounds; Plasticizer; Polymerization inhibitor; Ultraviolet absorber; Antioxidant; Gloss remover; Antifoam; Antistatic agent; Slip agent; Surface modifier; Thixotropic agents; Thixotropic aid; Quinone diazide compounds; Polyhydric phenol compound; Cationic polymerizable compounds; You may further contain 1 type, or 2 or more types, such as an acid generator. For example, when using the said curable resin composition for a color filter application, it is preferable to contain a color material. As described above, the form in which the curable resin composition further includes a colorant is also one of the preferred embodiments of the present invention. Further, a form containing at least one selected from the group consisting of a coloring material, a dispersant, a heat resistance improver, a leveling agent, a coupling agent, and a development aid is also preferable. Hereinafter, these components are described.

-Coloring material-

As the color material, for example, a pigment or dye is preferably used. These may be used individually or may be used in combination of 2 or more types. Moreover, you may combine a pigment and a dye. For example, when forming red, blue, and green pixels of a color filter, a technique in which a color material such as blue and purple, green and yellow, etc. is combined to exhibit the required color characteristics is preferably used. In addition, even when forming a black matrix, it can be formed using a black colorant.

Among the above pigments and dyes, for example, in terms of durability, pigments (for example, organic pigments or inorganic pigments) are excellent, and, for example, in terms of improving luminance of panels, etc. These may be appropriately selected or used in combination according to characteristics. Moreover, among the pigments, it is more preferably an organic pigment.

Examples of the pigments include azo pigments, phthalocyanine pigments, polycyclic pigments (e.g., quinacridone, perylene, perinone, isoindolinone, isoindolin, dioxazine, thioindigo , Anthraquinone-based, quinophthalone-based, metal complex-based, diketopyrrolopyrrole-based, etc.), and organic pigments such as dye lake-based pigments; White and extender pigments (e.g. titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), rapeseed pigments (e.g., sulfur, cadmium, chromium vermillion, nickel titanium, chromium titanium, yellow Iron oxide, bengala, zinc chromate, bristle, ultramarine, royal blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), black pigments (e.g. carbon black, bone black, graphite, iron black, titanium Black, etc.), inorganic pigments, such as a light pigment (for example, a pearl pigment, an aluminum pigment, a bronze pigment, etc.), and a fluorescent pigment (for example, zinc sulfide, strontium sulfide, strontium aluminate) are mentioned. Further, examples of the color of the pigment 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-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose or use.

Specific examples of the pigment are shown by color index (C.I.; issued by The Society of Dyers and Colourists) numbers below for each color, but the color material of the present invention is not limited thereto. Moreover, these may be used individually, and may be used combining two or more types. The following "C.I." refers to a color index, and a number refers to a color index number.

As a yellow pigment, for example, C.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, etc. are mentioned.

As an orange pigment, for example, C.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.

As a purple pigment, for example, C.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.

As a red pigment, for example, C.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, 144, 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.

As a blue pigment, for example, C.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.

As a green pigment, for example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, etc. are mentioned.

As a brown pigment, for example, C.I. Pigment Brown 5, 6, 23, 24, 25, 32, 41, 42, etc. are mentioned.

As a black pigment, for example, aniline black, carbon black, lamp black, bone black, black iron, titanium black, C.I. Pigment Black 1, 6, 7, 9, 10, 11, 12, 13, 20, 31, 32, 34, etc. are mentioned. As a white pigment, for example, C.I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28, etc. are mentioned.

Examples of the dye include organic dyes described in Japanese Patent Application Laid-Open No. 2010-9033, Japanese Patent Application Laid-Open No. 2010-211198, Japanese Patent Application Laid-Open No. 2009-51896, and Japanese Patent Application Laid-Open No. 2008-50599. You can use Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferred.

The content ratio of the coloring material (that is, the total ratio of the pigment and dye) can be appropriately set depending on the purpose and use, but the preferred range of the content rate of the coloring material is 3 to 70 mass% based on 100 mass% of the total solid content of the curable resin composition. % to be. It is more preferably 5 to 60 mass%, and still more preferably 10 to 50 mass%.

