TWI603983B - Hardening resin composition and its use - Google Patents

Description

Curable resin composition and use thereof

The present invention relates to a curable resin composition and use thereof. More specifically, the present invention relates to a color filter, an ink, a printing plate, a printed wiring board, a semiconductor element, a photoresist, and the like which are used in a liquid crystal display device or a solid-state image sensor or the like, or electrical- A curable resin composition for various uses such as an electronic device, a cured product thereof, a color filter using a cured product, and a display device.

A color filter, an ink, a printing plate, a printed wiring board, a semiconductor element, and a light used in a liquid crystal display device or a solid-state imaging device, for example, a curable resin composition which can be cured by heat or an active energy ray. Various applications such as various optical members and electric-electronic devices have been studied, and various types of curable resin compositions having excellent properties required for each application have been developed. In these applications, a color filter is a main component of a liquid crystal display device or a solid-state image sensor. Generally, it is a substrate, and at least three primary colors (red (R), green (G), and blue (B). The pixel and the resin black matrix (BM) separating the pixels, and a protective film or the like provided for covering and protecting the pixel and the resin black matrix and flattening the unevenness.

In general, in the case where a pixel of a color filter is formed using a curable resin composition, a method of performing the following steps on each color pixel and repeating the same steps for each color is employed: (1) on the entire substrate Coating step of coating the surface of the curable resin composition; (2) An exposure step of patterning the resist film formed by the coating step by a mask to cure the exposed portion, and then exposing the cured portion; and (3) removing the unexposed portion by the developer A development and calcination (baking) treatment step of calcining (baking) to further harden the exposed portion. When it is considered to be used in such a color filter application or the like, the curable resin composition is required to have curability, solvent resistance after curing, adhesion to a substrate (substrate), heat resistance, transparency, and the like. Various physical properties. In addition, in recent years, the industry is promoting the miniaturization, thinning, and energy saving of optical members, electric-electronic devices, and the like, and accordingly, high-quality performance is required for components such as color filters to be used.

As a composition suitable for a color filter, for example, a composition containing a binder resin, a colorant, a photopolymerizable compound, a photopolymerization initiator, and a solvent is disclosed. a resin composition 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 (refer to Patent Document 1); or A colored photosensitive resin composition containing a copolymer, a radiation-sensitive linear radical polymerization initiator, an ethylenically unsaturated compound, and a coloring agent, the copolymer containing a carboxyl group/phenolic hydroxyl group protected by a pyrolytic group A structural unit having a group, a structural unit having an epoxy group/oxetanyl group, and a structural unit having a carboxyl group/phenolic hydroxyl group (see Patent Document 2).

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-333847

[Patent Document 2] Japanese Patent Laid-Open 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 the cured product can stably exhibit transparency or solvent resistance, adhesion, heat resistance and the like. Further, in recent years, with the advancement of technologies such as display devices, higher performance has been strongly demanded for each member to be used. For example, in color filter applications, high transparency after hardening is required. However, the current situation is that the previous resin composition cannot adequately cope with such requirements. For example, the resin composition described in Patent Document 1 or 2 is insufficient in curability, and thus a cured product having high transparency cannot be obtained, and storage stability is also insufficient. Therefore, it is further carried out to further improve the resin composition. The hardening property of the material can stably exert a space for research such as high transparency. Further, there has been room for research to improve the storage stability of the resin composition.

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

The present inventors conducted various studies on a curable resin composition which can be used for various applications such as a color filter, and as a result, it has been focused on the preparation of a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator. The resin composition is curable. In addition, it has been found that the (meth) acrylate-based polymer is a structural unit having a (meth) acrylate-based monomer derived from a tertiary carbon, and the curable resin composition is set. Further, in the form of a polymer having a hydroxyl group and/or a form in which the (meth)acrylate polymer further has a hydroxyl group, the curable resin composition is excellent in storage stability, and on the other hand, hardening is obtained. The solvent resistance after the curing and the curing is drastically improved, and it is possible to stably exhibit a high degree of transparency, adhesion to a substrate (substrate), heat resistance, high hardness, and the like. Such a curable resin composition is particularly useful for color filter applications, and is suitably used as a resin composition for forming a protective film or an insulating film for a color filter. Therefore, the industry has found that by this kind of hard A cured product, a color filter, and a display device formed by the composition of the resin are extremely useful in the field of optics and electro-electronics, and are extremely useful in solving the above problems. The method thus completes the present invention.

Here, the (meth) acrylate-based polymer contained in the curable resin composition of the present invention has a structural unit derived from a (meth) acrylate-based monomer containing tertiary carbon, but the structural unit is susceptible to Heat and break down. Specifically, the OC bond between the oxygen atom adjacent to the (meth) acrylonitrile group and the tertiary carbon atom adjacent thereto is easily cleaved, whereby it is decomposed into (meth)acrylic acid and is produced in the third order. A stable compound on the side of the carbon atom. Therefore, for example, when the curable resin composition of the present invention is used in the case of forming a pixel of a color filter, the heating step (also referred to as a calcination step or a post-baking step) after development is derived from the above. The structural unit of the (meth) acrylate monomer containing a tertiary carbon is decomposed to form a (meth)acrylic acid and a compound which is stable on the side of the tertiary carbon atom. Further, it is considered that the curable resin composition may further contain a hydroxyl group in the polymer having a hydroxyl group, and/or the (meth)acrylate polymer may further have a hydroxyl group and the generated (meth)acrylic acid. An ester crosslinked structure is formed between them, and the hardenability of the resin composition and the solvent resistance after curing are drastically improved.

Further, the (meth) acrylate polymer or the polymer having a hydroxyl group is preferably a polymer having a polymerizable double bond in a side chain as described below. Thereby, the hardenability can be further improved, but in the case of using only a polymer having a polymerizable double bond in the side chain, in the present invention, the storage stability and the hardenability of the curable resin composition can be made one. And improved. The reason for this is that, in the present invention, as described above, a hardening reaction due to an ester crosslinked structure can be expected between the (meth)acrylic acid and the hydroxyl group generated by thermal decomposition, so that even if the polymerization in the polymer is reduced The content of the double bond can also exhibit sufficient curability, so that the polymerization double bond in the side chain during storage can be further reduced to cause gelation.

In other words, the present invention is a curable resin composition comprising a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, and the (meth) acrylate polymer device a polymer derived from a structural unit containing a (meth) acrylate monomer having a tertiary carbon, the curable resin composition being selected from the group consisting of a polymer further containing a hydroxyl group, and the (meth)acrylic acid The ester polymer further has at least one of a group consisting of a form of a hydroxyl group.

Further, the present invention is also a cured product obtained by curing the above-mentioned curable resin composition.

Further, the present invention is also a color filter having the above-mentioned cured product on a substrate.

Further, the present invention is also a display device which is constructed using the above-described color filter.

The invention is described in detail below. Further, a form in which two or more of the preferred embodiments of the present invention described below are combined 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. These components may be used alone or in combination of two or more. Further, one or two or more other components may be further contained as needed.

<(Meth)acrylate type polymer>

In the curable resin composition, the (meth) acrylate-based polymer has a polymer derived from a structural unit of a (meth) acrylate-based monomer containing a tertiary carbon. The structural unit derived from a (meth) acrylate monomer containing tertiary carbon means that the polymerizable carbon-carbon double bond (C=C) in the monomer is a structural unit of a single bond (CC). The monomer is suitably one having a structure in which an oxygen atom adjacent to a (meth) acrylonitrile group is bonded to a tertiary carbon atom. That is, the (meth) acrylate-based monomer containing the tertiary carbon is preferably a structure in which an oxygen atom adjacent to the (meth) acrylonitrile group is bonded to a tertiary carbon atom. Further, the term "third-order carbon atom" means that three carbon atoms bonded to the carbon atom are three carbon atoms.

The (meth) acrylate-based monomer having a tertiary carbon is preferably a compound having one polymerizable carbon-carbon double bond in the molecule, that is, having one (meth) acryloyl group (CH ₂ ) in the molecule. The compound of =C(R)-C(=O)-) is, for example, preferably a compound represented by the following 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 having a structure having a tertiary carbon atom on the side of an oxygen atom).

In the above formula (1), the organic group represented by A may be represented, for example, by -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 may be an unsaturated hydrocarbon group. Further, it may have a cyclic structure or may further have a substituent. Further, R ¹ , R ² and R ³ may be bonded to each other at the terminal sites to form a cyclic structure.

Further, in the present invention, as described below, a new compound formed by cleavage of an OC bond between an oxygen atom adjacent to a (meth)acryl fluorenyl group and a tertiary carbon atom in A adjacent thereto In terms of volatilization, the carbon number of the organic group represented by A is preferably 12 or less. Among them, the organic group represented by A is preferably derived from a group of a third butyl (meth) acrylate and/or a third pentyl (meth) acrylate. Further, the organic group represented by A may have a branched structure.

Here, in the above-mentioned (meth) acrylate-based monomer containing a tertiary carbon, a tertiary carbon atom bonded to an oxygen atom adjacent to the (meth) acrylonitrile group is preferably at least one of the adjacent carbon atoms. One is bonded to a hydrogen atom. For example, a compound represented by the above formula (1) in a (meth) acrylate system containing tertiary carbon, and A is a group represented by -C(R ¹ )(R ² )(R ³ ) In the case, it is preferred that at least one of R ¹ , R ² and R ³ has one or more hydrogen atoms. In such a form, the OC bond between the oxygen atom adjacent to the (meth)acryl fluorenyl group and the tertiary carbon atom adjacent thereto is cut by heating to form (meth)acrylic acid, and at the same time, the tertiary carbon A double bond (C=C) is formed between an atom and a carbon atom to which it is adjacent, and a new compound is formed more stably.

The new compound produced in the above manner is suitably a volatilizer. In this case, since the new compound is volatilized from the cured product, the film thickness of the cured product (cured film) is lowered, and when, for example, the above-mentioned curable resin composition further contains a colored material, the concentration of the colored material is Increase after heating. Therefore, further thinning can be achieved and high color purity or high light transmittance of the black matrix can be further achieved. In consideration of this aspect, the above R ¹ , R ² and R ^{3 are the} same or different, and are preferably a saturated hydrocarbon group having 1 to 15 carbon atoms. More preferably, it is a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

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

The acid group may be a functional group which can be neutralized with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group or a sulfonic acid group, and may have only one of these types, and may have 2 or more types. Among them, a carboxyl group or a carboxylic anhydride group is preferred, and a carboxyl group is more preferred.

In the case where the (meth) acrylate-based polymer is a polymer having an acid group in the molecule, the acid value (AV) of the polymer is not particularly limited, and is, for example, preferably 20 mgKOH/g or more. And less than 300mgKOH / g. Thereby, it is possible to exhibit more sufficient alkali solubility and obtain a cured product which is more excellent in developability. The lower limit of the acid value is more preferably 30 mgKOH/g or more, and still more preferably 40 mgKOH/g or more. Further, it is more preferably 200 mgKOH/g or less, further preferably 150 mgKOH/g or less.

The acid value of the polymer can be determined, for example, as follows.

Further, the (meth) acrylate-based polymer may be a polymer having a hydroxyl group in the molecule. That is, the (meth) acrylate-based polymer may be a polymer further having a hydroxyl group, and such a form is also one of preferred embodiments of the present invention. Thereby, it is possible to provide a cured product in which the curability of the curable resin composition is further improved and the transparency is further improved.

The (meth) acrylate-based polymer can be obtained, for example, by polymerizing a monomer component containing a (meth) acrylate-based monomer containing tertiary carbon. It is preferred that the monomer component further contains a monomer having an acid group and a polymerizable double bond. In the case where 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.

Further, one type or two or more types of each monomer to be used may be used.

The (meth) acrylate-based polymer may be a polymer obtained by polymerizing such a monomer component (also referred to as a base polymer), or as described below, or may be a base polymer a polymer obtained by reacting a compound having a functional group bonded to an acid group and a polymerizable double bond (also referred to as a polymer having a polymerizable double bond in a side chain or a polymer having a double bond in a side chain), Any of them is suitable. More preferably, the polymer having a double bond in the side chain can further improve the curability and further improve the transparency and adhesion. Further, the polymerizable double bond of the side chain is suitably a double bond of a radical polymerizable property.

