KR20140020777A - Curable resin composition and its use - Google Patents

Abstract

The present invention provides a curable resin composition which is able to stably exhibit all kinds of physical properties such as hardening properties or post-cure properties after hardening, adhesion with a substrate (basic material), heat resistance, transparency and the like, has excellent preservation stability and is useful to various purposes such as a color filter. The present invention provides a curable material formed by the curable resin composition, a color filter using the curable material and a display device. The curable resin composition comprises an acryl-based polymer, a polymerizable compound and a photopolymerization initiator. The (matte) acryl-based polymer has a composition unit originated from a (matte) acryl-based monomer containing third degree carbon. The curable resin composition is at least one selected from the group consisting of a form in which the curable resin composition includes a polymer additionally having a hydroxyl group, and a form in which the (matte) acryl-based polymer additionally has a hydroxyl group.

Description

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

The present invention relates to a curable resin composition and its use. In more detail, curable resin composition useful for various uses, such as a color filter, ink, a printing board, a printed wiring board, a semiconductor element, a photoresist, etc. used for a liquid crystal display device, a solid-state image sensor, etc., various optical members, electrical, electronic equipment, etc. The hardened | cured material and the color filter which used hardened | cured material, and a display apparatus are related.

The curable resin composition which can be hardened by heat or an active energy ray is various optical, such as a color filter, an ink, a printing board, a printed wiring board, a semiconductor element, and a photoresist used for a liquid crystal display device or a solid-state image sensor, etc., for example. Application to various uses, such as a member, an electric and electronic device, is examined variously, and the development of curable resin composition excellent in the characteristic calculated | required by each use is made | formed. Among these uses, a color filter is a main member constituting a liquid crystal display device, a solid-state image sensor, or the like, and generally includes a substrate, pixels of at least three primary colors (red (R), green (G), blue (B)), And a protective film formed in order to cover and protect the pixel and the resin black matrix and to planarize the unevenness in addition to the resin black matrix (BM) for shorting them.

Usually, when performing pixel formation of a color filter using curable resin composition, it is by the application | coating process of apply | coating curable resin composition to (1) whole board | substrate whole surface with respect to one pixel, and (2) application | coating process. After exposing the formed resist film through a patterned photomask through a patterned exposure to cure the exposed portion, the exposed portion was insolubilized, and (3) the unexposed portion was removed by a developer, and then the exposed portion was further baked by baking (baking). The method of performing the image development and baking (baking) process process to harden, and repeating the same process by each color is employ | adopted. Considering application to such a color filter use, the curable resin composition is required to have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance and transparency. In recent years, miniaturization, thinning, and energy saving of optical members, electrical and electronic devices, and the like have been progressing, and high quality performance is desired for members such as color filters to be used.

Regarding the conventional curable resin composition, suitable compositions for color filter applications include, for example, binder resins having structural units derived from monomers having aliphatic polycyclic epoxy groups and structural units derived from unsaturated carboxylic acid monomers; The structural unit which has the residue which the coloring photosensitive resin composition (refer patent document 1) containing a coloring agent, a photopolymerizable compound, a photoinitiator, and a solvent, and a carboxyl group / phenolic hydroxyl group was protected by a thermally decomposable group, epoxy group / oxeta Colored photosensitive resin composition containing the copolymer containing the structural unit which has a nilyl group, and the structural unit which has a carboxyl group / phenolic hydroxyl group, a radiation sensitive radical polymerization initiator, an ethylenically unsaturated compound, and a coloring agent (refer patent document 2). ) Is disclosed.

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

As described above, the curable resin composition is required to have various physical properties such as solvent resistance after curing, curing, adhesiveness with a substrate (also referred to as a substrate), heat resistance and transparency. On the other hand, from the viewpoint of handling, curable resin composition itself has storage stability (also called storage stability), and it is also required that hardened | cured material can exhibit transparency, solvent resistance, adhesiveness, heat resistance, etc. stably. In recent years, with advances in technology, such as a display device, more advanced performance is also strongly requested | required also about each member used, For example, in color filter use, high transparency is calculated | required after hardening. . However, in the conventional resin composition, it is a present situation that cannot fully satisfy these requirements. For example, since the resin composition of patent document 1 or 2 does not have sufficient sclerosis | hardenability, hardened | cured material with high transparency cannot be obtained, and since the storage stability is also not enough, the curability of a resin composition is raised more, There was room for research to ensure high transparency and stability. Moreover, there was also room for research to improve the storage stability of the resin composition.

This invention is made | formed in view of the said present situation, and can exhibit various physical properties, such as hardenability, the solvent resistance after hardening, adhesiveness with a board | substrate (base material), heat resistance, and transparency, is excellent in storage stability, and is excellent in color filters, etc. It is an object to provide a curable resin composition useful for various uses. Another object of the present invention is to provide a cured product formed of such a curable resin composition, and a color filter and a display device using the cured product.

MEANS TO SOLVE THE PROBLEM As a result of investigating the curable resin composition useful for various uses, such as a color filter, when it is set as the resin composition containing a (meth) acrylate type polymer, a polymeric compound, and a photoinitiator, it will become curable. Noticed. And the form which makes the (meth) acrylate type polymer have a structural unit derived from a tertiary carbon containing (meth) acrylate type monomer, and also contains the said curable resin composition the polymer which has a hydroxyl group, and / Or when the (meth) acrylate type polymer further has a hydroxyl group, while curable resin composition is excellent in storage stability, the curability and the solvent resistance after hardening improve remarkably, and high transparency and a board | substrate (base material The hardened | cured material which can express various physical properties, such as adhesiveness with heat, heat resistance, and high hardness, was found to be obtained. Such a curable resin composition is particularly useful for color filter applications, and is particularly preferred as a resin composition for forming a protective film, an insulating film, or the like for a color filter. Therefore, the hardened | cured material formed from such a curable resin composition, a color filter, and a display apparatus can find out that what is extremely useful in the optics field, an electric field, and an electronics field as it can fully respond to the demand of the recent high performance, The present invention has been reached in addition to what can be solved well.