-Dispersant-

The dispersant has an interaction site for a coloring material and an interaction site for a dispersion medium (for example, a solvent or a binder resin), and has a function of stabilizing the dispersion of the color material in a dispersion medium, and generally, a resin type dispersant (For example, polymer dispersants), surfactants (for example, low molecular weight dispersants), and pigment derivatives. It is preferable that the curable resin composition of this invention contains a dispersing agent together with a coloring material. Further, as the dispersing agent (ie, resin type dispersant, surfactant and/or pigment derivative), a commonly used dispersant can be used. Moreover, as a dispersing agent, 1 type may be used individually, and 2 or more types may be combined and used for it.

Examples of the resinous dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, and polycarboxyl Acid alkylamine salt, polysiloxane, long chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide formed by reaction of poly(lower alkyleneimine) and polyester having free carboxyl group, or salts 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/poly And propylene oxide adducts.

In addition, as the structure of the resin type dispersant, the main chain is an anchor chain having an interaction site for the colorant, and the graft chain is a resin or anchor chain having a graft structure such that the graft chain is a compatible chain having interaction with the dispersion medium. A resin in which the hypercompatible chain has a block structure is particularly preferably used.

When the brand name of the said resin-type dispersant is illustrated, the following things are mentioned, for example. 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, EDAPLAN470, 472, 480, 482, K-SPERSE131, 1525070, 5207 (above, manufactured by EFKA ADDITIVES); Anti-Terra-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 Vik Chemie ); SOLSPERSE3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 22000, 24000, 24000GR, 26000, 28000 (above, manufactured by Nippon Lubrizol); Disperlon7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 152MS (above, manufactured by Kusumoto Hwaseong Corporation); Azisper PB-711, 821, 822, 880, PN-411, PA-111 (above, manufactured by Ajinomoto Fine Techno); KP series (manufactured by Shin-Etsu Chemical Co., Ltd.); Polyflow series (made by Kyoeisha Chemical Co., Ltd.); MegaPak series (manufactured by DIC); Disperade series (manufactured by Sannovco), and the like.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, Anionic surfactants such as ammonium lauryl sulfate, sodium stearate, and sodium lauryl sulfate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; Alkyl betaines, such as alkyl dimethyl amino acetate betaine, and amphoteric surfactants, such as alkyl imidazoline, etc. are mentioned.

The dye derivative is a compound having a structure in which a functional group is introduced into a dye, and as a functional group, for example, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, a phthalimide And the like. As a structure of the parent pigment, for example, azo-based, anthraquinone-based, quinophthalone-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolin-based, dioxazine-based, indanthrene-based, Perylene system, diketopyrrolopyrrole system, etc. are mentioned.

The content ratio of the dispersant (i.e., resin type dispersant, surfactant, and/or pigment derivative) may be appropriately set according to the purpose or use, but from the viewpoint of balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency. , For example, it is preferable that it is 0.01-60 mass% with respect to 100 mass% of the total solid content of a curable resin composition. It is more preferably 0.1 to 50% by mass, and still more preferably 0.3 to 40% by mass.

-Heat resistance improver-

The heat resistance improver is preferably used to improve heat resistance or strength. As the heat resistance improving agent, for example, an N-(alkoxymethyl) melamine compound, a compound having two or more epoxy groups or oxetanyl groups, and the like are preferable. 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, their use is preferable.

-Leveling agent-

The leveling agent is preferably used to improve leveling properties. As the leveling agent, a fluorine-based or silicone-based surfactant is preferable.

-Coupling agent-

The coupling agent is preferably used to improve adhesion. As the coupling agent, a silane-based coupling agent is preferable, and examples thereof include an epoxy-based, methacrylic, and amino-based silane coupling agent. Among them, an epoxy-based silane coupling agent is preferable.