In the monomer component, the (meth) acrylate monomer containing a tertiary carbon is as described above, and the content ratio of the monomer is preferably 5% by mass or more based on 100% by mass of the total of the monomer components. Thereby, the effect of the present invention resulting from the structural unit derived from the (meth) acrylate type monomer containing the tertiary carbon can be further exhibited. More preferably, it is 15% by mass or more, and 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 the other monomer. For example, when it is used for a color filter, it is preferable to further improve pattern characteristics or developability. 90% by mass or less. More preferably, it is 75 mass% or less, More preferably, it is 60 mass% or less.

Examples of the monomer having an acid group and a polymerizable double bond include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; maleic acid and antibutyric acid; Unsaturated polycarboxylic acids such as enedic acid, itaconic acid, citraconic acid, mesaconic acid; mono(2-propenyloxyethyl) succinate, mono(2-methylpropenyloxy) succinate An unsaturated monocarboxylic acid which is extended by a chain between an unsaturated group such as an ester and a carboxyl group; an unsaturated acid anhydride such as maleic anhydride or itaconic anhydride; and a phosphoric acid such as Lightester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.) A base unsaturated compound or the like. Among these, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, and unsaturated acid anhydrides) are preferably used from the viewpoint of versatility, availability, and the like. More preferably, in terms of reactivity, alkali solubility, etc., it is preferred to use an unsaturated monocarboxylic acid, and more preferably a (meth) propylene. An acid, particularly preferably methacrylic acid.

Further, the term "(meth)acrylic acid" means acrylic acid and/or methacrylic acid.

The content ratio of the monomer having an acid group and a polymerizable double bond is preferably set such that the acid value of the (meth)acrylate polymer is within the above preferred range. For example, the content of the monomer having an acid group and a polymerizable double bond is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass based on 100% by mass of the total of the monomer components. %the above. Further, it is preferably 85% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

Further, the monomer component is preferably a monomer having a hydroxyl group and a polymerizable double bond as described above. The monomer is preferably a monomer having a hydroxyl group in its side chain, and is preferably a monomer having a hydroxyl group and a (meth)acrylonitrile group from the viewpoint of reactivity. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, A hydroxyalkyl (meth)acrylate such as 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate or 2,3-hydroxypropyl (meth)acrylate.

Further, the (meth) acrylonitrile group means a methacryl fluorenyl group and/or an acryl fluorenyl group.

In the case where the monomer component contains a monomer having a hydroxyl group and a polymerizable double bond, the content ratio of the monomer is, for example, preferably 1% by mass or more based on 100% by mass of the total of the monomer components. More preferably, it is 5% by mass or more, and further preferably 10% by mass or more. In addition, when the ratio of the monomer containing a tertiary carbon (meth)acrylate monomer or a monomer having an acid group and a polymerizable double bond is considered, it is preferably 70% by mass or less, and more preferably 50% by mass. the following.

The (meth) acrylate-based polymer contained in the curable resin composition of the present invention has a polymer derived from a structural unit of a (meth) acrylate-based monomer containing a tertiary carbon, and is preferably further The main chain has a ring structure. Examples of the ring structure include a quinone ring, a tetrahydropyran ring, a tetrahydrofuran ring, a lactone ring, and the like. Since the ring structure is provided, the monomer component may further contain other copolymerizable monomers (also referred to as other monomers) in addition to the above monomers.

As the other monomer, for example, an N-substituted maleimide-imine monomer other than the above monomer or a dialkyl 2,2'-(oxydimethylene) diacrylate system is preferably used. A monomer or an α-(unsaturated alkoxyalkyl)acrylate monomer (preferably an (α-allyloxymethyl)acrylic acid alkyl ester monomer) or the like. Thus, in one preferred embodiment of the present invention, the monomer component further contains a substituent selected from the group consisting of an N-substituted maleimide-imine monomer and a 2,2'-(oxydimethylene) diacrylate dialkyl group. A form of at least one monomer selected from the group consisting of an ester monomer and an α-(unsaturated alkoxyalkyl) acrylate monomer. In addition, one or two or more kinds of a (meth) acrylate monomer or an aromatic vinyl monomer are used as appropriate.

Here, for example, an N-substituted maleimide-based monomer and/or a 2,2'-(oxydimethylene) dialkyl acrylate monomer and/or (α-ene) are used. The propoxymethyl)alkyl acrylate monomer can provide a cured product which is further improved in heat resistance, hardness, and dispersibility of a colored material. In particular, if a 2,2'-(oxydimethylene) dialkyl acrylate monomer and/or an (α-allyloxymethyl) acrylate alkyl ester monomer is used, heat resistance is obtained. A cured product that is more excellent in terms of coloring properties.

In addition, the content ratio of the other monomer is preferably 100% by mass or less, and more preferably 50% by mass or less, based on 100% by mass of the total of the monomer components. In particular, it contains an N-substituted maleimide-imine monomer, a 2,2'-(oxydimethylene) dialkyl acrylate monomer, and/or an α-(unsaturated alkoxy group). In the case of an alkyl group-based acrylate monomer, the content ratio is preferably from 2 to 60% by mass, more preferably from 2 to 60% by mass, from the viewpoints of heat resistance, hardness, dispersibility of a colored material, development speed, transparency, and the like. 2 to 50% by mass, and more preferably 3 to 40% by mass.

Examples of the N-substituted maleimide-imine-based monomer include N-cyclohexylmethyleneimine, N-phenylmaleimide, and N-methylbutylene. Diimine, N-ethyl maleimide, N-isopropyl maleimide, N-tert-butyl maleimide, N-dodecyl Ethylene diimine, N-benzyl maleimide, N-naphthyl maleimide, and the like may be used alone or in combination of two or more. Among them, it is transparent From the viewpoint of nature, N-phenyl maleimide, N-benzyl maleimide, and preferably N-benzyl maleimide are preferred.

Examples of the above N-benzyl maleimide may include benzyl maleimide, p-methylbenzyl maleimide, and p-butylbenzyl maleate. An alkyl substituted benzyl maleimide such as quinone, a phenolic hydroxy substituted benzyl maleimide such as p-hydroxybenzyl maleimide or the like; o-chlorobenzylbutene A halogen-substituted benzyl maleimide or the like such as a diterpene imine, an o-dichlorobenzyl maleimide or a p-dichlorobenzyl maleimide.

Examples of the dialkyl 2,2′-(oxydimethylidene) diacrylate monomer include 2,2′-[oxybis(methylene)]diacrylic acid and 2,2. At least one of '-[oxybis(methylene)]bis-2-alkyl acrylate, 2,2'-[oxybis(methylene)]bis-2-propenoic acid dialkyl ester The ester moiety contains a compound of tertiary carbon or the like. Among these, for example, 2,2'-[oxybis(methylene)]bis-2-acrylic acid dimethyl ester or the like is preferably used from the viewpoints of transparency, dispersibility, industrial availability, and the like.

Examples of the α-(unsaturated alkoxyalkyl)acrylate monomer include α-allyloxymethacrylic acid, α-allyloxymethyl methacrylate, and α-allyloxyl. Ethyl methacrylate, α-allyloxypropyl n-propyl methacrylate, α-allyloxy isopropyl methacrylate, α-allyloxy methacrylate n-butyl ester, α-allyl Dibutyl oxymethacrylate, tert-butyl α-allyloxymethacrylate, n-amyl α-allyloxymethyl methacrylate, second amyl ester of α-allyloxymethyl methacrylate And α-allyloxymethacrylic acid third amyl ester, α-allyloxymethyl methacrylate neopentyl ester and the like. Among them, a (α-allyloxymethyl) acrylate alkyl ester monomer is suitable. As the (α-allyloxymethyl) acrylate alkyl ester monomer, for example, (α-allyloxymethyl) is suitably used from the viewpoints of transparency, dispersibility, industrial availability, and the like. Methyl acrylate and the like.

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

As the (meth) acrylate monomer, for example, a monomer having an alicyclic skeleton is preferable in consideration of the surface hardness of the cured product or the like. Specific examples thereof include cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isodecyl (meth)acrylate, and 1-adamantyl (meth)acrylate. (3,4-epoxycyclohexyl)methyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecyl (meth) acrylate , dimethylol-tricyclodecane di(meth) acrylate, pentacyclopentadecane dimethanol di(meth) acrylate, cyclohexane dimethanol di(meth) acrylate, norbornane II Methanol di(meth) acrylate, p-menthane-1,8-diol di(meth) acrylate, p-menthan-2,8-diol di(meth) acrylate, p-menthane-3 , 8-diol di(meth)acrylate, bicyclo[2.2.2]-octane-1-methyl-4-isopropyl-5,6-dimethylol di(meth)acrylate, etc. . Among these, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid are suitably used from the viewpoint of versatility, availability, and the like. Tricyclic oxime ester. Further, an alicyclic epoxy compound such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate or ethyl glycidyl (meth)acrylate is preferably used.

Further, examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. , n-butyl (meth)acrylate, second butyl (meth)acrylate, n-amyl (meth)acrylate, second amyl (meth)acrylate, n-hexyl (meth)acrylate, (methyl) ) 2-ethylhexyl acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (methyl) Lauryl acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethyl (meth) acrylate Oxyethyl ester, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, alpha-hydroxymethyl acrylate Ester, α-hydroxyethyl methacrylate, α-hydroxy methacrylate tert-butyl ester, α-hydroxy methacrylate third amyl ester, etc., and may also be exemplified by: 1,4-dioxaspiro methacrylate [4,5]non-2-yl ester, (methyl) Alkenyl group it XI Fuline, tetrahydrofurfuryl acrylate, 4-(methyl) propylene methoxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(methyl) propylene醯oxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(methyl)propenyloxymethyl-2-methyl-2-cyclohexyl -1,3-dioxolane, 4-(meth)acryloxymethyl-2,2-dimethyl-1,3-dioxolane, and the like. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are preferable in terms of easy availability of heat resistance or dispersibility of a colored material and solvent resolubility. An alkyl (meth)acrylate such as benzyl (meth)acrylate.

Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methylstyrene, and methoxystyrene. Among them, styrene and/or vinyl toluene is preferable in terms of heat-resistant coloring property or heat-resistant decomposition property of the resin.

In addition, the other monomer may be one or more selected from the group consisting of the following compounds.

(meth) acrylamide such as N,N-dimethyl(meth)acrylamide or N-hydroxymethyl(meth)acrylamide; polystyrene, poly(methyl) methacrylate, a macromonomer having a (meth) acrylonitrile group at a single terminal of a polymer molecular chain such as polyethylene oxide, polypropylene oxide, polyoxyalkylene, polycaprolactone or polycaprolactam; a conjugated diene such as 3-butadiene, isoprene or chloroprene; a vinyl ester such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl benzoate; methyl vinyl ether, Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-decyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxy ethyl vinyl ether, ethoxylate Ethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, vinyl ether such as 4-hydroxybutyl vinyl ether; N-vinyl N-vinyl compounds such as pyrrolidone, N-vinyl caprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide; (meth)acrylic acid isocyanate Ester, isocyanate Unsaturated isocyanates such as propyl ester.

As a method of polymerizing the above monomer components, block polymerization and dissolution can be used. A method generally used for liquid polymerization, emulsion polymerization, or the like may be appropriately selected depending on the purpose and use. Among them, solution polymerization is industrially advantageous, and it is easy to carry out structural adjustment of a molecular weight or the like, and is therefore preferable. Further, the polymerization mechanism of the above monomer component can be carried out by a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, and a polymerization method based on a radical polymerization mechanism is also industrially advantageous, which is preferable.

In the polymerization initiation method in the polymerization reaction, as long as the energy required for the polymerization start is supplied to the monomer component by an active energy source such as heat or electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) or an electron beam, the polymerization is further used in combination. The starting agent can greatly reduce the energy required to start the polymerization, and is easy to control the reaction, so that it is suitable.

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, the type or amount of the chain transfer agent, and the like.