Here, although the (meth) acrylate type polymer contained in curable resin composition of this invention has a structural unit derived from a tertiary carbon containing (meth) acrylate type monomer, this structural unit is easy to decompose | disassemble by heat. Specifically, the OC bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto is easily broken, whereby the (meth) acrylic acid and the tertiary carbon atom are generated. Decomposes into stable compounds. Therefore, for example, when the curable resin composition of this invention is used for pixel formation of a color filter, the above-mentioned tertiary carbon containing (also called a baking process or a postbaking process) after image development (meth) The structural unit derived from an acrylate-type monomer is decomposed | disassembled, and the stable compound which generate | occur | produces on the side of (meth) acrylic acid and a tertiary carbon atom is produced. And the ester crosslinking structure between the hydroxyl group in the polymer which has a hydroxyl group which curable resin composition can have further, and / or the hydroxyl group which a (meth) acrylate type polymer can further have, and the (meth) acrylic acid produced | generated Due to the occurrence, it is considered that the curability of the resin composition and the solvent resistance after curing are remarkably improved.

It is preferable that the said (meth) acrylate type polymer and the polymer which has a hydroxyl group are a polymer which has a polymerizable double bond in a side chain as mentioned later. Thereby, although sclerosis | hardenability can be improved further, in this invention, it becomes possible to improve storage stability with sclerosis | hardenability of curable resin composition rather than using the polymer which has a polymerizable double bond in a side chain. Even so, in the present invention, as described above, a curing reaction by an ester crosslinked structure between (meth) acrylic acid and hydroxyl groups generated by pyrolysis can be expected, and as such, the content of the polymerizable double bond in the polymer is increased. Since a sufficient curability can be expressed even if it is small, the possibility that the polymerizable double bond of a side chain may react and gelatinize during storage can be reduced more.

That is, this invention is curable resin composition containing a (meth) acrylate type polymer, a polymeric compound, and a photoinitiator, The (meth) acrylate type polymer is a structural unit derived from a tertiary carbon containing (meth) acrylate type monomer. The curable resin composition is a form containing a polymer further having a hydroxyl group, and the (meth) acrylate-based polymer is at least one type selected from the group consisting of a form further having a hydroxyl group. Curable resin composition.

This invention is also hardened | cured material formed by hardening | curing the said curable resin composition.

This invention is also a color filter which has the said hardened | cured material further on a board | substrate.

This invention is also a display apparatus comprised using the said color filter.

Hereinafter, the present invention will be described in detail. Moreover, the form which combined 2 or 3 or more of individual preferable aspects of this invention described below is also a preferable aspect of this invention.

[Curable resin composition]

Although the curable resin composition of this invention contains a (meth) acrylate type polymer, a polymeric compound, and a photoinitiator, these containing components can use 1 type (s) or 2 or more types, respectively. Moreover, you may contain 1 type (s) or 2 or more types further as needed.

<(Meth) acrylate type polymer>

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

To the tertiary carbon-containing (meth) acrylate-based monomers, polymerizable carbon in the molecule - a compound having one carbon-carbon double bond, that is, a (meth) acryloyl group in the molecule _{(CH 2 = C (R)} -C ( It is preferable that it is a compound which has one = O)-), For example, following General formula (1):

CH ₂ = C (R) -C (= O) -OA (1)

It is preferable that it is a compound represented by (R represents a hydrogen atom or a methyl group. A represents a monovalent organic group containing the structure which has a tertiary carbon atom on the oxygen atom side.).

In the general formula (1), organic groups represented by A, for example, can be represented by ^{-C (R 1) (R 2} ) (R 3). In this case, R <^1> , R <^2> and R <^3> are the same or different, It is preferable that it is a C1-C30 hydrocarbon group, A saturated hydrocarbon group may be sufficient as the said hydrocarbon group, and an unsaturated hydrocarbon group may be sufficient as it. Moreover, you may have a cyclic structure and may have a substituent further. In addition, R <^1> , R <^2> and R <^3> may connect with each other at the terminal site, and may form the cyclic structure.

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

In the tertiary carbon-containing (meth) acrylate-based monomer, in the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group, at least one of the adjacent carbon atoms is bonded to the hydrogen atom. It is desirable to have. For example, as the compound is a tertiary carbon-containing (meth) acrylate-based monomer represented by the general formula (1), A is ^{-C (R 1) (R 2} ) (R 3) , if a group represented by, R ¹ It is preferable that at least 1 of R <^2> and R <^3> has 1 or more of hydrogen atoms. In such a form, by heating, the OC bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto is cleaved to generate (meth) acrylic acid, and at the same time, the third A double bond (C = C) is formed between the upper carbon atom and the carbon atom adjacent to it so that a new compound is produced more stably.

It is preferable that the new compound produced as mentioned above is volatilized. In this case, when the said new compound volatilizes from hardened | cured material, the film thickness of hardened | cured material (cured film) reduces, for example, when the said curable resin composition contains a coloring material further, a color material The concentration becomes high after heating. As a result, the film can be further thinned, and the color can be more highly purified and the black matrix can be more highly light-shielded. In consideration of this point, the R ¹ , R ² and R ³ are the same or different and preferably a saturated hydrocarbon group having 1 to 15 carbon atoms. More preferably, they are 1-10 saturated hydrocarbon groups, More preferably, they are 1-5 saturated hydrocarbon groups, Especially preferably, they are 1-3 saturated hydrocarbon groups.

It is preferable that the said (meth) acrylate type polymer is a polymer which shows alkali solubility from a developable viewpoint, and it is preferable that it is a polymer which has an acidic radical in a molecule | numerator.

As said acid group, functional groups which neutralize-react with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, a sulfonic acid group, may be mentioned, for example, You may have only 1 type of these, and 2 or more types You may have it. Especially, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxyl group is more preferable.

When the said (meth) acrylate type polymer is a polymer which has an acidic radical in a molecule | numerator, although it does not specifically limit as acid value (AV) of the said polymer, For example, it is preferable that it is 20 mgKOH / g or more and less than 300 mgKOH / g. Do. Thereby, sufficient alkali solubility is expressed and it becomes possible to obtain the hardened | cured material excellent in developability. As a lower limit of an acid value, More preferably, it is 30 mgKOH / g or more, More preferably, it is 40 mgKOH / g or more. Moreover, 200 mgKOH / g or less is more preferable, More preferably, it is 150 mgKOH / g or less.