-Development aid-

The developing aid is preferably used to improve developability. Examples of the developing auxiliary agent include monocarboxylic acids such as (meth)acrylic acid, acetic acid, and propionic acid; Polyhydric carboxylic acids such as maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, and trimellitic acid; Carboxylic anhydrides, such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride, are preferable.

It does not specifically limit as a manufacturing method of the said curable resin composition, For example, it can prepare by mixing and dispersing the above-mentioned containing component using various mixers and dispersing machines. The mixing/dispersing process is not particularly limited and may be carried out by a conventional method. Moreover, you may further include other processes which are normally performed. Moreover, when the said curable resin composition contains a coloring material, it is preferable to manufacture through the dispersion treatment process of a coloring material.

As the dispersion treatment process of the color material, for example, first, a color material (preferably an organic pigment), a dispersant and a solvent are weighed in predetermined amounts, and a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homo A method of dispersing the colorant fine particles using a dispersing machine such as a genizer, a kneader, or a blender to obtain a liquid colorant dispersion (also referred to as a mill base) is mentioned. Preferably, kneading and dispersion treatment is performed by a roll mill, a kneader, a blender, or the like, and then fine dispersion treatment is performed using a media mill such as a bead mill filled with beads of 0.01 to 1 mm. To the obtained mill base, a composition (preferably a transparent liquid) containing a (meth)acrylate-based polymer, a polymerizable monomer, and a photoinitiator, and a solvent or leveling agent, etc., which have been separately stirred and mixed, is added. Then, it mixes and sets it as a uniform dispersion solution, and a curable resin composition can be obtained.

In addition, it is preferable that the obtained curable resin composition is subjected to filtration treatment with a filter or the like to remove fine dust.

[Hardened cargo]

The curable resin composition of the present invention, as described above, is particularly excellent in photosensitivity and curability, and provides a cured product having excellent basic performance such as developability, solvent resistance, adhesion to a substrate (substrate), heat resistance, and transparency. will be. Such a cured product is also excellent in image formation properties and surface smoothness, and, for example, has no residue of an unexposed portion or soil contamination after development. A cured product obtained by curing such a curable resin composition is also one of the present invention.

The cured product (cured film) preferably has a film thickness (thickness) of 0.1 to 20 µm. Thereby, it is possible to sufficiently cope with the demand for reduction of the magnification of a member or a display device using the cured product. It is more preferably 0.5 to 10 µm, and still more preferably 0.5 to 8 µm.

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

<Color filter>

The color filter of the present invention has the cured product on a substrate.

In the color filter, the cured product formed from the curable resin composition of the present invention is particularly preferable as a segment requiring coloring, such as a black matrix or each pixel such as red, green, blue, and yellow, It is preferable also as a segment which does not necessarily require coloring, such as a photo spacer, a protective layer, and the rib for orientation control.

Examples of the substrate used for the color filter include glass substrates such as white plate glass, blue plate glass, alkali tempered glass, and silica coated blue plate glass; Sheets, films, or substrates made of thermoplastic resins such as polyester, polycarbonate, polyolefin, polysulfone, ring-opening polymer of cyclic olefin and hydrogenated products thereof; Sheets, films, or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates, such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate; 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) provided with a color material layer on its surface, etc. are mentioned. Among them, from the viewpoint of heat resistance, a glass substrate or a sheet, film, or substrate made of a heat-resistant resin is preferable. In addition, it is preferable that the substrate is a transparent substrate.

Further, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent or the like, if necessary.

<Production method of color filter>

In obtaining the color filter, for example, for one pixel color, a step of disposing the curable resin composition on a substrate (also referred to as a placement step), and light to the curable resin composition disposed on the substrate A method including a step of irradiating (also referred to as a light irradiation step), a step of developing treatment with a developer (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step) is adopted, and the same method as this It is preferable to employ a manufacturing method that repeats with each color. In addition, the order of formation of the pixels of each color is not particularly limited.

-Batch process (preferably coating process)-

It is preferable to perform the said arrangement process by application. As a method of applying the curable resin composition on a substrate, for example, spin coating, slit coating, roll coating, cast coating, and the like, and any method can be preferably used.