In the case where the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is not active in the polymerization reaction. For example, it may be appropriately set according to a polymerization mechanism, a type or amount of a monomer to be used, a polymerization temperature, a polymerization concentration, and the like, and when a curable resin composition is subsequently formed, a solvent is used as a diluent or the like. In terms of efficiency, it is preferred to use a solvent containing the solvent in solution polymerization of a monomer component.

For the above-mentioned solvent, for example, the following compounds and the like can be used, and one type or two or more types can be used.

Monools such as methanol, ethanol, isopropanol, n-butanol, and second butanol; glycols such as ethylene glycol and propylene glycol; tetrahydrofuran, a cyclic ether such as an alkane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, two Glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol single Methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, acetic acid 3- Esters of diol monoethers such as methoxybutyl ester; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate Ester, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane An alkyl ester such as ethyl acetate, methyl acetoxyacetate or ethyl acetoxyacetate; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; benzene, toluene, and An aromatic hydrocarbon such as toluene or ethylbenzene; an aliphatic hydrocarbon such as hexane, cyclohexane or octane; or a guanamine such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone Classes, etc.

Among these solvents, propylene glycol monomethyl ether is more preferably used in terms of solubility of the obtained polymer, surface smoothness at the time of film formation, less influence on human body and environment, and industrial availability. , propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethyl lactate.

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

In the case where the above monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous to use a polymerization initiator which generates a radical by heat. The polymerization initiator is not particularly limited as long as it generates a radical by supplying thermal energy, and may be appropriately selected depending on polymerization conditions such as a polymerization temperature, a solvent, and a type of the monomer to be polymerized. Further, a reducing agent such as a transition metal salt or an amine may be used in combination with the polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, lauric acid peroxide, benzammonium peroxide, and peroxidation. Isobutyl butyl carbonate, tributyl acrylate (2-ethylhexanoate), azobisisobutyl Nitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropane) A peroxide, an azo compound or the like which is usually used as a polymerization initiator, such as dimethyl ester, hydrogen peroxide or persulfate, may be used singly or in combination of two or more kinds.

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

Further, in the above polymerization, a chain transfer agent which is usually used may be used as needed. It is preferred to use a polymerization initiator and a chain transfer agent in combination. Further, when a chain transfer agent is used in the polymerization, there is a tendency to suppress an increase in molecular weight distribution or gelation.

Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and 3- N-octyl decyl propionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), neopentyltetraol (3- Mercaptocarboxylic acid esters such as mercaptopropionate, dipentaerythritol hexa(3-mercaptopropionate); ethyl mercaptan, tert-butyl mercaptan, n-dodecyl mercaptan, 1,2 - alkyl mercaptans such as dimercaptoethane; mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; phenyl mercaptan, m-toluene mercaptan, p-toluene mercaptan, 2-naphthyl mercaptan, etc. Aromatic thiols; decyl isocyanurates such as tris[(3-mercaptopropoxy)-ethyl]isocyanurate; 2-hydroxyethyl disulfide, tetraethyl thiuram disulfide Dithioethers such as ethers; dithiocarbamates such as benzyl diethyldithiocarbamate; monomeric dimers such as α-methylstyrene dimer; carbon tetrabromide, etc. Halogenated alkane and the like. These may be used alone or in combination of two or more.

Among these, a mercaptocarboxylic acid, a mercaptocarboxylic acid ester, an alkyl mercaptan, a mercapto alcohol, an aromatic sulfur is suitably used in terms of availability, resistance to cross-linking, and a small decrease in polymerization rate. A compound having a mercapto group such as an alcohol or a mercapto isocyanurate. More preferably an alkyl group The mercaptan, the mercaptocarboxylic acid, and the mercaptocarboxylic acid ester are more preferably n-dodecyl mercaptan or mercaptopropionic acid.

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

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, and the like, and is preferably, for example, 50 to 150 ° C, more preferably 70 to 70 °. 120 ° C. Further, the polymerization time can be appropriately set in the same manner, and is, for example, preferably 1 to 6 hours, more preferably 2 to 5 hours.

a polymer obtained by reacting a base polymer obtained by polymerizing the monomer component with a compound having a functional group capable of bonding with an acid group and a polymerizable double bond in the above (meth)acrylate polymer In the case of a compound having a double bond-containing polymer, the compound having a functional group and a polymerizable double bond which may be bonded to an acid group may be used alone or in combination of two or more. In the compound, examples of the polymerizable double bond include a (meth) acrylonitrile group, a vinyl group, an allyl group, and a methallyl group. The compound is preferably one or two of these compounds. More than one. Among them, in terms of reactivity, a (meth) acrylonitrile group is preferred. In addition, examples of the functional group which may be bonded to an acid group include a hydroxyl group, an epoxy group, an oxetanyl group, and an isocyanate group, and the compound is preferably one or more selected from the group consisting of the above-mentioned compounds. Among them, an epoxy group (including a glycidyl group) is preferred in terms of the speed of the denaturation treatment reaction, heat resistance, and dispersibility.

Examples of the compound having a functional group bondable to an acid group and a polymerizable double bond include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, and (methyl). Β-ethyl glycidyl acrylate, vinylbenzyl glycidyl ether, allyl One or two or more kinds of these may be used, such as glycidyl ether, (meth)acrylic acid (3, 4-epoxycyclohexyl) methyl ester, vinyl epoxy cyclohexane, etc.. Among them, a compound (monomer) having an epoxy group and a (meth) acrylonitrile group is suitably used.

As a method of obtaining the polymer having a double bond in the side chain, for example, when the base polymer is reacted with a compound having a functional group capable of bonding with an acid group and a polymerizable double bond, a method in which the amount of the acid group (preferably a carboxyl group) of the base polymer is excessively larger than the amount of the compound having a functional group and a polymerizable double bond bondable to the acid group; and the base polymer and the acid group are A method in which a compound having a bonded functional group and a polymerizable double bond is reacted, and then reacted with a compound having a polybasic acid anhydride group.

In order to ensure a good reaction rate and prevent gelation, the above 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 are subjected to a compound. The reaction step is preferably carried out at a temperature ranging from 50 to 160 °C. More preferably, it is 70 to 140 ° C, and further preferably 90 to 130 ° C. Further, in order to increase the reaction rate, a basic catalyst or an acid catalyst for esterification or transesterification which is usually used can be used as the catalyst. Among them, since the side reaction is small, it is preferred to use an alkaline catalyst.

Examples of the basic catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tri-n-octylamine, and tetramethylethylenediamine; tetramethylammonium chloride and tetramethylammonium bromide; a quaternary ammonium salt such as tetrabutylammonium bromide or n-dodecyltrimethylammonium chloride; a urea compound such as tetramethylurea; an alkyl hydrazine such as tetramethylhydrazine; dimethylformamide; a guanamine compound such as methyl acetamide; a tertiary phosphine such as triphenylphosphine or tributylphosphine; a quaternary phosphonium salt such as tetraphenylphosphonium bromide or benzyltriphenylphosphonium bromide; One or two or more. Among them, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferred in terms of reactivity, workability, or halogen-free.

The amount of the catalyst to be used is preferably 0.01 in terms of the total amount of the monomer component and the compound having a functional group (for example, an epoxy group or the like) and a polymerizable double bond bondable to an acid group. ~5.0 parts by mass. More preferably, it is 0.1 to 3.0 parts by mass.

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

As the polymerization inhibitor, a polymerization inhibitor for a radical polymerizable monomer which is usually used can be used, and examples thereof include hydroquinone, methyl hydroquinone, trimethyl hydroquinone, and third. Butyl hydroquinone, p-methoxyphenol, 6-tert-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl a phenolic inhibitor such as -4-methoxyphenol or 2,2'-methylenebis(4-methyl-6-tert-butylphenol); an organic acid copper salt or phenol thiophene One or two or more of these may be used. Among them, a phenolic inhibitor is preferred in terms of low coloration, polymerization prevention ability, and the like, and 2,2'-methylenebis(4-methyl-6) is more preferable in terms of availability and economy. -T-butylphenol), p-methoxyphenol, 6-t-butyl-2,4-xylenol, 2,6-di-t-butylphenol.

The amount of the polymerization inhibitor to be used is such that, in order to secure a sufficient polymerization prevention effect and the curability in forming a curable resin composition, the monomer component has a functional group capable of bonding with an acid group. The total amount of the compound of the group and the polymerizable double bond is 100 parts by mass, preferably 0.001 to 1.0 part by mass. More preferably, it is 0.01 to 0.5 parts by mass.

Examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenylsuccinic acid, pentadecylsuccinic acid, octadecenylsuccinic acid, tetrahydrophthalic anhydride, and methyltetrahydroortho Phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, cis The butene dianhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride may be used alone or in combination of two or more.

The above (meth) acrylate-based polymer is suitably a weight average molecular weight of 2000~250000. By such a range, better developability can be exhibited. More preferably, it is 3,000 to 100,000, and more preferably 4,000 to 50,000. Further, when the (meth) acrylate-based polymer has a high molecular weight (for example, 10,000 to 50,000), there is a tendency to obtain a cured product having a higher hardness by controlling the acid value to be higher (more It is preferably 150 mgKOH/g or more and 200 mgKOH/g or less, and tends to be easily developed.

The weight average molecular weight of the polymer can be obtained, for example, in the following manner.

In the case where the (meth) acrylate-based polymer is a polymer having a double bond in a side chain (that is, a polymer having a double bond in a side chain), the double bond equivalent is preferably from 200 to 10,000. By such a range, the storage stability of the polymer is made better. More preferably, it is 200 to 5,000, and further preferably 250 to 4,000, and more preferably 300 to 4,000.

The double bond equivalent means the mass of the solid component per 1 mol of the polymer solution (also referred to as a resin solution) with respect to the double bond of the polymer. The mass of the solid content of the polymer solution herein means the total mass of the constituent components of the above monomer component and the mass of the polymerization inhibitor. It can be determined by dividing the mass of the solid component of the polymer solution by the amount of the double bond of the polymer. The amount of the double bond of the polymer can be determined from the amount of the acid group to be added and the compound having a bondable functional group and a polymerizable double bond.

In addition, the curable resin composition of the present invention is selected from at least one of a group further comprising a polymer having a hydroxyl group and a form having a hydroxyl group further comprising a hydroxyl group. . An ester crosslinked structure is produced between (meth)acrylic acid produced by decomposition of a structural unit derived from a (meth) acrylate-based monomer containing a tertiary carbon by having a hydroxyl group in the system as described above. Therefore, it is possible to provide a cured product having remarkably improved hardenability and particularly excellent transparency. Further, the curable resin composition further contains 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 base polymerization obtained by polymerizing the following monomer component is preferably used. The monomer component comprises a (meth) acrylate monomer having a tertiary carbon, and a monomer having a hydroxyl group and a polymerizable double bond, and preferably further comprising a monomer having an acid group and a polymerizable double bond. A polymer obtained by reacting the base polymer with a compound having a functional group bondable with an acid group and a polymerizable double bond to obtain a side chain containing a double bond. Among them, a polymer in which the side chain of the latter contains a double bond is preferred.

<Polymer having a hydroxyl group>

In the case where the curable resin composition further contains a polymer having a hydroxyl group in addition to the above (meth)acrylate polymer, the polymer having a hydroxyl group is not particularly limited as long as it has a hydroxyl group in the molecule. limited. Among them, from the viewpoint of further improving the developability, a polymer which exhibits alkali solubility is preferable, and a polymer having an acid group in the molecule is preferable. Regarding the acid group, as described in the above (meth)acrylate polymer, the acid value of the polymer having a hydroxyl group is also preferably as described in the above (meth)acrylate polymer. Within the scope.

The polymer having a hydroxyl group is preferably, for example, polymerized a monomer component containing a monomer having a hydroxyl group and a polymerizable double bond, preferably further containing a monomer having an acid group and a polymerizable double bond. The obtained base polymer; a polymer obtained by reacting the base polymer with a compound having a functional group capable of bonding with an acid group and a polymerizable double bond, and a side chain containing a double bond. Among them, a polymer in which the side chain of the latter contains a double bond is preferred.