The acid value of a polymer can be calculated | required as it mentions later, for example.

The (meth) acrylate polymer may also be a polymer having a hydroxyl group (hydroxyl group) in the molecule. That is, the said (meth) acrylate type polymer may further be a polymer which has a hydroxyl group, and such a form is also one of the preferable forms of this invention. Thereby, the curability of curable resin composition improves more and the hardened | cured material excellent in transparency can be provided.

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

In addition, each monomer used can use 1 type (s) or 2 or more types, respectively.

The (meth) acrylate polymer may be a polymer obtained by polymerizing such a monomer component (also referred to as a base polymer), and as described later, a functional group capable of bonding to an acid group and a polymerizable double bond may be incorporated into the base polymer. A polymer (referred to as a polymer having a polymerizable double bond in the side chain or a side chain double bond-containing polymer) obtained by reacting a compound having a compound may be used, either of which is preferable. More preferably, it is a side chain double bond containing polymer, and by this, hardenability improves further and the hardened | cured material excellent in transparency, adhesiveness, etc. can be obtained. Moreover, it is preferable that the polymerizable double bond of a side chain is a radically polymerizable double bond.

In the said monomer component, although a tertiary carbon containing (meth) acrylate type monomer is as above-mentioned, it is preferable that the content rate of this monomer is 5 mass% or more with respect to 100 mass% of total amounts of the said monomer component. Thereby, the effect of this invention resulting from the structural unit derived from a tertiary carbon containing (meth) acrylate type monomer is further expressed. More preferably, it is 15 mass% or more, Especially preferably, it is 20 mass% or more. In addition, what is necessary is just to set the upper limit of the said content ratio suitably in consideration of the content ratio of another monomer, For example, when using for a color filter use, it is 90 mass% or less from a viewpoint of further improving a pattern characteristic and developability. desirable. More preferably, it is 75 mass% or less, More preferably, it is 60 mass% or less.

As a monomer which has the said acidic radical and a polymerizable double bond, For example, unsaturated monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl benzoic acid; Unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; Unsaturated monocarboxylic acids in which an unsaturated group such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxyethyl) and a carboxyl group is extended in chain; Unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; And phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyowa Co., Ltd.). Among these, it is preferable to use a carboxylic acid monomer (unsaturated monocarboxylic acids, unsaturated polyhydric carboxylic acids, unsaturated acid anhydrides) from a viewpoint of versatility, availability, etc. More preferably, it is preferable to use unsaturated monocarboxylic acids from a viewpoint of reactivity, alkali solubility, etc., More preferably, it is (meth) acrylic acid, Especially preferably, it is methacrylic acid.

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

It is preferable to set the content rate of the monomer which has the said acidic radical and polymerizable double bond so that the acid value of a (meth) acrylate type polymer may be in the preferable range mentioned above. For example, it is preferable that the content rate of the monomer which has an acidic radical and a polymerizable double bond is 5 mass% or more with respect to 100 mass% of total amounts of the said monomer component, More preferably, it is 10 mass% or more, More preferably, 20 It is mass% or more. Moreover, it is preferable that it is 85 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less.

It is also preferable that the said monomer component also contains the monomer which has a hydroxyl group and a polymerizable double bond as mentioned above. It is preferable that such a monomer is a monomer which has a hydroxyl group in a side chain, and it is preferable that it is a monomer which has a hydroxyl group and a (meth) acryloyl group from a reactive viewpoint. For example, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3- Hydroxyalkyl (meth) acrylates, such as hydroxybutyl, 4-hydroxybutyl (meth) acrylic acid, and 2,3-hydroxypropyl (meth) acrylic acid, are mentioned preferably.

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

When the said monomer component contains the monomer which has a hydroxyl group and a polymerizable double bond, it is preferable that the content rate of the monomer is 1 mass% or more with respect to 100 mass% of total amounts of the said monomer component, for example. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more. Moreover, when considering the content ratio of a tertiary carbon containing (meth) acrylate type monomer, an acidic radical, and the monomer which has a polymerizable double bond, it is preferable that it is 70 mass% or less, More preferably, it is 50 mass% or less.

Although the (meth) acrylate type polymer contained in curable resin composition of this invention is a polymer which has a structural unit derived from a tertiary carbon containing (meth) acrylate type monomer, it is preferable to have a ring structure in a principal chain further. Examples of the ring structure include an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring and a lactone ring. In order to have these ring structures, the said monomer component may contain the other copolymerizable monomer (it is also called another monomer) other than the monomer mentioned above.

As said other monomer, the N substituted maleimide type monomer, the dialkyl-2,2'- (oxydimethylene) diacrylate type monomer, and (alpha)-(unsaturated alkoxyalkyl) other than the above-mentioned monomers are mentioned, for example. It is preferable to use an acrylate monomer (preferably an alkyl- (α-allyloxymethyl) acrylate monomer) and the like. As such, the monomer component further comprises an N-substituted maleimide monomer, a dialkyl-2,2 '-(oxydimethylene) diacrylate monomer and an α- (unsaturated alkoxyalkyl) acrylate monomer. The form containing at least 1 sort (s) of monomer chosen from the group is one of the preferable forms of this invention. In addition, 1 type (s) or 2 or more types, such as a (meth) acrylic acid ester type monomer and an aromatic vinyl type monomer, are used suitably according to a required physical property.

Here, for example, an N-substituted maleimide monomer and / or a dialkyl-2,2 '-(oxydimethylene) diacrylate monomer and / or an alkyl- (α-allyloxymethyl) acrylate monomer may be used. When used, it becomes possible to provide hardened | cured material which improved heat resistance, hardness, color material dispersibility, etc. more. In particular, when a dialkyl-2,2 '-(oxydimethylene) diacrylate-based monomer and / or an alkyl- (α-allyloxymethyl) acrylate-based monomer are used, a cured product that is more excellent in terms of heat colorability can be obtained. Obtained.

Moreover, it is preferable to set it as 60 mass% or less in 100 mass% of total amounts of the said monomer component, and, as for the content rate of the said other monomer, it is more preferable to set it as 50 mass% or less. In particular, when the N-substituted maleimide monomer, the dialkyl-2,2 '-(oxydimethylene) diacrylate monomer and / or the α- (unsaturated alkoxyalkyl) acrylate monomer are included, the content ratio is From the standpoints of heat resistance and hardness, colorant dispersibility, development speed, transparency, and the like, it is preferably 2 to 60 mass%, more preferably 2 to 50 mass%, still more preferably 3 to 40 mass%.