In the above arrangement step, it is preferable to dry the coating film after further applying the curable resin composition on the substrate. Drying of the coating film can be performed using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected depending on the boiling point of the contained solvent component, the type of the curing component, the film thickness, the performance of the dryer, and the like, but it is usually carried out at a temperature of 50 to 160°C for 10 to 300 seconds.

-Light irradiation process-

In the light irradiation step, as a light source of active light used, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp. A lamp light source such as, an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, a laser light source such as a semiconductor laser, and the like are used. Further, as the exposure machine method, a proximity method, a mirror projection method, and a stepper method may be mentioned, but a proximity method is preferably used.

In addition, in the irradiation step of the active energy ray, depending on the application, the active energy ray may be irradiated through a predetermined mask pattern. In this case, the exposed portion is cured, and the cured portion is insolubilized or poorly dissolved in the developer.

-Development process-

The developing step is a step of forming a pattern by performing a developing treatment with a developer and removing an unexposed portion after the above-described light irradiation step. Thereby, a patterned cured film can be obtained. The developing treatment can be performed by a method such as immersion development, spray development, brush development, and ultrasonic development at a development temperature of 10 to 50°C.

The developer used in the above developing 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 an alkaline aqueous solution is used as a developer, it is preferable to wash with water after development.

As an organic solvent preferable as the said developer, an ether type solvent, an alcohol type solvent, etc. are mentioned, for example. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkylphenyl ethers, aralkyl Phenyl ethers, diaromatic ethers, isopropanol, benzyl alcohol, and the like.

In addition to an alkali agent, the alkaline aqueous solution may contain surfactants, organic solvents, buffers, dyes, pigments, and the like, if necessary. As an organic solvent in this case, an organic solvent etc. which are preferable as the above-mentioned developing solution are mentioned.

Examples of the alkali agent include inorganic alkali agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tertiary sodium phosphate, second sodium phosphate, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate; Amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide, and these It may be, or two or more types may be combined.

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

-Heating process-

The heating step is a step (also referred to as a post curing step) of further curing the exposed portion (cured portion) by firing after the above-described developing step. For example, using a light source such as a high-pressure mercury lamp, for example, a step of post-exposing with a light amount of 0.5 to 5 J/cm 2, or after heating at a temperature of, for example, 60 to 260 °C over 10 seconds to 120 minutes The process of doing it, etc. are mentioned. By performing such a post-curing process, it becomes possible to make the hardness and adhesiveness of the patterned cured film further stronger. In addition, by this heating step, part of the constituent units of the (meth)acrylate polymer contained in the curable resin composition (i.e., the part derived from a part of the tertiary carbon-containing (meth)acrylate monomer) is decomposed As a result, curing properties and solvent resistance can be improved.

It is preferable that the film thickness of the cured film obtained by the said heating process (that is, the cured film obtained by thermosetting the said curable resin composition) is 0.1-20 micrometers. By using the curable resin composition of the present invention, a cured film having a sufficiently reduced film thickness can be provided. It is more preferably 0.5 to 10 µm, and still more preferably 0.5 to 8 µm.

Moreover, it is preferable that the film thickness of the coating film (that is, a cured film) obtained by the heating step is 90% or less, assuming that the film thickness of the coating film before heating is 100%. More preferably, it is 80% or less, More preferably, it is 70% or less.

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

Although the heating time in the said heating process is not specifically limited, For example, it is preferable to set it as 5 to 60 minutes. In addition, the heating method is also not particularly limited, but can be carried out using, for example, 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 constructed by using the color filter.

Further, a member for a display device and a display device having a cured product formed from the curable resin composition are also included in preferred embodiments of the present invention. The cured product (cured film) formed by the curable resin composition is stable, has excellent adhesion to a substrate, etc., has high hardness, has high smoothness, and has a high transmittance, so it is particularly preferable as a transparent member. In addition, it is useful also as a protective film or an insulating film in various display devices.

As the display device, a liquid crystal display device, a solid-state imaging device, a touch panel display device, and the like are preferable, for example.