As described above, the (meth)acrylate polymer and/or the polymer having a hydroxyl group are in the form of a polymer having a polymerizable double bond in a side chain, and are included in the preferred embodiment of the present invention.

Among the monomer components forming the polymer having a hydroxyl group, a monomer having a hydroxyl group and a polymerizable double bond, and a preferred embodiment or specific example of a monomer having an acid group and a polymerizable double bond are as described above. One type or two or more types may be used for the body.

The content ratio of the monomer having a hydroxyl group and a polymerizable double bond is, for example, preferably 100% by mass based on 100% by mass of the total of the monomer components forming the polymer having a hydroxyl group. More than %. More preferably, it is 5% by mass or more, and further preferably 10% by mass or more. Further, it is preferably 90% by mass or less, more preferably 50% by mass or less, and still more preferably 25% by mass or less.

The content ratio of the monomer having an acid group and a polymerizable double bond is preferably set so that the acid value is within the above preferred range, for example, 100% of the total monomer component of the polymer having the hydroxyl group. The mass% is preferably a content ratio of a monomer having an acid group and a polymerizable double bond of 5% by mass or more. It is more preferably 10% by mass or more, and still more preferably 20% by mass or more. Further, it is preferably 99% by mass or less, more preferably 85% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less.

Further, the monomer component forming the polymer having a hydroxyl group may contain other copolymerizable monomers in addition to the above monomers. As the other monomer, for example, an N-substituted maleimide-imine monomer other than the above monomers and a dialkyl 2,2'-(oxydimethylene) diacrylate system can be preferably used. One or two or more kinds of the monomer, the (α-allyloxymethyl) acrylate alkyl ester monomer, the (meth) acrylate monomer, and the aromatic vinyl monomer. These preferred forms or specific examples are as described above.

In addition, the content ratio of the other monomer is preferably 100% by mass or less, and more preferably 50% by mass or less, based on 100% by mass of the total of the monomer components forming the polymer having a hydroxyl group. In particular, in the case of containing an N-substituted maleimide-based monomer, the content ratio is preferably set to 2 from the viewpoints of heat resistance, hardness, dispersibility of a colored material, development speed, transparency, and the like. ~60% by mass, more preferably 2 to 50% by mass, still more preferably 3 to 40% by mass.

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

In the above-mentioned curable resin composition, the content ratio of the (meth)acrylate polymer and the polymer having a hydroxyl group may be appropriately set according to the use or the blending of other components, for example, the total solid content of the aggregate. (in the case of a polymer without a hydroxyl group, The solid content of the (meth)acrylate-based polymer is preferably 100% by mass or more based on 100% by mass of the total solid content of the curable resin composition. Further, it is preferably 80% by mass or less. By being within such a range, the effects of the present invention can be more significantly exerted. More preferably, it is 7 to 70% by mass, and further preferably 10 to 60% by mass.

In addition, the "total amount of solid content" means the total amount of the component which forms a hardened material (except the solvent etc. which volatilized at the time of formation of a hardened material).

Here, in the case of containing both the (meth) acrylate-based polymer and the polymer having a hydroxyl group, the blending ratio is as long as it is derived from a (meth) acrylate-based single sheet containing tertiary carbon. The structural unit of the body is not particularly limited as long as the blending ratio is set such that (meth)acrylic acid generated by thermal decomposition and the hydroxyl group in the system are easily crosslinked by ester. For example, the mass ratio ((meth)acrylate polymer/polymer having a hydroxyl group) is preferably set to be 1 to 99/99 to 1. More preferably 10~90/90~10.

<Polymerizable compound>

Further, the curable resin composition contains a polymerizable compound. The polymerizable compound is also called a polymerizable monomer, and is a polymerizable unsaturated bond which can be polymerized by irradiation of an active energy ray such as a radical, an electromagnetic wave (for example, infrared rays, ultraviolet rays, X-rays, etc.) or an electron beam. A low molecular compound (also known as a polymeric unsaturated group). For example, a monofunctional compound having one polymerizable unsaturated group in the molecule and a polyfunctional compound having two or more polymerizable unsaturated groups may be mentioned.

The monofunctional polymerizable monomer is, for example, a compound which is preferably a monomer which is preferably contained in the monomer component of the (meth)acrylate polymer, and includes N-substituted maleic acid. Imine or (meth) acrylates; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; chain extended extended monocarboxylic acids between unsaturated groups and carboxyl groups; Saturated anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates.

Examples of the polyfunctional polymerizable monomer include the following compounds. Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(a) Acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide a bifunctional (meth) acrylate compound such as (meth) acrylate; trimethylolpropane tri(meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, glycerol tris(methyl) Acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (methyl) ) acrylate, pentaerythritol hepta (meth) acrylate, tripentenol octa (meth) acrylate, ethylene oxide addition trimethylolpropane tri (meth) acrylate, ring Oxyethane addition di-trimethylolpropane tetra(meth) acrylate, ethylene oxide addition neopentyl alcohol tetra(meth) acrylate, ethylene oxide addition dipentaerythritol (meth) acrylate, propylene c Addition of trimethylolpropane tri(meth)acrylate, propylene oxide addition di-trimethylolpropane tetra(meth)acrylate, propylene oxide addition neopentyl alcohol tetra(meth)acrylic acid Ester, propylene oxide addition dipentaerythritol hexa(meth) acrylate, ε-caprolactone addition trimethylolpropane tri(meth) acrylate, ε-caprolactone addition two-three Hydroxymethylpropane tetra(meth)acrylate, ε-caprolactone addition pentaerythritol tetra(meth)acrylate, ε-caprolactone addition dipentaerythritol hexa(meth)acrylate a trifunctional or higher polyfunctional (meth) acrylate compound; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, Hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, di-trimethylolpropane tetravinyl ether, glycerol triethylene Ether, neopentyl alcohol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition two -three Methyl vinyl ether propane tetraacrylate, pentaerythritol ethylene oxide adduct of four new vinyl ether, ethylene oxide adduct of pentaerythritol six new two vinyl ether polyfunctional vinyl ethers; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, (meth)acrylic acid 2 -vinyloxypropyl ester, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, (methyl) 6-vinyloxyhexyl acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(meth)acrylate a (vinyl) acrylate-containing (meth) acrylate such as (vinyloxyethoxy)ethyl ester or 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate; Alcohol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butanediol diallyl ether, hexanediol diallyl ether, bisphenol A ring Oxydiene diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, di-trimethylolpropane tetraallyl ether, glyceryl triallyl ether, neopentyl alcohol Telyl ether, dinepentaerythritol pentamethicone, dipentaerythritol hexene propyl ether, ring Oxyethane addition trimethylolpropane triallyl ether, ethylene oxide addition di-trimethylolpropane tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, epoxy Ethane addition polyfunctional allyl ethers such as dipentaerythritol hexene allylate; allyl group-containing (meth) acrylates such as allyl (meth) acrylate; isocyanuric acid tris(propylene hydride) Oxyethyl) ester, tris(methacryloxyethyl) isocyanurate, alkylene oxide triiso(methacryloxyethyl) ester, alkylene oxide addition isocyanuric acid A polyfunctional (meth)acrylonitrile-containing isocyanurate such as tris(methacryloxyethyl)ester; a polyfunctional allyl-containing isocyanurate such as triallyl isocyanurate; ; toluene diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate, etc. by containing a polyfunctional isocyanate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. A polyfunctional (meth)acrylic acid urethane obtained by a reaction of a hydroxyl group (meth) acrylate; a polyfunctional aromatic vinyl group such as divinyl benzene or the like.

Among the above polymerizable compounds, the curable resin group of the present invention is further improved From the viewpoint of the curability of the product, a polyfunctional polymerizable compound is suitably used. When a polyfunctional polymerizable compound is used as the polymerizable compound, the number of the functional groups is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more. Further, from the viewpoint of further suppressing the curing shrinkage, the number of functional groups is preferably 10 or less, more preferably 8 or less.

In addition, the molecular weight of the polymerizable compound is not particularly limited, and is preferably, for example, 2,000 or less from the viewpoint of handling.

When a polyfunctional polymerizable compound is used as the polymerizable compound, a polyfunctional (meth) acrylate compound is preferably used in the polymerizable compound from the viewpoints of reactivity, economy, availability, and the like. A compound having a (meth)acryl oxime group such as a functional (meth)acrylic acid urethane compound or a (meth) acrylonitrile-based isocyanurate compound. Further, the polyfunctional (meth) acrylate compound is more preferable because the curable resin composition is more excellent in photosensitivity and curability, and a cured product having higher hardness and high transparency can be obtained. Further, a trifunctional or higher polyfunctional (meth) acrylate compound is preferably used.

In addition to the type of the polymerizable compound or the (meth)acrylate polymer to be used, the content of the polymerizable compound can be appropriately set according to the purpose, use, etc., and the developability or plate-making property is further improved. The total amount of the solid content of the curable resin composition is preferably 100% by mass or more, and more preferably 80% by mass or less. The lower limit is more preferably 5% by mass or more, further preferably 8% by mass or more, and particularly preferably 10% by mass or more, and more preferably 70% by mass or less, still more preferably 50% by mass. In the following, it is preferably 30% by mass or less, and most preferably 20% by mass or less.

<Photopolymerization initiator>

The curable resin composition further contains a photopolymerization initiator. As the photopolymerization initiator, a radically polymerizable photopolymerization initiator is preferred. The radically polymerizable photopolymerization initiator refers to a radical polymerization radical generated by irradiation of an active energy ray such as an electromagnetic wave or an electron beam, and one or two or more kinds of ordinary users can be used. Also, one or two can be used together as needed. More than one kind of light sensitizer or photoradical polymerization accelerator. A photosensitizer and/or a photoradical polymerization accelerator may be used together with the photopolymerization initiator, or may not be used. Even if the photosensitizer and/or the photoradical polymerization accelerator are not used together, the effects of the present invention can be sufficiently exerted, but when used in combination, the sensitivity or the curability is further improved.

Specific examples of the photopolymerization initiator include the following compounds.

2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-benzene Propane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4- [4-(2-Hydroxy-2-methylpropenyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)- 2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamine Alkylphenone-based compound such as 2-((4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone; a benzophenone compound such as ketone, 4,4'-bis(dimethylamino)benzophenone or 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Benzoin compound such as ether; 9-oxygen sulfur 2-ethyl 9-oxosulfur 2-isopropyl 9-oxygen sulfur 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 9-oxosulfur Compound; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric three , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric three , 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric three , 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-symmetric three Isohalogen methylation Compound; 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- Diazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- Diazole, 4- Diazole, 2-trichloromethyl-5-furanyl-1,3,4- Halogenation of oxadiazole Diazole compound; 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'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O -benzimidamide]], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetonitrile肟) oxime ester compound; bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl a titanocene compound such as titanium; a benzoate compound such as p-dimethylaminobenzoic acid or p-diethylaminobenzoic acid; an acridine compound such as 9-phenyl acridine; and the like.

As a photosensitizer or photoradical polymerization accelerator which can also be used together with the above photopolymerization initiator, for example, a pigment compound such as a pigment, a coumarin pigment, a 3-ketocoumarin compound or a pyrromethylene dye; ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2- a dialkylamino benzene compound such as ethylhexyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoene A mercaptan such as azole or 2-mercaptobenzimidazole is a hydrogen donor or the like.

The content of the photopolymerization initiator is not particularly limited as long as it is appropriately set according to the purpose, the use, and the like, and is preferably 100 parts by mass based on the total solid content of the curable resin composition other than the photopolymerization initiator. 0.1 parts by mass or more. Thereby, a cured product having more excellent adhesion can be obtained, and the peeling can be further sufficiently suppressed after exposure to high temperature. In addition, it is preferably 30 parts by mass or less in consideration of the balance with the influence of the decomposition product of the photopolymerization initiator or the economy. The lower limit is more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and the upper limit is more preferably 25 parts by mass or less, still more preferably 20 parts by mass. the following.

The photo sensitizer and the photoradical polymerization accelerator may not be used in the above manner, and in terms of use, in terms of hardenability, the influence of the decomposition product, and the balance of economy, The total solid content of the curable resin composition is 100% by mass, preferably 0.001 to 20% by mass. More preferably, it is 0.01 to 15% by mass, and further preferably 0.05 to 10% by mass.