As said N substituted maleimide type monomer, For example, N-cyclohexyl maleimide, N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, Nt-butyl maleim Mid, N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide, etc. are mentioned, These 1 type, or 2 or more types can be used. Especially, from a transparency viewpoint, N-phenylmaleimide and N-benzyl maleimide are preferable, and N-benzyl maleimide is especially preferable.

As said N-benzyl maleimide, For example, benzyl maleimide; alkyl substituted benzyl maleimides such as p-methylbenzyl maleimide and p-butylbenzyl maleimide; Phenolic hydroxyl group substituted benzyl maleimide, such as p-hydroxybenzyl maleimide; Halogen-substituted benzyl maleimide, such as o-chloro benzyl maleimide, o- dichloro benzyl maleimide, and p- dichloro benzyl maleimide, etc. are mentioned.

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

Examples of the α- (unsaturated alkoxyalkyl) acrylate monomer include α-allyloxymethylacrylic acid, α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, and α-allyloxymethyl acrylate n-. Propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α-allyloxymethyl acrylate n- Amyl, (alpha)-allyl oxymethyl acrylate s-amyl, (alpha)-allyl oxymethyl acrylate t-amyl, (alpha)-allyl oxymethyl acrylate neopentyl, etc. are mentioned. Especially, the alkyl-((alpha) -allyloxymethyl) acrylate type monomer is preferable. As the alkyl- (α-allyloxymethyl) acrylate-based monomer, for example, methyl- (α-allyloxymethyl) acrylate or the like is used from the viewpoints of transparency, dispersibility, and ease of industrial availability. It is preferable.

The said (alpha)-(unsaturated alkoxyalkyl) acrylate can be manufactured by the manufacturing method disclosed by the international publication 2010/114077 pamphlet, for example.

As said (meth) acrylic acid ester monomer, when the surface hardness etc. of hardened | cured material are considered, the monomer which has an alicyclic skeleton is preferable, for example. Specifically, for example, cyclohexyl (meth) acrylate, cyclohexyl methyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (3,4- Epoxycyclohexyl) methyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol-tricyclodecane (Meth) acrylate, pentacyclopentadecandimethanoldi (meth) acrylate, cyclohexanedimethanoldi (meth) acrylate, norbornanedimethanoldi (meth) acrylate, p-mentan-1,8-diol Di (meth) acrylate, p-mentane-2,8-dioldi (meth) acrylate, p-mentan-3,8-dioldi (meth) acrylate, bicyclo [2.2.2] -octane-1 -Methyl-4-isopropyl-5,6-dimethylol di (meth) acrylate, etc. are mentioned. Among these, cyclohexyl (meth) acrylate, cyclohexyl methyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclo decanyl (meth) acrylate are used from the viewpoint of versatility and availability. It is preferable. Moreover, it is also preferable to use alicyclic epoxy compounds, such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and ethyl glycidyl (meth) acrylate.

Examples of the (meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth) acrylate. S-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, ( Tridecyl methacrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic acid -Methoxyethyl, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, α-hydroxymethylacrylic acid Methyl, α-hydroxymethyl acrylate, α-hydroxymethyl acrylate t-butyl, α-below 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloyl morpholine, tetrahydrofurfuryl acrylate, 4- in addition to hydroxymethyl acrylate t-amyl etc. (Meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane and 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-di Oxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1, 3-dioxolane etc. are mentioned. Among them, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate in terms of easily balancing the heat resistance, colorant dispersibility, and solvent re-dissolution properties. This is preferred.

As said aromatic vinylic monomer, styrene, vinyltoluene, (alpha) -methylstyrene, methoxy styrene, etc. are mentioned, for example. Especially, styrene and / or vinyltoluene are preferable at the point of heat-coloring property of resin, and heat-decomposability.

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

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

As a method of polymerizing the said monomer component, the method normally used, such as bulk polymerization, solution polymerization, emulsion polymerization, can be used, What is necessary is just to select suitably according to the objective and a use. Especially, since solution polymerization is industrially advantageous and structural adjustment, such as molecular weight, is also easy, it is preferable. Moreover, although the polymerization mechanism of the said monomer component can use the polymerization method based on mechanisms, such as radical polymerization, anion polymerization, cationic polymerization, and coordination polymerization, since the polymerization method based on radical polymerization mechanism is industrially advantageous, it is preferable. Do.

The polymerization initiation method in the polymerization reaction may supply energy required for polymerization initiation from the active energy sources such as heat, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and the like into the monomer component. When used together, since the energy required for polymerization start can be greatly reduced, and reaction control becomes easy, it is preferable.

Moreover, the molecular weight of the polymer obtained by superposing | polymerizing the said monomer component can be controlled by adjustment of the quantity or kind of a polymerization initiator, polymerization temperature, the kind and quantity of a chain transfer agent, etc.

When superposing | polymerizing the said monomer component by the solution polymerization method, it will not specifically limit, if it is inert to a polymerization reaction as a solvent used for superposition | polymerization. For example, what is necessary is just to set suitably according to superposition | polymerization conditions, such as a polymerization mechanism, the kind and quantity of monomers to be used, superposition | polymerization temperature, superposition | polymerization density | concentration, and when using a solvent as a diluent etc. later, It is preferable to use the solvent containing a solvent by solution polymerization of a monomer component, and it is preferable.

As said solvent, the following compound etc. are mentioned preferably, For example, these 1 type, or 2 or more types can be used.

Monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; Glycols such as ethylene glycol and propylene glycol; Cyclic ethers such as tetrahydrofuran and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Glycol monoethers such as propylene glycol monobutyl ether and 3-methoxybutanol; Glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether Ethers; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Glycol mono, such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate Esters of ethers; Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxypropionate, methyl 3-methoxypropionate, 3- Alkyl esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Aliphatic hydrocarbons such as hexane, cyclohexane and octane; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

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

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

When superposing | polymerizing the said monomer component by a radical polymerization mechanism, it is industrially advantageous to use the polymerization initiator which generate | occur | produces a radical by heat, and it is preferable. Such polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy, and may be appropriately selected depending on polymerization conditions such as polymerization temperature, solvent, and type of monomer to be polymerized. Moreover, you may use together reducing agents, such as a transition metal salt and amines, with a polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxy isopropyl carbonate, t -Butyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1'- azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) And peroxides and azo compounds commonly used as polymerization initiators such as dimethyl 2,2'-azobis (2-methylpropionate), hydrogen peroxide, persulfate, and the like, and these may be used alone or in combination. You may use the above together.

What is necessary is just to set suitably the usage-amount of the said polymerization initiator suitably according to the kind and quantity of the monomer to be used, superposition | polymerization conditions, such as superposition | polymerization temperature, superposition | polymerization concentration, molecular weight of a target polymer, etc., and are not specifically limited. For example, in obtaining a polymer with a weight average molecular weight of thousands to tens of thousands, it is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of said monomer components. More preferably, it is 0.5-15 mass parts.

In the said polymerization, you may use the chain transfer agent normally used as needed. Preferably, it uses together a polymerization initiator and a chain transfer agent. Moreover, when a chain transfer agent is used at the time of superposition | polymerization, there exists a tendency which can suppress increase of molecular weight distribution, or gelatinization.

As said chain transfer agent, For example, mercaptocarboxylic acids, such as mercaptoacetic acid and 3-mercaptopropionic acid; Methyl mercaptopropionate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, Mercaptocarboxylic acid esters such as propane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) Ryu; Alkyl mercaptans such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, and 1,2-dimercaptoethane; Mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; Aromatic mercaptans such as benzene thiol, m-toluene thiol, p-toluene thiol, and 2-naphthalene thiol; Mercapto isocyanurates, such as tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate; Disulfides such as 2-hydroxyethyl disulfide and tetraethyl thiuram disulfide; Dithiocarbamates such as benzyldiethyldithiocarbamate; monomeric dimers such as α-methylstyrene dimer; Halogenated alkyls, such as carbon tetrabromide, etc. are mentioned. These may be used independently and may use 2 or more types together.

Among these, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans, mercaptoalcohols, and aromatic mercaptans from the viewpoint of availability, crosslinking prevention ability, and the degree of reduction in polymerization rate are small. It is preferable to use the compound which has mercapto groups, such as mercapto isocyanurate. More preferably, they are alkyl mercaptans, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, More preferably, they are n-dodecyl mercaptan and mercaptopropionic acid.

What is necessary is just to set suitably the usage-amount of the said chain transfer agent according to the kind and quantity of the monomer to be used, superposition | polymerization conditions, such as superposition | polymerization temperature, superposition | polymerization concentration, molecular weight of a target polymer, etc., and are not specifically limited. For example, in obtaining a polymer with a weight average molecular weight of thousands to tens of thousands, it is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of said monomer components. More preferably, it is 0.5-15 mass%.

Regarding the polymerization conditions, the polymerization temperature may be appropriately set depending on the kind and amount of the monomer to be used, the kind and amount of the polymerization initiator, and the like, for example, 50 to 150 ° C. is preferable, and More preferred. Moreover, although superposition | polymerization time can also be set suitably similarly, 1 to 6 hours are preferable, for example, 2 to 5 hours are more preferable.

The polymer obtained by making the said (meth) acrylate type polymer react with the base polymer obtained by superposing | polymerizing the said monomer component to the compound which has a functional group and polymerizable double bond which can couple | bond with an acidic radical (it is also called a side chain double bond containing polymer). ), One type or two or more types can be used as the compound having a functional group capable of bonding with an acid group and a polymerizable double bond. In such a compound, as a polymerizable double bond, a (meth) acryloyl group, a vinyl group, an allyl group, a metalyl group, etc. are mentioned, for example, As these compounds, 1 type (s) or 2 or more types are mentioned. It is desirable to have. Especially, from a reactive point, a (meth) acryloyl group is preferable. Moreover, as a functional group which can couple | bond with an acidic group, a hydroxyl group, an epoxy group, an oxetanyl group, an isocyanate group, etc. are mentioned, for example, It is preferable to have these 1 type, or 2 or more types as these compounds. . Especially, an epoxy group (including glycidyl group) is preferable at the point of the speed | rate, heat resistance, and dispersibility of a modification process reaction.

As a compound which has a functional group and a polymerizable double bond which can couple | bond with the said acidic radical, For example, (meth) acrylic acid glycidyl, (meth) acrylic acid (beta) -methylglycidyl, (meth) acrylic acid (beta) -ethylglycol Cydyl, vinylbenzyl glycidyl ether, allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide, and the like. Can be used. Especially, it is preferable to use the compound (monomer) which has an epoxy group and a (meth) acryloyl group.

As a method of obtaining the said side chain double bond containing polymer, For example, when reacting the said base polymer with the compound which has a functional group couple | bonded with an acidic radical, and a polymerizable double bond, the acid group of the base polymer (preferably Is a method in which the amount of the carboxyl group is greater than the amount of the compound having a functional group and a polymerizable double bond capable of bonding with the acid group; After reacting the said base polymer with the compound which has a functional group which can couple | bond with an acidic radical, and a polymerizable double bond, the method of reacting the compound which has a polybasic acid anhydride group further, etc. are mentioned.

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

As said basic catalyst, For example, tertiary amines, such as dimethylbenzylamine, triethylamine, tri-n-octylamine, and tetramethylethylenediamine; Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide and n-dodecyltrimethylammonium chloride; Urea compounds such as tetramethylurea; Alkylguanidines such as tetramethylguanidine; Amide compounds such as dimethylformamide and dimethylacetamide; Tertiary phosphines, such as triphenyl phosphine and tributyl phosphine; And quaternary phosphonium salts such as tetraphenylphosphonium bromide and benzyl triphenylphosphonium bromide, and the like, and one or two or more thereof can be used. Among them, dimethylbenzylamine, triethylamine, tetramethylurea and triphenylphosphine are preferable from the viewpoints of reactivity, handleability, halogen free, and the like.