In addition, when the cured product (cured film) is used as a member for a display device, the member may be a film-like single layer or multilayer member composed of the cured film, and other layers may be added to the single layer or multilayer member. It may be a combined member or a member including the cured film in its constitution.

Since the curable resin composition of the present invention has the configuration as described above, it can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to the substrate (substrate), heat resistance and transparency, and is excellent in storage stability. It is useful for various applications such as color filters, etc. Accordingly, 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 or the electric/electronic field.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "part" means "mass part".

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

<weight average molecular weight>

Using polystyrene as a standard material and tetrahydrofuran as an eluent, the weight average molecular weight was determined by HLC-8220GPC (manufactured by Tosoh Corporation), column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) by GPC (gel permeation chromatography) method. Measured.

<solid content>

About 1 g of a polymer solution (also referred to as a resin solution or a polymer solution) was weighed and contained in an aluminum cup, and about 3 g of acetone was added and dissolved, followed by air drying at room temperature. And after drying for 1.5 hours at 140 degreeC under vacuum using a hot air dryer (made by SPEC, brand name: PHH-101), it stood to cool in a desiccator, and the mass was measured. From the mass reduction amount, the solid content (mass%) of the polymer solution was calculated.

<acid value>

3 g of the resin solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an aqueous 0.1 N KOH solution was used as a titration solution, and an automatic titration apparatus (manufactured by Hiranuma Industrial Co., Ltd., brand name: COM-555) By, the acid value of the polymer solution was measured, and the acid value (AV) per 1 g of solid content was obtained from the acid value of the solution and the solid content of the solution.

<Absorbance of the curable resin composition>

The curable resin composition was spin-coated on a 5 cm wide glass substrate, dried at 80°C for 3 minutes, exposed to 100 mJ with a high pressure mercury lamp, heat treated at 220°C for 30 minutes, and a film thickness of 5 μm To obtain a thin film. Thereafter, it was immersed in 20 g of 1-methyl-2-pyrrolidone at 25° C. for 2 hours, and the color of 1-methyl-2-pyrrolidone eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). It measured and calculated|required the absorbance of 450 nm.

Synthesis Example 1

Synthesis of resin solution 1 (BzMI-CHMA-t-BMA-MAA copolymer solution)

844.57 g of propylene glycol monomethyl ether acetate was injected into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube and a dropping tank inlet port, substituted with nitrogen, and heated to raise the temperature to 90°C. On the other hand, as a dropping tank (A), 50 g of N-benzyl maleimide, 125 g of cyclohexyl methacrylate, 225 g of t-butyl methacrylate, 100 g of methacrylic acid, and t-butylperoxy-2 in a beaker -10 g of ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil Corporation) was prepared by stirring and mixing, and in a dropping tank (B), 21 g of n-dodecyl mercaptan, 84 g of propylene glycol monomethyl ether acetate The mixture was prepared by stirring. After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was increased to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 7800, the acid value was 129 mgKOH/g, and the resin solid content was 35.0 mass%.

Synthesis Example 2

Synthesis of resin solution 2 (BzMI-CHMA-HEMA-MAA copolymer solution)

844.57 g of propylene glycol monomethyl ether acetate was injected into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube and a dropping tank inlet port, substituted with nitrogen, and heated to raise the temperature 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 A thing obtained by stirring and mixing 10 g of -2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil Co., Ltd.) was prepared, and in a dropping tank (B), 21 g of n-dodecyl mercaptan, propylene glycol monomethyl ether acetate 84 g was prepared by stirring and mixing. After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was increased to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 7700, the acid value was 129 mgKOH/g, and the resin solid content was 35.0 mass%.