<Other ingredients>

- solvent -

Moreover, it is preferable that the said curable resin composition contains a solvent. The solvent can be preferably used as a diluent or the like. Specifically, it is suitably used for the purpose of dissolving or dispersing a low-viscosity organic solvent or water containing each component in the curable resin composition for the purpose of lowering the viscosity and improving the operability. A coating film is formed by drying, a dispersion medium as a colored material, or the like.

The solvent 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.

Monools such as methanol, ethanol, isopropanol, n-butanol, and second butanol; glycols such as ethylene glycol and propylene glycol; tetrahydrofuran, a cyclic ether such as an alkane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, two Glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol single Methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, acetic acid 3- Esters of diol monoethers such as methoxybutyl ester; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate Ester, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane An alkyl ester such as ethyl acetate, methyl acetoxyacetate or ethyl acetoxyacetate; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; benzene, toluene, and An aromatic hydrocarbon such as toluene or ethylbenzene; an aliphatic hydrocarbon such as hexane, cyclohexane or octane; or a guanamine such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone Class; water, etc.

The amount of the solvent to be used is not particularly limited as long as it is appropriately set according to the purpose and use, and it is preferably contained in an amount of 10 to 90% by mass based on 100% by mass of the total amount of the curable resin composition of the present invention. . More preferably, it is 20 to 80% by mass.

The curable resin composition may further contain, for example, one or two or more kinds of colored materials (also referred to as colorants); a dispersing agent; a heat-resistant improving agent; a leveling agent; and development, depending on the required properties of each application to which it is applied. Additives; inorganic fine particles such as cerium oxide microparticles; coupling agents such as decane, aluminum, and titanium; thermosetting resins such as fillers, epoxy resins, phenol resins, and polyvinyl phenol; and hardening aids such as polyfunctional thiol compounds Agent; plasticizer; polymerization inhibitor; ultraviolet absorber; antioxidant; matting agent; defoamer; antistatic agent; slip agent; surface modifier; thixotropic agent; thixotropic agent; a compound; a polyphenol compound; a cationically polymerizable compound; an acid generator; and the like. For example, when the curable resin composition is used for a color filter, it is preferred to contain a colored material. Thus, the form in which the curable resin composition further contains a colored material is also one of preferred embodiments of the present invention. Further, it is also preferable to contain at least one selected from the group consisting of a colored material, a dispersing agent, a heat-resistant improving agent, a leveling agent, a coupling agent, and a developing auxiliary. Hereinafter, the components to be contained will be described.

- colored materials -

As the above colored material, for example, a pigment or a dye can be suitably used. These may be used alone or in combination of two or more. Further, the pigment and the dye may be combined. For example, in the case of forming red, blue, or green pixels of a color filter, a method in which blue and a colored material such as violet, green, and yellow are combined to exhibit desired color characteristics is suitably used. Further, in the case of forming a black matrix, it may be formed using a black colored material.

Among the above-mentioned 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 brightness improvement of a panel or the like, dyes It is excellent, and therefore, it is only necessary to select or use them in accordance with the required characteristics. Further, among the pigments, organic pigments are more preferred.

Examples of the pigment include an azo-based pigment, a phthalocyanine-based pigment, and a polycyclic pigment (for example, a quinacridone-based, an anthraquinone-based, a purple-ringone-based, an isoindolinone-based, or an iso-porphyrin-based). ,two Organic pigments such as thio-indigo, lanthanide, quinophthalone, metal complex, diketopyrrolopyrrole, etc., dye lake pigments; white-physical pigments (eg titanium oxide, Zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), color pigments (such as chrome yellow, cadmium, chrome red, nickel titanium, chrome titanium, yellow iron oxide, iron oxide, zinc chromate, lead dan , ultramarine blue, iron blue, cobalt blue, chrome green, chromium oxide, barium vanadate, etc.), black pigments (such as carbon black, bone black, graphite, iron black, titanium black, etc.), glitter pigments (such as pearl pigments, aluminum Inorganic pigments such as pigments, bronze pigments, etc., and fluorescent pigments (for example, zinc sulfide, barium sulfide, barium aluminate, etc.). Further, examples of the color of the pigment that can be used include yellow, red, purple, blue, green, brown, black, white, and the like.

Further, the pigment may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, ruthenium dioxide coating, or wax coating depending on the purpose or use.

Specific examples of the above pigments are indicated by the color index according to the dye index (C.I.; The Society of Dyers and Colourists), but the colored materials of the present invention are not limited to these. Further, these may be used alone or in combination of two or more. The following "C.I." means the dye index, and the number means the dye index number.

Examples of the yellow pigment include CI Pigment Yellow 1, Pigment Yellow 2, Pigment Yellow 3, Pigment Yellow 4, Pigment Yellow 5, Pigment Yellow 6, Pigment Yellow 7, Pigment Yellow 9, Pigment Yellow 10, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 15, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 20, Pigment Yellow 24, Pigment Yellow 31, Pigment Yellow 32, Pigment Yellow 34, Pigment Yellow 35, Pigment Yellow 35:1, Pigment Yellow 36, Pigment Yellow 36:1, Pigment Yellow 37, Pigment Yellow 37:1, Pigment Yellow 40, Pigment Yellow 41, Pigment Yellow 42, Pigment Yellow 43, Pigment Yellow 48, Pigment Yellow 49, Pigment Yellow 53, Pigment Yellow 55, Pigment Yellow 60, Pigment Yellow 61, Pigment Yellow 61: 1, Pigment Yellow 62, Pigment Yellow 62: 1. Pigment Yellow 63, Pigment Yellow 65, Pigment Yellow 71, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75, Pigment Yellow 77, Pigment Yellow 81, Pigment Yellow 83, Pigment Yellow 87, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 99, Pigment Yellow 100, Pigment Yellow 101, Pigment Yellow 104, Pigment Yellow 105, Pigment Yellow 106, Pigment Yellow 108, Pigment Yellow 109, Pigment Yellow 110, Pigment Yellow 111, Pigment Yellow 113, Pigment Yellow 114, Pigment Yellow 116, Pigment Yellow 117, Pigment Yellow 119, Pigment Yellow 120, Pigment Yellow 123, Pigment Yellow 124, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 127: 1, Pigment Yellow 128, pigment yellow 129, pigment yellow 130, pigment yellow 133, pigment yellow 134, pigment yellow 136, pigment yellow 138, pigment yellow 139, pigment yellow 142, pigment yellow 147, pigment yellow 148, pigment yellow 150, pigment yellow 151, Pigment Yellow 152, Pigment Yellow 153, Pigment Yellow 154, Pigment Yellow 155, Pigment Yellow 156, Pigment Yellow 157, Pigment Yellow 15 8. Pigment Yellow 159, Pigment Yellow 160, Pigment Yellow 161, Pigment Yellow 162, Pigment Yellow 163, Pigment Yellow 164, Pigment Yellow 165, Pigment Yellow 166, Pigment Yellow 167, Pigment Yellow 168, Pigment Yellow 169, Pigment Yellow 170, Pigment Yellow 172, Pigment Yellow 173, Pigment Yellow 174, Pigment Yellow 175, Pigment Yellow 176, Pigment Yellow 179, Pigment Yellow 180, Pigment Yellow 181, Pigment Yellow 182, Pigment Yellow 183, Pigment Yellow 184, Pigment Yellow 185, Pigment Yellow 188, Pigment Yellow 189, Pigment Yellow 190, Pigment Yellow 191, Pigment Yellow 191: 1, Pigment Yellow 192, Pigment Yellow 193, Pigment Yellow 194, Pigment Yellow 195, Pigment Yellow 196, Pigment Yellow 197, Pigment Yellow 198, Pigment Yellow 199, pigment yellow 200, pigment yellow 202, pigment yellow 203, pigment yellow 204, pigment yellow 205, pigment yellow 206, pigment yellow 207, pigment yellow 208, pigment yellow 209, pigment yellow 209: 1, pigment yellow 212, pigment yellow 213, Pigment Yellow 214, Pigment Yellow 215, Pigment Yellow 219, and the like.

Examples of the orange pigment include CI Pigment Orange 1, Pigment Orange 2, Pigment Orange 3, Pigment Orange 4, Pigment Orange 5, Pigment Orange 13, Pigment Orange 15, Pigment Orange 16, Pigment Orange 17, Pigment Orange 19, Pigment Orange 20, Pigment Orange 21, Pigment Orange 22, Pigment Orange 23, Pigment Orange 24, Pigment Orange 31, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 39, Pigment Orange 40, Pigment Orange 43, Pigment Orange 46, Pigment Orange 48, Pigment Orange 49, Pigment Orange 51, Pigment Orange 60, Pigment Orange 61, Pigment Orange 62, Pigment Orange 64, Pigment Orange 65, Pigment Orange 67, Pigment Orange 68, Pigment Orange 69 , Pigment Orange 70, Pigment Orange 71, Pigment Orange 72, Pigment Orange 73, Pigment Orange 74, Pigment Orange 75, Pigment Orange 77, Pigment Orange 78, Pigment Orange 79, Pigment Orange 81 and the like.

Examples of the violet pigment include CI Pigment Violet 1, Pigment Violet 1:1, Pigment Violet 2, Pigment Violet 2: 2, Pigment Violet 3, Pigment Violet 3: 1, Pigment Violet 3:3, Pigment Violet 5, Pigment Violet 5:1, Pigment Violet 13, Pigment Violet 14, Pigment Violet 15, Pigment Violet 16, Pigment Violet 17, Pigment Violet 19, Pigment Violet 23, Pigment Violet 25, Pigment Violet 27, Pigment Violet 29, Pigment Violet 31, Pigment Violet 32, pigment violet 36, pigment violet 37, pigment violet 38, pigment violet 39, pigment violet 42, pigment violet 44, pigment violet 47, pigment violet 49, pigment violet 50, and the like.

Examples of the red pigment include CI Pigment Red 1, Pigment Red 2, Pigment Red 3, Pigment Red 4, Pigment Red 5, Pigment Red 6, Pigment Red 7, Pigment Red 8, Pigment Red 9, Pigment Red 10, Pigment Red 11, Pigment Red 12, Pigment Red 14, Pigment Red 15, Pigment Red 16, Pigment Red 17, Pigment Red 18, Pigment Red 21, Pigment Red 22, Pigment Red 23, Pigment Red 31, Pigment Red 32, Pigment Red 37 , Pigment Red 38, Pigment Red 40, Pigment Red 41, Pigment Red 42, Pigment Red 47, Pigment Red 48, Pigment Red 48:1, Pigment Red 48:2, Pigment Red 48:3, Pigment Red 48:4, Pigment Red 48:5, Pigment Red 49, Pigment Red 49:1, Pigment Red 49:2, Pigment Red 50:1, Pigment Red 52, Pigment Red 52:1, Pigment Red 52:2, Pigment Red 53, Pigment Red 53 : 1, Pigment Red 53:2, Pigment Red 53:3, Pigment Red 54, Pigment Red 57, Pigment Red 57:1, Pigment Red 57:2, Pigment Red 58, Pigment Red 58:2, Pigment Red 58:4 , pigment red 60, pigment red 60: 1, pigment red 63, pigment red 63: 1, pigment red 63: 2, pigment red 64, pigment red 64: 1, pigment red 68, pigment red 69, pigment red 81, pigment Red 81: 1. Pigment red 81:2, pigment red 81:3, pigment red 81:4, pigment red 83, pigment red 88, pigment red 89, pigment red 90:1, pigment red 95, pigment red 97, pigment red 101, Pigment Red 101:1, Pigment Red 102, Pigment Red 104, Pigment Red 105, Pigment Red 106, Pigment Red 108, Pigment Red 108:1, Pigment Red 109, Pigment Red 112, Pigment red 113, pigment red 114, pigment red 122, pigment red 123, pigment red 136, pigment red 144, pigment red 146, pigment red 147, pigment red 149, pigment red 150, pigment red 151, pigment red 164, pigment red 166, Pigment Red 168, Pigment Red 169, Pigment Red 170, Pigment Red 171, Pigment Red 172, Pigment Red 173, Pigment Red 174, Pigment Red 175, Pigment Red 176, Pigment Red 177, Pigment Red 178, Pigment Red 179, Pigment Red 180, Pigment Red 181, Pigment Red 182, Pigment Red 183, Pigment Red 184, Pigment Red 185, Pigment Red 187, Pigment Red 188, Pigment Red 190, Pigment Red 193, Pigment Red 194, Pigment Red 200, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 208, Pigment Red 209, Pigment Red 210, Pigment Red 211, Pigment Red 213, Pigment Red 214, Pigment Red 215, Pigment Red 216, Pigment Red 220, Pigment Red 221, Pigment Red 224, Pigment Red 226, Pigment Red 230, Pigment Red 231, Pigment Red 232, Pigment Red 233, Pigment Red 235, Pigment Red 236, Pigment Red 237, Pigment Red 238, Pigment Red 239, Pigment Red 242, Pigment Red 243, Pigment Red 245, Pigment Red 247, Pigment Red 248, Pigment Red 2 49, Pigment Red 250, Pigment Red 251, Pigment Red 253, Pigment Red 254, Pigment Red 255, Pigment Red 256, Pigment Red 257, Pigment Red 258, Pigment Red 259, Pigment Red 260, Pigment Red 262, Pigment Red 263, Pigment Red 264, Pigment Red 265, Pigment Red 266, Pigment Red 267, Pigment Red 268, Pigment Red 269, Pigment Red 270, Pigment Red 271, Pigment Red 272, Pigment Red 273, Pigment Red 274, Pigment Red 275, Pigment Red 276, Pigment Red 279, etc.