It is preferable that the usage-amount of the said catalyst shall be 0.01-5.0 mass parts with respect to 100 mass parts of total amounts of the said monomer component, the functional group (for example, epoxy group, etc.) which can couple | bond with an acidic radical, and the compound which has a polymerizable double bond. . More preferably, it is 0.1-3.0 mass parts.

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

As said polymerization inhibitor, the polymerization inhibitor for radically polymerizable monomers normally used can be used, For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, metoquinone, 6- t-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl Phenol type inhibitors, such as -6-t-butylphenol), an organic acid copper salt, phenothiazine, etc. are mentioned, These 1 type, or 2 or more types can be used. Especially, a phenolic inhibitor is preferable at the point of low coloring, a polymerization prevention ability, etc. From a viewpoint of availability and economical efficiency, 2,2'- methylenebis (4-methyl-6-t-butylphenol) and a metoquinone , 6-t-butyl-2,4-xylenol and 2,6-di-t-butylphenol are more preferred.

As a usage-amount of the said polymerization inhibitor, the compound which has a functional group and a polymerizable double bond which can couple | bond with the said monomer component from an acidic radical from a viewpoint of ensuring sufficient polymerization prevention effect, curability, etc. when it is set as curable resin composition. It is preferable that they are 0.001-1.0 mass part with respect to 100 mass parts of total amounts of. More preferably, it is 0.01-0.5 mass part.

As a compound which has the said polybasic acid anhydride group, For example, succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyl hexa Hydrophthalic anhydride, endmethylenetetrahydro phthalic anhydride, methylendmethylenetetrahydro phthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. One kind or two or more kinds thereof can be used.

It is preferable that the weight average molecular weights of the said (meth) acrylate type polymer are 2000-250000. By being in such a range, it becomes possible to exhibit more favorable developability. More preferably, it is 3000-100000, More preferably, it is 4000-500000. Moreover, when the said (meth) acrylate type polymer is high molecular weight (for example, 10000-500000), the hardened | cured material of a higher hardness tends to be obtained, and the higher the acid value (preferably 150 mgKOH / g As mentioned above, it exists in the tendency to develop easily by controlling to 200 mgKOH / g or less).

The weight average molecular weight of a polymer can be calculated | required as it mentions later, for example.

When the said (meth) acrylate type polymer is a polymer which has a double bond in a side chain (namely, a side chain double bond containing polymer), it is preferable that a double bond equivalent is 200-10000. By being in such a range, storage stability of a polymer will become more favorable. More preferably, it is 200-5000, More preferably, it is 250-4000, Especially preferably, it is 300-4000.

A double bond equivalent is the mass of solid content of the polymer solution (also called resin solution) per 1 mol of double bonds of a polymer. The mass of solid content of the polymer solution here adds the mass of the structural component of the said monomer component, and the mass of a polymerization inhibitor. It is possible to obtain by dividing the mass of the solid content of the polymer solution by the double bond amount of the polymer. The double bond amount of a polymer can be calculated | required from the quantity of the compound which has the acid group injected, the functional group which can couple | bond, and a polymerizable double bond.

Curable resin composition of this invention is a thing of the form containing the polymer which has a hydroxyl group further, and the (meth) acrylate type polymer of at least 1 sort (s) chosen from the group which consists of a form which further has a hydroxyl group further. By having a hydroxyl group in the system in this way, it originates in the ester crosslinked structure generate | occur | producing between (meth) acrylic acid which arises by decomposition | disassembly of the structural unit derived from the tertiary carbon containing (meth) acrylate type monomer mentioned above. Curing property becomes remarkably high, and it becomes possible to give especially the hardened | cured material excellent in transparency. Moreover, while the said curable resin composition contains the polymer which has a hydroxyl group further, the said (meth) acrylate type polymer may further have a hydroxyl group.

As a form in which the said (meth) acrylate type polymer has a hydroxyl group further, as mentioned above, it contains a tertiary carbon containing (meth) acrylate type monomer, and the monomer which has a hydroxyl group and a polymerizable double bond, Base polymer obtained by polymerizing the monomer component which further preferably contains the monomer which has an acidic radical and a polymerizable double bond; The side chain double bond containing polymer obtained by making the base polymer react with the compound which has a functional group which can couple | bond with an acidic radical, and a polymerizable double bond is mentioned preferably. Especially, the latter side chain double bond containing polymer is preferable.

<Polymer having a hydroxyl group>

In the case where the curable resin composition further includes a polymer having a hydroxyl group in addition to the (meth) acrylate polymer, the polymer having the hydroxyl group is not particularly limited as long as the polymer has a hydroxyl group in a molecule. Especially, it is preferable that it is a polymer which shows alkali solubility from a viewpoint of improving developability more, and it is preferable that it is a polymer which has an acidic radical in a molecule | numerator. About an acidic radical, it is as having mentioned above in the said (meth) acrylate type polymer, and also about the acid value of the polymer which has the said hydroxyl group, it is preferable to exist in the preferable range mentioned above in the said (meth) acrylate type polymer. .

As the polymer having a hydroxyl group, for example, a base polymer obtained by polymerizing a monomer component including 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. ; The side chain double bond containing polymer obtained by making the base polymer react with the compound which has a functional group which can couple | bond with an acidic radical, and a polymerizable double bond is mentioned preferably. Especially, the latter side chain double bond containing polymer is preferable.

Thus, the form whose said (meth) acrylate type polymer and / or a hydroxyl group is a polymer which has a polymerizable double bond in a side chain is contained in the preferable aspect of this invention.

In the monomer component which forms the polymer which has the said hydroxyl group, the preferable form, specific example, etc. of the monomer which has a hydroxyl group and a polymerizable double bond, and the monomer which has an acidic radical and a polymerizable double bond are as having mentioned above, and each monomer Each can use 1 type (s) or 2 or more types.

It is preferable that the content rate of the monomer which has the said hydroxyl group and polymerizable double bond is 1 mass% or more with respect to 100 mass% of total amounts of the monomer component which forms the polymer which has the said hydroxyl group, for example. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more. Moreover, it is preferable that it is 90 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 25 mass% or less.