Synthesis Example 3

Synthesis of resin solution 3 (side chain double bond-containing copolymer; BzMI-t-BA-AA//GMA copolymer solution)

Into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube, and a dropping tank inlet, 1006.67 g of propylene glycol monomethyl ether was injected, replaced with nitrogen, and heated to 90°C. On the other hand, as a dropping tank (A), 20 g of N-benzyl maleimide, 250 g of t-butyl acrylate, 230 g of acrylic acid, and t-butylperoxy-2-ethylhexanoate (manufactured by Nippon Oil &amp; A thing obtained by stirring and mixing 10 g of butyl O") was prepared, and a mixture of 40 g of n-dodecyl mercaptan and 160 g of propylene glycol monomethyl ether was prepared in a dropping tank (B). After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was raised to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

Thereafter, nitrogen in the gas introduction pipe was changed to an oxygen/nitrogen mixed gas (oxygen/nitrogen = 5/95 vol%), and 2,2'-methylenebis(4-methyl-6-t-butylphenol) as an inhibitor (Kawaguchi Chemical Co., Ltd. make, "Antage w-400") 1.34 g and triethylamine 2.68 g as a catalyst were added, and after stirring and mixing, glycidyl methacrylate 393.74 g as an additional compound was added, and 115 After 8 hours, the reaction was terminated when the residual GMA amount by GC (gas chromatography) analysis became 0.5% by mass or less, and the acid group having a radically polymerizable double bond in the side chain A polymer solution of the containing copolymer was obtained.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 6800, the acid value was 58 mgKOH/g, and the resin solid content was 39.0 mass%.

Synthesis Example 4

Synthesis of resin solution 4 (side chain double bond-containing copolymer; BzMI-CHA-HEA-AA//GMA copolymer solution)

Into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube, and a dropping tank inlet, 1006.67 g of propylene glycol monomethyl ether was injected, replaced with nitrogen, and heated to 90°C. On the other hand, as a dropping tank (A), in a beaker, 20 g of N-benzyl maleimide, 150 g of cyclohexyl acrylate, 100 g of 2-hydroxyethyl acrylate, 230 g of acrylic acid, and t-butylperoxy-2-ethylhexano A thing prepared by stirring and mixing 10 g of Eight ("Perbutyl O" manufactured by Nippon Oil Corporation) was stirred and mixed with 40 g of n-dodecyl mercaptan and 160 g of propylene glycol monomethyl ether in a dropping tank (B). Ready. After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was increased to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

Thereafter, nitrogen in the gas introduction pipe was changed to an oxygen/nitrogen mixed gas (oxygen/nitrogen = 5/95 vol%), and 2,2'-methylenebis(4-methyl-6-t-butylphenol) as an inhibitor (Kawaguchi Chemical Co., Ltd. make, "Antage w-400") 1.34 g and triethylamine 2.68 g as a catalyst were added, and after stirring and mixing, glycidyl methacrylate 393.74 g as an additional compound was added, and 115 After 8 hours, the reaction was terminated when the residual GMA amount by GC (gas chromatography) analysis became 0.5% by mass or less, and the acid group having a radically polymerizable double bond in the side chain A polymer solution of the containing copolymer was obtained.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 6800, the acid value was 58 mgKOH/g, and the resin solid content was 39.0 mass%.

Synthesis Example 5

Synthesis of resin solution 5 (BzMI-CHMA-t-BMA-HEMA-MAA copolymer solution)

844.57 g of propylene glycol monomethyl ether acetate was injected into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube and a dropping tank inlet port, substituted with nitrogen, and heated to raise the temperature to 90°C. On the other hand, as a dropping tank (A), in a beaker, 50 g of N-benzyl maleimide, 125 g of cyclohexyl methacrylate, 125 g of t-butyl methacrylate, 100 g of 2-hydroxyethyl methacrylate, and metallylic acid A mixture of 100 g and 10 g of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil Corporation) was prepared by stirring, and n-dodecylmercaptan 21 was added to the dropping tank (B). g and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was raised to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

As a result of analyzing the obtained polymer solution, 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 of resin solution 6 (side chain double bond-containing copolymer; BzMI-t-BA-HEA-AA//GMA copolymer solution)