Examples of the blue pigment include CI Pigment Blue 1, Pigment Blue 1: 2, Pigment Blue 9, Pigment Blue 14, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:5, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 17, Pigment Blue 17:1, Pigment Blue 19, Pigment Blue 24, Pigment Blue 24:1, Pigment Blue 25, Pigment Blue 26, Pigment Blue 27, Pigment Blue 28, Pigment Blue 29, Pigment Blue 33, Pigment Blue 35, Pigment Blue 36, Pigment Blue 56, Pigment Blue 56: 1, Pigment Blue 60, Pigment Blue 61, Pigment Blue 61: 1. Pigment Blue 62, Pigment Blue 63, Pigment Blue 66, Pigment Blue 67, Pigment Blue 68, Pigment Blue 71, Pigment Blue 72, Pigment Blue 73, Pigment Blue 74, Pigment Blue 75, Pigment Blue 76, Pigment Blue 78, Pigment Blue 79, Pigment Blue 80, and the like.

Examples of the green pigment include CI Pigment Green 1, Pigment Green 2, Pigment Green 4, Pigment Green 7, Pigment Green 8, Pigment Green 10, Pigment Green 13, Pigment Green 15, Pigment Green 17, Pigment Green 18, Pigment Green 19, Pigment Green 26, Pigment Green 36, Pigment Green 45, Pigment Green 48, Pigment Green 50, Pigment Green 51, Pigment Green 54, Pigment Green 55, Pigment Green 58, and the like.

Examples of the brown pigment include C.I. Pigment Brown 5, Pigment Brown 6, Pigment Brown 23, Pigment Brown 24, Pigment Brown 25, Pigment Brown 32, Pigment Brown 41, and Pigment Brown 42.

Examples of the black pigment include aniline black, carbon black, lamp black, bone black, black iron, titanium black, CI pigment black 1, pigment black 6, pigment black 7, pigment black 9, pigment black 10, and pigment black 11 , Pigment Black 12, Pigment Black 13, Pigment Black 20, Pigment Black 31, Pigment Black 32, Pigment Black 34, and the like. Examples of the white pigment include CI Pigment White 1, Pigment White 2, Pigment White 4, Pigment White 5, Pigment White 6, Pigment White 7, Pigment White 11, Pigment White 12, Pigment White 18, Pigment White 19, Pigment White 21, Pigment White 22, Pigment White 23, Pigment White 26, Pigment White 27, Pigment White 28, and the like.

For example, the organic dyes described in JP-A-2010-103, pp. Among them, an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone imine dye, a quinoline dye, a nitro dye, a carbonyl dye, a methine dye, or the like is preferable.

The content ratio of the above-mentioned colored material (that is, the total ratio of the pigment and the dye) can be appropriately set according to the purpose and use, and the preferable range of the content ratio of the colored material is 100% by mass based on the total solid content of the curable resin composition. It is 3 to 70% by mass. More preferably, it is 5 to 60% by mass, and further preferably 10 to 50% by mass.

-Dispersant-

The dispersant is a member having an interaction site between a colored material and a dispersion medium (for example, a solvent or a binder resin), and has a function of stabilizing the dispersion of the colored medium to the dispersion medium, and is usually Divided into resin type dispersants (such as polymer dispersion) Agent), surfactant (for example, low molecular weight dispersant), pigment derivative. The curable resin composition of the present invention suitably contains a colored material and a dispersing agent. Further, as a dispersing agent (that is, a resin type dispersing agent, a surfactant, and/or a dye derivative), a commonly used dispersing agent can be used. Further, as the dispersing agent, one type may be used alone or two or more types may be used in combination.

Examples of the resin-type dispersant include polycarboxylates such as polyurethanes and polyacrylates; unsaturated polyamines, polycarboxylic acids, polycarboxylates, polycarboxylates, and polycarboxylic acids. An alkylamine salt, a polyoxyalkylene oxide, a long-chain polyamine guanamine phosphate, a hydrogen-containing polycarboxylate, by reacting a poly(lower alkylene imine) with a polyester having a free carboxyl group The formed guanamine or a salt thereof; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, Polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide/polypropylene oxide adduct, and the like.

Further, as the structure of the above-mentioned resin-type dispersant, it is particularly preferable to use an affinity chain such as an anchor chain having a main chain having an interaction site with a colored material and a graft chain having an interaction with a dispersion medium. The resin of the graft structure or the resin in which the anchor chain and the compatible chain form a block structure.

When the trade name of the above-mentioned resin type dispersing agent is mentioned, the following are mentioned, for example. However, it is not limited to these.

Can be listed as: EFKA-46, EFKA-47, EFKA-48, EFKA-745, EFKA-1101, EFKA-1120, EFKA-1125, EFKA-4008, EFKA-4009, EFKA-4046, EFKA-4047, EFKA-4520 , EFKA-4540, EFKA-4550, EFKA-6750, EFKA-4010, EFKA-4015, EFKA-4020, EFKA-4050, EFKA-4055, EFKA-4060, EFKA-4080, EFKA-4300, EFKA-4330, EFKA -4400, EFKA-4402, EFKA-4402, EFKA-4403, EFKA-4406, EFKA-4800, EFKA-5010, EFKA-5044, EFKA-5244, EFKA-5054, EFKA-5055, EFKA-5063, EFKA-5064 , EFKA-5065, EFKA-5066, EFKA-1210, EFKA-2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 1525070, 5207 (above 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 (the above is manufactured by BYK-Chemie); SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 22000, 24000, 24000GR, 26000, 28000 (above is made by Japan Lubrisol); Disperlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 152MS (above is Nanben) Chemical company); Ajisper PB-711, 821, 822, 880, PN-411, PA-111 (above is Ajinomoto Fine-Techno); KP series (manufactured by Shin-Etsu Chemical Co., Ltd.); Polyflow series (Kyoeisha) Made by a chemical company; Megaface series (manufactured by DIC Corporation); Disperaid series (manufactured by Sannopco Co., Ltd.).

Examples of the above surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, and monoethanolamine lauryl sulfate. , anionic surfactants such as lauryl sulfate triethanolamine, ammonium lauryl sulfate, sodium stearate, sodium lauryl sulfate; polyoxyethylene ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxygen a nonionic surfactant such as ethylene sorbitan monostearate or polyethylene glycol monolaurate; a cationic quaternary surfactant such as an alkyl quaternary ammonium salt or such an ethylene oxide adduct; An amphoteric surfactant such as an alkylbetaine or an alkylimidazoline such as an alkyldimethylaminoacetic acid betaine.

The compound having a structure in which a functional group is introduced into the dye-derived dye is exemplified by a sulfonic acid group, a sulfonylamino group, a quaternary salt thereof, a dialkylamine group, a hydroxyl group, a carboxyl group, and a hydrazine. Amine group, phthalic acid imine group and the like. Examples of the structure of the pigment to be the precursor include an azo type, an anthraquinone type, a quinophthalone type, a phthalocyanine type, a quinacridone type, a benzimidazolone type, an isoporphyrin type, and the like. Department, indanthrene, lanthanide, diketopyrrolopyrrole and the like.

The content ratio of the dispersing agent (that is, the resin type dispersing agent, the surfactant, and/or the dye derivative) can be appropriately set according to the purpose or use, and the dispersion stability and durability (heat resistance, light resistance, and weather resistance) From the viewpoint of the balance of the transparency, for example, it is preferably from 0.01 to 60% by mass based on 100% by mass of the total solid content of the curable resin composition. More preferably, it is 0.1 to 50% by mass, and further preferably 0.3 to 40% by mass.

- Heat resistance improver -

The above heat resistance improving agent can be preferably used for improving heat resistance or strength. The heat-resistant improver is, for example, preferably an N-(alkoxymethyl)melamine compound or a compound having two or more epoxy groups or oxetanyl groups. In particular, when the above-mentioned curable resin composition is used as a resist for a photosensitive spacer, a resist for a protective film, or a resist for an interlayer insulating film, it is preferred to use these.

- Leveling agent -

The above leveling agent can preferably be used to improve the leveling property. As the leveling agent, a fluorine-based or lanthanide-based surfactant is preferred.

- coupling agent -

The above coupling agent can be preferably used to improve the adhesion. The coupling agent is preferably a decane-based coupling agent, and examples thereof include an epoxy-based, methacrylic-based, and amine-based decane coupling agent. Among them, an epoxy-based decane coupling agent is preferred.

-Development aids -

The above development aid can be preferably used to improve developability. As the developing assistant, for example, monocarboxylic acids such as (meth)acrylic acid, acetic acid, and propionic acid; maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, trimellitic acid, etc. are preferable. Polycarboxylic acids; carboxylic anhydrides such as maleic anhydride, anhydride succinic acid, tetrahydrophthalic anhydride, and trimellitic anhydride.

The method for producing the curable resin composition is not particularly limited, and for example, it can be prepared by mixing and dispersing the above-mentioned components using various mixers or dispersers. The mixing and dispersing steps are not particularly limited and may be carried out by a usual method. Further, other steps that are generally performed may be further included. In the case where the curable resin composition contains a colored material, it is preferably produced by a dispersion treatment step of a colored material.

Examples of the dispersion treatment step of the colored material include a method of first weighing a predetermined amount of a colored material (preferably an organic pigment), a dispersant, and a solvent, and using a paint surface conditioner, a bead mill, and a roll mill. A dispersing machine such as a ball mill, a jet mill, a homogenizer, a kneader or a blender disperses the colored material to form a liquid colored material dispersion (also referred to as a slurry). Preferably, it is first subjected to kneading dispersion treatment using a roll mill, a kneader, a blender, or the like, and then subjected to a micro-dispersion treatment using a media mill such as a bead mill filled with beads of 0.01 to 1 mm. A composition containing a (meth) acrylate-based polymer, a polymerizable monomer, and a photopolymerization initiator, and optionally a solvent or a leveling agent may be added to the obtained slurry. The material (preferably a transparent liquid) is mixed and mixed to obtain a uniform dispersion solution to obtain a curable resin composition.

Further, the curable resin composition obtained is preferably subjected to a filtration treatment by a filter or the like to remove fine dust.

[hardened material]

As described above, the curable resin composition of the present invention is excellent in photosensitivity and curability, and is excellent in developability, solvent resistance, adhesion to a substrate (substrate), heat resistance, and transparency. A hardened person with excellent performance. Moreover, such a cured product is also excellent in image formability and surface smoothness, and for example, there is no residue or light in the unexposed portion after development. Further, a cured product obtained by curing such a curable resin composition is also one of the inventions.