It is preferable to set the content rate of the monomer which has the said acidic radical and polymerizable double bond so that acid value may be in the preferable range mentioned above, for example, with respect to 100 mass% of the total amount of the monomer component which forms the polymer which has the said hydroxyl group. It is preferable that the content rate of the monomer which has an acidic radical and a polymerizable double bond is 5 mass% or more. More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. Moreover, it is preferable that it is 99 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 60 mass% or less, Especially preferably, it is 50 mass% or less.

The monomer component which forms the polymer which has the said hydroxyl group may also contain the other copolymerizable monomer other than the monomer mentioned above. As another monomer, For example, N substituted maleimide type monomers other than the above-mentioned monomer, a dialkyl-2,2'- (oxydimethylene) diacrylate type monomer, and alkyl- ((alpha)-allyloxymethyl ) 1 type, or 2 or more types, such as an acrylate monomer, a (meth) acrylic acid ester monomer, and an aromatic vinyl monomer, are used preferably. These preferable forms, specific examples, etc. are as above-mentioned.

Moreover, it is preferable to set it as 60 mass% or less in 100 mass% of total amounts of the monomer component which forms the polymer which has the said hydroxyl group, and, as for the content rate of another monomer, it is more preferable to set it as 50 mass% or less. In particular, in the case of containing an N-substituted maleimide monomer, the content thereof is preferably 2 to 60% by mass, more preferably 2 from the viewpoints of heat resistance, hardness, colorant dispersibility, development speed, transparency, and the like. It is-50 mass%, More preferably, it is 3-40 mass%.

The method of polymerizing the said monomer component and the method of making the base polymer obtained by superposing | polymerizing the said monomer component react with the compound which has a functional group which can couple | bond with an acidic radical, and a polymerizable double bond are as mentioned above.

In the said curable resin composition, what is necessary is just to set the content rate of the (meth) acrylate type polymer and the polymer which has a hydroxyl group suitably according to a use, the compounding of another component, etc. For example, those total solid content (the polymer which has a hydroxyl group is When it does not contain, it means solid content only of a (meth) acrylate type polymer) It is preferable that it is 5 mass% or more with respect to 100 mass% of solid content total amount of curable resin composition. Moreover, it is preferable that it is 80 mass% or less. By being in such a range, it becomes possible to show the effect of this invention more remarkably. More preferably, it is 7-70 mass%, More preferably, it is 10-60 mass%.

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

Here, when including both the said (meth) acrylate type polymer and the polymer which has a hydroxyl group, these compounding ratios generate | occur | produce by the thermal decomposition of the structural unit derived from a tertiary carbon containing (meth) acrylate type monomer (meth What is necessary is just to set a compounding ratio so that acrylic acid and the hydroxyl group in a system may crosslink easily, and it is not specifically limited. For example, it is preferable to set these mass ratio (polymer which has a (meth) acrylate type polymer / hydroxyl group) = 1-99 / 99-1. More preferably, it is 10-90 / 90-10.

<Polymerizable compound>

The curable resin composition also includes a polymerizable compound. A polymerizable compound is also called a polymerizable monomer and can superpose | polymerize by irradiation of active energy rays, such as a free radical, an electromagnetic wave (for example, infrared rays, an ultraviolet-ray, X-rays, etc.), an electron beam, etc. (polymerizable unsaturated Also referred to as a group). For example, the monofunctional compound which has one polymerizable unsaturated group in a molecule | numerator, and the polyfunctional compound which has two or more are mentioned.

As said monofunctional polymerizable monomer, For example, N substituted maleimide and (meth) acrylic acid ester in the compound illustrated as another monomer contained preferably in the monomer component of the said (meth) acrylate type polymer; (Meth) acrylamides; Unsaturated monocarboxylic acids; Unsaturated polyhydric carboxylic acids; Unsaturated monocarboxylic acids having a chain extending between the unsaturated group and the carboxyl group; Unsaturated acid anhydrides; Aromatic vinyls; Conjugated dienes; Vinyl esters; Vinyl ethers; N-vinyl compounds; Unsaturated isocyanates etc. are mentioned.

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

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di Bifunctional (meth) acrylate compounds, such as (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, and bisphenol F alkylene oxide di (meth) acrylate ;

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide addition trimethylolpropane tree (Meth) acrylate, ethylene oxide addition ditrimethylolpropane tetra (meth) acrylate, ethylene oxide addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipentaerythritol hexa (meth) acrylate, propylene oxide addition Trimethylolpropane tri (meth) acrylate, propylene oxide addition di Limethylolpropane tetra (meth) acrylate, propylene oxide addition pentaerythritol tetra (meth) acrylate, propylene oxide addition dipentaerythritol hexa (meth) acrylate, epsilon -caprolactone addition trimethylolpropane tree (meth) Acrylate, ε-caprolactone addition ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone addition pentaerythritol tetra (meth) acrylate, ε-caprolactone addition dipentaerythritol hexa (meth) acrylate, etc. Trifunctional or higher polyfunctional (meth) acrylate compounds;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkyl Len oxide divinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene Polyfunctional vinyl ethers such as oxide addition trimethylol propane trivinyl ether, ethylene oxide addition ditrimethylol propane tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, and ethylene oxide addition dipentaerythritol hexavinyl ether;

2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4- (meth) acrylic acid Vinyloxybutyl, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth Vinyl ether group-containing (meth) acrylic acid, such as p-vinyloxymethylphenylmethyl acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylic acid, and 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylic acid Esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkyl Len oxide diallyl ether, trimethylol propane triallyl ether, ditrimethylol propane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene Polyfunctional allyl ethers such as oxide addition trimethylolpropanetriallyl ether, ethylene oxide addition ditrimethylolpropane tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, and ethylene oxide addition dipentaerythritol hexaallyl ether;

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

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

Polyfunctional allyl group-containing isocyanurate, such as triallyl isocyanurate;

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

Polyfunctional aromatic vinyls such as divinylbenzene, and the like.

It is preferable to use a polyfunctional polymerizable compound from a viewpoint of improving curability of the curable resin composition of this invention among the said polymeric compounds further. When using a polyfunctional polymeric compound as a polymeric compound, Preferably it is three or more as the functional number, More preferably, it is four or more, More preferably, it is five or more. Moreover, from a viewpoint of suppressing hardening shrinkage more, 10 or less are preferable, and, as for a functional number, 8 or less are more preferable.