Into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube, and a dropping tank inlet, 1006.67 g of propylene glycol monomethyl ether was injected, replaced with nitrogen, and heated to 90°C. On the other hand, as a dropping tank (A), 20 g of N-benzyl maleimide, 150 g of t-butyl acrylate, 100 g of 2-hydroxyethyl acrylate, 230 g of acrylic acid, and t-butylperoxy-2-ethylhexa in a beaker A thing obtained by stirring and mixing 10 g of noate ("Perbutyl O" manufactured by Nippon Oil & Co., Ltd.) was prepared, and 40 g of n-dodecyl mercaptan and 160 g of propylene glycol monomethyl ether were stirred and mixed in a dropping tank (B). I prepared it. After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was raised to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

Thereafter, nitrogen in the gas introduction pipe was changed to an oxygen/nitrogen mixed gas (oxygen/nitrogen = 5/95 vol%), and 2,2'-methylenebis(4-methyl-6-t-butylphenol) as an inhibitor (Kawaguchi Chemical Co., Ltd. make, "Antage w-400") 1.34 g and triethylamine 2.68 g as a catalyst were added, and after stirring and mixing, glycidyl methacrylate 393.74 g as an additional compound was added, and 115 After 8 hours, the reaction was terminated when the residual GMA amount by GC (gas chromatography) analysis became 0.5% by mass or less, and the acid group having a radically polymerizable double bond in the side chain A polymer solution of the containing copolymer was obtained.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 6800, the acid value was 58 mgKOH/g, and the resin solid content was 39.0 mass%.

Synthesis Example 7

Synthesis of resin solution 7 (MMA-MAA copolymer solution)

844.57 g of propylene glycol monomethyl ether acetate was injected into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube and a dropping tank inlet port, substituted with nitrogen, and heated to raise the temperature to 90°C. On the other hand, as a dropping tank (A), 400 g of methyl methacrylate, 100 g of metalyl acid, and 10 g of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Co., Ltd.) were added to a beaker. The thing which stirred and mixed was prepared, and the thing which stirred and mixed 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate was prepared in the dropping tank (B). After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was raised to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

As a result of analyzing the obtained polymer solution, 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

Synthesis of resin solution 8 (BzMI-t-BMA-HEMA-MAA copolymer solution)

874.57 g of propylene glycol monomethyl ether acetate was injected into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube, and a dropping tank inlet port, replaced with nitrogen, and heated to raise the temperature to 90°C. On the other hand, as a dropping tank (A), 50 g of N-benzyl maleimide, 235 g of t-butyl methacrylate, 100 g of 2-hydroxyethyl methacrylate, 115 g of metalyl acid, and t-butyl peroxy in a beaker A thing obtained by stirring and mixing 10 g of -2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil Co., Ltd.) was prepared, and in a dropping tank (B), 6 g of n-dodecyl mercaptan, propylene glycol monomethyl ether acetate 54 g was prepared by stirring and mixing. After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was increased to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 15500, the acid value was 150 mgKOH/g, and the resin solid content was 35.0 mass%.

Synthesis Example 9

Synthesis of resin solution 9 (MD-t-BMA-HEMA-MAA copolymer solution)

844.57 g of propylene glycol monomethyl ether acetate was injected into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube and a dropping tank inlet port, substituted with nitrogen, and heated to raise the temperature 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, and methacrylic in a beaker A mixture of 100 g of acid 2-hydroxyethyl, 100 g of metallic acid and 10 g of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil Corporation) was prepared by stirring, and a dropping tank ( To B), 15 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was increased to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

As a result of analyzing the obtained polymer solution, 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

Synthesis of resin solution 10 (AMA-t-BMA-HEMA-MAA copolymer solution)

844.57 g of propylene glycol monomethyl ether acetate was injected into a reaction tank equipped with a thermometer, agitator, a gas inlet tube, a cooling tube and a dropping tank inlet port, substituted with nitrogen, and heated to raise the temperature 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, and metal in a beaker A thing obtained by stirring and mixing 100 g of lylic acid and 10 g of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil Corporation) was prepared, and n-dodecylmercaptan 15 g and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 90°C, dropping was started over 3 hours from the dropping tank while maintaining the same temperature, and polymerization was performed. After the dropwise addition was completed, the temperature was raised to 115°C after maintaining at 90°C for 30 minutes, followed by aging for 90 minutes.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 12300, the acid value was 132 mgKOH/g, and the resin solid content was 35.2 mass%.