The film thickness (thickness) of the cured product (cured film) is preferably 0.1 to 20 μm. Thereby, it is possible to sufficiently satisfy the requirements for lowering the member such as the cured product or the display device. More preferably, it is 0.5 to 10 μm, and further preferably 0.5 to 8 μm.

The cured product can be preferably used for, for example, a color filter, an ink, a printing plate, a printed wiring board, a semiconductor element, a photoresist, or the like, or an electric-electronic device used in a liquid crystal display device or a solid-state image sensor. Use. Among them, it is preferably used for a color filter. Further, a color filter obtained by using the curable resin composition as described above, that is, a color filter having the above-described cured product specifically on a substrate is also one of the inventions. Hereinafter, the color filter will be further described.

<Color Filter>

The color filter of the present invention is constituted by a form having the above-mentioned cured product on a substrate.

In the above color filter, the cured product formed of the curable resin composition of the present invention is particularly suitable as, for example, a black matrix or a segment which needs to be colored for each pixel such as red, green, blue or yellow. A photosensitive spacer, a protective layer, a barrier for alignment control, and the like do not necessarily need to be colored.

Examples of the substrate used for the color filter include a glass substrate such as white plate glass, blue plate glass, alkali-strengthened glass, and ceria coated blue plate glass; and polyester, polycarbonate, and polyolefin. a sheet, a film or a substrate comprising a thermoplastic resin such as a ring-opening polymer of a cyclic olefin or a hydrogenated product thereof; a sheet composed of a thermosetting resin such as an epoxy resin or an unsaturated polyester resin; a metal substrate such as an aluminum plate, a copper plate, a nickel plate, or a stainless steel plate; a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a glass substrate having a surface containing a colored material layer (for example, a color filter for LCD), and the like. Components such as components. Among them, in terms of heat resistance, a glass substrate or a sheet, film or substrate composed of a heat resistant resin is preferable. Further, the substrate is preferably a transparent substrate.

Further, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a decane coupling agent or the like as necessary.

<Method of Manufacturing Color Filter>

In order to obtain the color filter described above, for example, it is preferable to adopt the following manufacturing method: the following steps are applied to the pixels of each color, and the same method is repeated for each color, the step comprising: disposing the above-mentioned hardening resin composition on the substrate a step of the object (also referred to as a step of arranging), a step of irradiating light to the curable resin composition disposed on the substrate (also referred to as a light irradiation step), and a step of developing treatment by the developer (also referred to as development) Step), and a method of performing a heat treatment step (also referred to as a heating step). Furthermore, the order in which the pixels of each color are formed is not particularly limited.

- configuration step (preferably coating step) -

The above configuration steps are suitably carried out by coating. Examples of the method of applying the curable resin composition to the substrate include spin coating, slit coating, roll coating, and cast coating, and any method can be preferably used.

Moreover, in the above arrangement step, it is preferable to apply the curable resin composition onto the substrate and then dry the coating film. Drying of the coating film can be carried out, for example, using 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 solvent component contained, the type of the hardening component, the film thickness, the performance of the dryer, and the like, and it is usually suitably carried out at a temperature of 50 to 160 ° C for 10 seconds to 300 seconds.

- Light irradiation step -

In the above light irradiation step, as a light source of the active light used, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp are used. , fluorescent light and other light sources; argon ion laser, YAG laser, excimer laser, nitrogen laser, cadmium-cadmium laser, semiconductor laser and other laser sources. Further, as an embodiment of the exposure machine, a proximity method, a mirror projection method, and a stepping method are exemplified, and a proximity mode can be preferably used.

Furthermore, in the step of irradiating the active energy light, the active energy ray may be irradiated through a predetermined reticle pattern depending on the application. In this case, the exposed portion is hardened to make the hardened portion insoluble or poorly soluble in the developer.

- development step -

The developing step is a step of forming a pattern by removing the unexposed portion by performing development processing by the developing solution after the light irradiation step. Thereby, a patterned cured film can be obtained. The development treatment is usually carried out by a method such as dip development, spray development, brush development, ultrasonic development, or the like at a developing temperature of 10 to 50 °C.

The developer to be used in the above-mentioned development step is not particularly limited as long as it dissolves the curable resin composition of the present invention, and an organic solvent or an aqueous alkaline solution can be usually used, and a mixture thereof can also be used. Further, in the case where an alkaline aqueous solution is used as the developing solution, it is preferred to wash with water after development.

Examples of a suitable organic solvent for the developer include an ether solvent or an alcohol solvent. Specific examples thereof include dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, and triethylene glycol dialkyl ethers. Classes, alkyl phenyl ethers, aralkyl phenyl ethers, di aromatic ethers, isopropanol, benzyl alcohol, and the like.

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffer, a dye, a pigment, or the like as needed. The organic solvent in this case may, for example, be an organic solvent suitable as the above developing solution.

Examples of the alkaline agent include inorganic bases such as sodium citrate, potassium citrate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, disodium hydrogen phosphate, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate. a reagent such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide or tetraethylammonium hydroxide, which may be used alone or in combination 2 More than one species.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates; alkylbetaines, amines An amphoteric surfactant such as a basic acid or the like may be used alone or in combination of two or more.

- heating step -

The heating step is a step of further curing the exposed portion (hardened portion) by calcination after the development step (also referred to as a post-hardening step). For example, a light source such as a high-pressure mercury lamp, for example, a step of post-exposure with a light amount of 0.5 to 5 J/cm ² or a step of post-heating at a temperature of 60 to 260 ° C for 10 seconds to 120 minutes, or the like may be mentioned. By performing such a post-hardening step, the hardness and adhesion of the patterned cured film can be made stronger. Further, a part of the structural unit of the (meth) acrylate-based polymer contained in the curable resin composition by the heating step (that is, a (meth) acrylate monomer derived from a tertiary carbon-containing monomer A part of the portion is decomposed, so that the hardenability and the solvent resistance can be improved.

The film thickness of the cured film obtained by the above heating step (that is, the cured film obtained by thermally curing the curable resin composition) is suitably 0.1 to 20 μm. By using the curable resin composition of the present invention, a cured film having a sufficiently reduced film thickness can be provided. More preferably, it is 0.5 to 10 μm, and further preferably 0.5 to 8 μm.

In addition, when the film thickness of the coating film before heating is 100%, the film thickness of the coating film (that is, the cured film) obtained by the above heating step is preferably 90% or less. More preferably, it is 80% or less, and further preferably 70% or less.

In the above heating step, the heating temperature is suitably 150 ° C or higher. As a result, a portion derived from a part of the (meth) acrylate-based monomer containing the tertiary carbon is more effectively decomposed, so that the curability and the solvent resistance can be further improved. More preferably, it is 160 ° C or more, further preferably 170 ° C or more, and particularly preferably 180 ° C or more. Further, it is preferably 260 ° C or lower, more preferably 250 ° C or lower.

The heating time in the above heating step is not particularly limited, and is, for example, preferably 5 to 60 minutes. Further, the heating method is not particularly limited, and can be carried out, for example, by using a heating device such as a hot plate, a convection oven, or a high-frequency heater.

[display device]

Further, the present invention is also a display device comprising the above color filter.

Furthermore, in a preferred embodiment of the present invention, a member for a display device and a display device having a cured product formed of the curable resin composition are also included. The cured product (cured film) formed of the curable resin composition is relatively stable, has excellent adhesion to a substrate or the like, has high hardness, exhibits high smoothness, and has high transmittance, and thus is particularly It is suitable as a transparent member, and can also be used as a protective film or an insulating film in various display devices.

The display device is preferably, for example, a liquid crystal display device, a solid-state imaging device, or a touch panel display device.

Further, 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 a plurality of layers composed of the cured film, or may be the single layer or Further, members of the plurality of layers may be combined with members of other layers, or may be members having the above-mentioned cured film.

Since the curable resin composition of the present invention is configured as described above, it is possible to stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (substrate), heat resistance, and transparency. It has excellent storage stability and can be used in various applications such as color filters. Therefore, a color filter and a display device having a cured product (cured film) formed of such a curable resin composition are very useful in the field of optics, motors, and electronics.

The invention is further illustrated by the following examples, but the invention is not limited to the examples. Furthermore, "parts" means "parts by mass" unless otherwise specified.

In the following synthesis examples and the like, various physical properties and the like were measured in the following manner.

<weight average molecular weight>

Using polystyrene as a standard substance, tetrahydrofuran as a solution, and using GPC (gel permeation chromatography) by HLC-8220GPC (manufactured by Tosoh Corporation), column: TSK gel Super HZM-M (manufactured by Tosoh Corporation) The method measures the weight average molecular weight.

<solid content>

About 1 g of a polymer solution (also referred to as a resin solution or a polymer solution) was weighed in an aluminum cup, and about 3 g of acetone was added and dissolved, and then naturally dried at normal temperature. Further, the product was dried in a vacuum oven at 140 ° C for 1.5 hours under a vacuum using a hot air dryer (trade name: PHH-101), and then cooled in a desiccator to measure the mass. The solid content (% by mass) of the polymer solution was calculated from the mass reduction amount.

<acid value>

3 g of the resin solution was accurately weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and a 0.1 N KOH aqueous solution was used as a titration solution, and polymerization was measured by an automatic titration apparatus (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555). The acid value of the solution was determined from the acid value of the solution and the solid content of the solution to determine the acid value (AV) per 1 g of the solid content.

<Absorbance of a curable resin composition>

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

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 added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and was replaced with nitrogen, and then heated. The temperature is raised to 90 °C. On the other hand, 50 g of N-benzyl maleimide, 125 g of cyclohexyl methacrylate, and 225 g of tributyl methacrylate were mixed and stirred in a beaker as a dropping tank (A). 100 g of acrylic acid and 10 g of perbutyl (2-ethylhexanoic acid) tributyl acrylate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and prepared to be mixed with n-dodecane in a dropping tank (B). 21 g of thiol and glycerol monomethyl ether acetate were 84 g. After the temperature of the reaction vessel became 90 ° C, the mixture was dropped from the dropping tank while maintaining the same temperature, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

The polymer solution obtained was analyzed to give a weight average molecular weight of 7,800, an acid value of 129 mgKOH/g, and a resin solid content of 35.0% by 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 added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and the mixture was purged with nitrogen, and then heated to 90 ° C. On the other hand, 50 g of N-benzyl maleimide, 250 g of cyclohexyl methacrylate, and 100 g of 2-hydroxyethyl methacrylate were mixed and stirred in a beaker as a dropping tank (A). 100 g of methacrylic acid and 10 g of perbutyl (2-ethylhexanoic acid) tributyl acrylate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and prepared to be stirred and mixed in a dropping tank (B). 21 g of alkyl mercaptan and 84 g of propylene glycol monomethyl ether acetate. After the temperature of the reaction vessel became 90 ° C, the mixture was dropped from the dropping tank while maintaining the same temperature, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

The polymer solution obtained was analyzed to give a weight average molecular weight of 7,700, an acid value of 129 mgKOH/g, and a resin solid content of 35.0% by mass.

Synthesis Example 3

Synthesis of Resin Solution 3 (Copolymer with Side Chains Containing Double Bonds; BzMI-t-BA-AA//GMA Copolymer Solution)

1006.67 g of propylene glycol monomethyl ether was added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and nitrogen substitution was carried out, followed by heating to raise the temperature to 90 °C. On the other hand, 20 g of N-benzyl maleimide, 250 g of tributyl acrylate, 230 g of acrylic acid, and peroxidation (2-ethylhexyl) were prepared by stirring in a beaker as a dropping tank (A). 10% of acid) tert-butyl ester ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and prepared to mix and mix 40 g of n-dodecyl mercaptan and 160 g of propylene glycol monomethyl ether in a dropping tank (B). By. After the temperature of the reaction vessel became 90 ° C, the mixture was dropped from the dropping tank while maintaining the same temperature, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

Thereafter, the nitrogen gas 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- Tributylphenol) (manufactured by Kawaguchi Chemical Co., Ltd., "Antage w-400") 1.34 g, and 2.68 g of triethylamine as a catalyst, and stirred and mixed, and then added glycidyl methacrylate as an addition compound 393.74 g, the temperature is raised to 115 ° C, and the addition reaction is carried out. After 8 hours, the amount of residual GMA obtained by GC (gas chromatography) is 0.5% by mass or less, and the reaction is terminated to obtain a radical polymerizable double bond in the side chain. a polymer solution of an acid group-containing copolymer.