In Table 1, the details of resin solutions 1-10 are shown.

In addition, with respect to the compounding amount of the monomers constituting the resin in Table 1, the numerical values of the respective monomers constituting the base polymer describe the respective compounding ratios (mass%) when the total amount thereof is 100% by mass. In addition, in Synthesis Examples 4 and 6, the value of GMA (a compound having a functional group capable of bonding with an acid group and a polymerizable double bond) added to the base polymer is a monomer having an acid group and a polymerizable double bond (in this case, It is described as the ratio of GMA added to the carboxylic acid component of "A", "GMA compounding ratio (AA compounding ratio (mass%) to which GMA was added)) = (molar amount of GMA (mol)/molar amount of AA (mol )} × AA compounding ratio (mass%)". For example, in Synthesis Example 4, AA in the base polymer (100% by mass) was constituted by 46% by mass, and 2769 mmol of GMA was added to this 46% by mass (3191 mmol) of AA, The blending ratio (mass%) of the GMA was defined as "40".

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

Propylene glycol monomethyl ether acetate was 12.9 parts, dispalon DA-7301 was 0.4 parts as a dispersant, and C.I. 2.25 parts of Pigment Green 36 (Monastral Green 6Y-CL, manufactured by Heubach), and C.I. Pigment Yellow 150 (Yellow Pigment E4GN-GT, manufactured by Lanxess) 1.5 parts were mixed, and the pigment dispersion 1 was obtained by dispersing for 3 hours with a paint shaker.

Example 1

1.0 part of resin solution 1, 1.0 part of resin solution 2, 0.70 parts of dipentaerythritol hexaacrylate as a radical polymerizable compound, Irgacure 369 (manufactured by Chiba Specialty Chemicals) as a radical polymerizable photoinitiator 0.35 parts, 7.88 parts of pigment dispersion 1, and 6.57 parts of propylene glycol monomethyl ether acetate were mixed as a solvent, and curable resin composition 1 was obtained. When absorbance was measured for this curable resin composition 1, it was 1.6×10 ^-2 .

Examples 2 to 8, Comparative Examples 1 to 7

Except having made it the compounding shown in Tables 2 and 3, it carried out similarly to Example 1, and after obtaining each curable resin composition 2-15, each absorbance was measured. The results are shown in Tables 2 and 3.

From the results of Tables 2 and 3, the following were 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 are examples in which the absorbance was measured by obtaining a cured product under the same conditions, respectively. When comparing these, both absorbance was remarkably large in the comparative example compared to the Example, and the transparency of the cured product was It can be seen that it is inferior. Here, if the curing property or solvent resistance of the curable resin composition is insufficient, the absorbance of the cured product increases due to the elution of the colorant, so from the results of Tables 2 and 3, the curable resin composition of the comparative example compared to the example has curability and content. You can see that the sanctions were insufficient. In addition, 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)

As a curable resin composition comprising a (meth)acrylate-based polymer, a polymerizable compound and a photoinitiator,
The (meth)acrylate-based polymer is a polymer having a structural unit derived from a tertiary carbon-containing (meth)acrylate-based monomer,
The tertiary carbon-containing (meth)acrylate-based monomer is 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 having 12 or less carbon atoms, including a structure having a tertiary carbon atom on the oxygen atom side.)
The curable resin composition further comprises at least one type selected from the group consisting of a polymer having a hydroxyl group, and the (meth)acrylate-based polymer further having a hydroxyl group. Resin composition. delete The method of claim 1,
The (meth)acrylate-based polymer and/or the polymer having a hydroxyl group is a polymer having a polymerizable double bond in a side chain. A cured product obtained by curing the curable resin composition according to claim 1 or 3. A color filter comprising the cured product according to claim 4 on a substrate. A display device configured by using the color filter according to claim 5.