The polymer solution obtained was analyzed, and the weight average molecular weight was 6,800, the acid value was 58 mgKOH/g, and the resin solid content was 39.0% by mass.

Synthesis Example 4

Synthesis of Resin Solution 4 (Copolymer with Side Chains Containing Double Bonds; BzMI-CHA-HEA-AA//GMA Copolymer Solution)

1006.67 g of propylene glycol monomethyl ether was added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and nitrogen substitution was carried out, followed by heating to raise the temperature to 90 °C. On the other hand, 20 g of N-benzyl maleimide, 150 g of cyclohexyl acrylate, and 100 g of 2-hydroxyethyl acrylate were stirred and mixed in a beaker as a dropping tank (A). 230 g of acrylic acid and 10 g of perbutyl (2-ethylhexanoic acid) tributyl acrylate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and prepared to be mixed with n-dodecyl group in a dropping tank (B). 40 g of thiol and 160 g of propylene glycol monomethyl ether. After the temperature of the reaction vessel became 90 ° C, the mixture was dropped from the dropping tank while maintaining the same temperature, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

Thereafter, the nitrogen gas 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- Tributylphenol) (manufactured by Kawaguchi Chemical Co., Ltd., "Antage w-400") 1.34 g, and 2.68 g of triethylamine as a catalyst, and stirred and mixed, and then added glycidyl methacrylate as an addition compound 393.74 g, the temperature is raised to 115 ° C, and the addition reaction is carried out. After 8 hours, the amount of residual GMA obtained by GC (gas chromatography) is 0.5% by mass or less, and the reaction is terminated to obtain a radical polymerizable double bond in the side chain. a polymer solution of an acid group-containing copolymer.

The polymer solution obtained was analyzed, and the weight average molecular weight was 6,800, the acid value was 58 mgKOH/g, and the resin solid content was 39.0% by 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 added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and the mixture was purged with nitrogen, and then heated to 90 ° C. On the other hand, 50 g of N-benzyl maleimide, 125 g of cyclohexyl methacrylate, and 125 g of butyl methacrylate were mixed and stirred in a beaker as a dropping tank (A). 100 g of 2-hydroxyethyl acrylate, 100 g of methacrylic acid, and 10 g of perbutyl (2-ethylhexanoic acid) tributyl acrylate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and prepared for dropping tanks ( B) A mixture of 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate was stirred and mixed. After the temperature of the reaction tank becomes 90 ° C, the tank is self-drip while maintaining the same temperature. The dropwise addition was started, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

The polymer solution obtained was analyzed to give a weight average molecular weight of 7,700, an acid value of 133 mgKOH/g, and a resin solid content of 35.0% by mass.

Synthesis Example 6

Synthesis of Resin Solution 6 (Copolymer with Side Chains Containing Double Bonds; BzMI-t-BA-HEA-AA//GMA Copolymer Solution)

1006.67 g of propylene glycol monomethyl ether was added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and nitrogen substitution was carried out, followed by heating to raise the temperature to 90 °C. On the other hand, 20 g of N-benzyl maleimide, 150 g of tributyl acrylate, 100 g of 2-hydroxyethyl acrylate, and 230 g of acrylic acid were mixed and stirred in a beaker as a dropping tank (A). 10 g of perbutyl (2-ethylhexanoic acid) tributyl acrylate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and prepared to mix and mix n-dodecyl mercaptan 40 g in a dropping tank (B). And propylene glycol monomethyl ether 160g. After the temperature of the reaction vessel became 90 ° C, the mixture was dropped from the dropping tank while maintaining the same temperature, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

Thereafter, the nitrogen gas 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- Tributylphenol) (manufactured by Kawaguchi Chemical Co., Ltd., "Antage w-400") 1.34 g, and 2.68 g of triethylamine as a catalyst, and stirred and mixed, and then added glycidyl methacrylate as an addition compound 393.74 g, the temperature is raised to 115 ° C, and the addition reaction is carried out. After 8 hours, the amount of residual GMA obtained by GC (gas chromatography) is 0.5% by mass or less, and the reaction is terminated to obtain a radical polymerizable double bond in the side chain. a polymer solution of an acid group-containing copolymer.

The polymer solution obtained was analyzed, and the weight average molecular weight was 6,800, the acid value was 58 mgKOH/g, and the resin solid content was 39.0% by mass.

Synthesis Example 7

Synthesis of Resin Solution 7 (MMA-MAA Copolymer Solution)

844.57 g of propylene glycol monomethyl ether acetate was added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and the mixture was purged with nitrogen, and then heated to 90 ° C. On the other hand, 400 g of methyl methacrylate, 100 g of methacrylic acid, and tributyl acrylate (2-ethylhexanoic acid) were prepared by stirring in a beaker as a dropping tank (A) (manufactured by Nippon Oil & Fats Co., Ltd.) In the case of 10 g of "Perbutyl O", it is prepared to mix and mix 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate in a dropping tank (B). After the temperature of the reaction vessel became 90 ° C, the mixture was dropped from the dropping tank while maintaining the same temperature, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

The polymer solution obtained was analyzed to give a weight average molecular weight of 7,700, an acid value of 133 mgKOH/g, and a resin solid content of 35.0% by 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 added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and the mixture was purged with nitrogen, and then heated to 90 ° C. On the other hand, 50 g of N-benzyl maleimide, 235 g of butyl methacrylate, and 100 g of 2-hydroxyethyl methacrylate were mixed and stirred in a beaker as a dropping tank (A). 115g of methacrylic acid and 10g of perbutyl peroxide (2-ethylhexanoic acid) (Perbutyl O) manufactured by Nippon Oil & Fats Co., Ltd., and prepared to be mixed and mixed in the dropping tank (B). 6 g of dialkyl thiol and 54 g of propylene glycol monomethyl ether acetate. After the temperature of the reaction vessel became 90 ° C, the mixture was dropped from the dropping tank while maintaining the same temperature, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C, and aged for 90 minutes.

The obtained polymer solution was analyzed, and the weight average molecular weight was 15,500, and the acid value was obtained. The resin solid content was 150% KOH/g, which was 35.0% by 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 added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and the mixture was purged with nitrogen, and then heated to 90 ° C. On the other hand, a 2,2'-[oxybis(methylene)]bisdimethyl acrylate (MD) 50 g, methacrylic acid, was prepared by stirring in a beaker as a dropping tank (A). 250 g of a third butyl ester, 100 g of 2-hydroxyethyl methacrylate, 100 g of methacrylic acid, and a third butyl peroxy (2-ethylhexanoate) ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), 10 g, Further, 15 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were mixed and stirred in the dropping tank (B). After the temperature of the reaction vessel became 90 ° C, the mixture was dropped from the dropping tank while maintaining the same temperature, and polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

The polymer solution obtained was analyzed, and as a result, the weight average molecular weight was 12,000, the acid value was 133 mgKOH/g, and the resin solid content was 35.0% by 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 added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dropping inlet, and the mixture was purged with nitrogen, and then heated to 90 ° C. On the other hand, 50 g of (α-allyloxymethyl) acrylate (AMA), 250 g of butyl methacrylate, and methacrylic acid 2 were mixed and stirred in a beaker as a dropping tank (A). - 100 g of hydroxyethyl ester, 100 g of methacrylic acid, and 10 g of perbutyl (2-ethylhexanoic acid) tributyl acrylate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and prepared in a dropping tank (B) The mixture was stirred and mixed with 15 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate. After the temperature of the reaction tank is 90 ° C, the temperature is maintained at the same temperature, and the dropping is started from the dropping tank. The polymerization was carried out for 3 hours. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C and aged for 90 minutes.

The polymer solution obtained was analyzed, and as a result, the weight average molecular weight was 12,300, the acid value was 132 mgKOH/g, and the resin solid content was 35.2% by mass.

Table 1 shows the details of the resin solutions 1 to 10.

In addition, the blending amount of the monomer constituting the resin in Table 1 is the value of each monomer constituting the base polymer, and the blending ratio (% by mass) when the total amount is 100% by mass ). Further, 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 such that it has an acid group and a polymerizable property. The amount of the carboxylic acid of the double bond monomer (in this case, AA) is described as the GMA ratio of addition, and by the "GMA blend ratio (AA blend ratio with GMA addition (% by mass)) = {MMA molar amount (mol) / AA molar amount (mol)} × AA blending ratio (% by mass)". For example, in Synthesis Example 4, the AA in the base polymer (100% by mass) is composed of 46% by mass, and the 46% by mass (3191 mmol) of AA is added to 2769 mmol of GMA, whereby the GMA is added. The blending ratio (% by mass) is defined as "40".

The symbols in Table 1 are as follows.

BzMI: N-benzyl maleimide

MD: 2,2'-[oxybis(methylene)] bis-2-propenoic acid dimethyl ester

AMA: (α-allyloxymethyl) acrylate

MMA: Methyl methacrylate

CHMA: cyclohexyl methacrylate

CHA: cyclohexyl acrylate

t-BMA: tert-butyl methacrylate

t-BA: tert-butyl acrylate

HEMA: 2-hydroxyethyl methacrylate

HEA: 2-hydroxyethyl acrylate

MAA: Methacrylic acid

AA: Acrylic

GMA: glycidyl methacrylate

Production example 1

Production of Pigment Dispersion 1

12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disperlon DA-7301 as a dispersing agent, 2.25 parts of CI Pigment Green 36 (Monastral Green 6Y-CL, manufactured by Heubach Co., Ltd.) as a colored material, and CI Pigment Yellow 150 ( 1.5 parts of Yellow Pigment E4GN-GT (manufactured by Lanxess Co., Ltd.) were mixed and dispersed by a paint shaker for 3 hours, whereby Pigment Dispersion 1 was obtained.

Example 1

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

Examples 2 to 8 and Comparative Examples 1 to 7

Each of the curable resin compositions 2 to 15 was obtained in the same manner as in Example 1 except that the blending shown in Tables 2 and 3 was carried out, and the respective absorbances were measured. The results are shown in Tables 2 and 3.

Based on the results of Tables 2 and 3, the following contents were confirmed.

It can be seen that Example 1 and Comparative Examples 1, 2, 5 and 6, Example 2 and Comparative Examples 3 and 4, Examples 3, 6, 7, 8 and Comparative Example 7, Example 4 and Comparative Examples 3 and 4 are respectively An example in which the cured product was obtained under the same conditions and the absorbance was measured. If these were compared, the absorbance of the comparative example was significantly larger than that of the examples, and the transparency of the cured product was inferior. When the curability or the solvent resistance of the curable resin composition is insufficient, the absorbance of the cured product is increased due to the elution of the colored material. Therefore, according to the results of Tables 2 and 3, it is understood that compared with the examples. The curable resin composition of the comparative example was insufficient in curability and solvent resistance. Further, although not shown in the table, the cured product obtained in the examples is excellent in various physical properties such as developability, adhesion to a substrate, and heat resistance.

Claims (6)

A curable resin composition comprising a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, wherein the (meth) acrylate polymer has a third-order carbon-containing polymer a structural unit of a (meth) acrylate monomer, and a polymer having a ring structure in a main chain, wherein the curable resin composition is selected from the group consisting of a polymer further containing a hydroxyl group, and the (meth) The acrylate-based polymer further has at least one of a group consisting of a form of a hydroxyl group. The sclerosing resin composition of claim 1, wherein the (meth) acrylate monomer having a tertiary carbon has an oxygen atom adjacent to a (meth) acryl fluorenyl group and a tertiary carbon atom bond The structure of the knot. The curable resin composition according to claim 1 or 2, wherein the (meth) acrylate-based polymer and/or the polymer-based side chain having a hydroxyl group has a polymerizable double bond. A cured product obtained by hardening a curable resin composition according to any one of claims 1 to 3. A color filter having a cured product of claim 4 on a substrate. A display device constructed using a color filter of claim 5 of the patent application.