Moreover, although it does not specifically limit as molecular weight of the said polymeric compound, From a viewpoint of handling, 2000 or less is preferable, for example.

When using a polyfunctional polymeric compound as said polymeric compound, a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate from a viewpoint of reactivity, economy, availability, etc. also in the said polymeric compound. It is preferable to use the compound which has a (meth) acryloyl group, such as a compound and a (meth) acryloyl group containing isocyanurate compound. More preferably, it is a polyfunctional (meth) acrylate compound, and by this, curable resin composition becomes more excellent in photosensitivity and sclerosis | hardenability, and it becomes possible to obtain hardened | cured material with high hardness and high transparency. More preferably, trifunctional or more than trifunctional (meth) acrylate compound is used.

As content rate of the said polymeric compound, what is necessary is just to set suitably according to the objective and a use other than the kind of the polymeric compound to be used and the said (meth) acrylate type polymer, From a viewpoint which is more developable and plate-making property, it is curable It is preferable that it is 2 mass% or more with respect to 100 mass% of solid content total amount of a resin composition, and it is preferable that it is 80 mass% or less. As a lower limit, More preferably, it is 5 mass% or more, More preferably, it is 8 mass% or more, Especially preferably, it is 10 mass% or more, More preferably, as an upper limit, 70 mass% or less, More preferably, 50 mass% or less, Especially preferably, it is 30 mass% or less, Most preferably, it is 20 mass% or less.

<Photopolymerization initiator>

The curable resin composition further includes a photopolymerization initiator. As a photoinitiator, Preferably, it is a radically polymerizable photoinitiator. A radically polymerizable photoinitiator is what generate | occur | produces a polymerization start radical by irradiation of active energy rays, such as an electromagnetic wave and an electron beam, and can use normally 1 type (s) or 2 or more types. Moreover, you may use together 1 type, or 2 or more types of photosensitizer, radical photopolymerization promoter, etc. as needed. In addition to a photoinitiator, you may use the photosensitizer and / or radical photopolymerization promoter, and do not need to use it. Although the effect of this invention is fully exhibited even if it does not use together a photosensitizer and / or a radical photopolymerization promoter, when used together, a sensitivity and sclerosis | hardenability are improved more.

Specifically as said photoinitiator, the following compounds etc. are mentioned, for example.

2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -[4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy -2-methylpropionyl) benzyl] phenyl} -2-methylpropane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl Alkyl phenone compounds such as) phenyl] -1-butanone; Benzophenone compounds such as benzophenone, 4,4'-bis (dimethylamino) benzophenone and 2-carboxybenzophenone; Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Thioxanthones, such as thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2, 4- dimethyl thioxanthone, and 2, 4- diethyl thioxanthone Compound;

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

As a photosensitizer and optical radical polymerization promoter which may be used together with the said photoinitiator, For example, Pigment compounds, such as a xanthene dye, a coumarin dye, a 3-ketocoumarin type compound, and a pyrromethene dye; Dialkylaminobenzene-based compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoic acid; And mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoimidazole.

What is necessary is just to set content of the said photoinitiator suitably according to an objective, a use, etc., but it is not specifically limited, It is preferable that it is 0.1 mass part or more with respect to 100 mass parts of solid content total amounts of curable resin composition except a photoinitiator. Thereby, hardened | cured material excellent in adhesiveness can be obtained and peeling is suppressed more fully even after high temperature exposure. Moreover, it is preferable that it is 30 mass parts or less, considering the balance of the influence of the decomposition product of a photoinitiator, economical efficiency, etc .. As a lower limit, More preferably, it is 0.5 mass part or more, More preferably, it is 1 mass part or more, Especially preferably, it is 2 mass parts or more, As an upper limit, More preferably, it is 25 mass parts or less, More preferably, it is 20 mass parts or less. .

Although the said photosensitizer and the radical photopolymerization promoter do not need to be used as mentioned above, when it uses, it is based on 100 mass% of solid content total amount of curable resin composition from a viewpoint of the balance of hardenability, the decomposition products, and economical efficiency. It is preferable that it is 0.001-20 mass% with respect to. More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

<Other Ingredients>

-solvent-

It is preferable that the said curable resin composition contains a solvent further. The solvent is preferably used as a diluent or the like. Specifically, the viscosity is lowered and the handleability is improved; Forming a coating film by drying; It is used suitably for making it into the dispersion medium of a color material, and is a low viscosity organic solvent or water which can melt | dissolve or disperse each containing component in curable resin composition.

What is normally used can be used as said solvent, What is necessary is just to select suitably according to the objective and a use, Although it does not specifically limit, For example, the following compound etc. are mentioned. These may be used independently and may use 2 or more types together.

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

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

As the usage-amount of the said solvent, what is necessary is just to set suitably according to an objective and a use, Although it does not specifically limit, It is preferable to make it contain 10-90 mass% in 100 mass% of total amounts of curable resin composition of this invention. More preferably, it is 20-80 mass%.

The curable resin composition may further be, for example, a colorant (also referred to as a colorant) according to required properties of each application to which it is applied; Dispersant; Heat improver; Leveling agent; Developing aid; Inorganic fine particles such as silica fine particles; Coupling agents such as silane, aluminum and titanium; Thermosetting resins such as fillers, epoxy resins, phenol resins, and polyvinyl phenols; Curing aids such as polyfunctional thiol compounds; Plasticizers; Polymerization inhibitors; UV absorber; Antioxidants; Polish remover; Antifoaming agent; An antistatic agent; Slip agent; Surface modifier; Thixotropic agent; Thixotropic aid; Quinonediazide compounds; Polyhydric phenol compounds; Cationic polymerizable compounds; It may further contain 1 type (s) or 2 or more types, such as an acid generator. For example, when using the said curable resin composition for a color filter use, it is preferable to contain a coloring material. Thus, the form in which the said curable resin composition contains a coloring material further is also one of the preferable forms of this invention. Moreover, the form containing at least 1 sort (s) chosen from the group which consists of a coloring material, a dispersing agent, a heat resistance improving agent, a leveling agent, a coupling agent, and a development auxiliary agent is also preferable. Hereinafter, these containing components are demonstrated.

Color materials

As said color material, a pigment and dye are used preferably, for example. These may be used alone or in combination of two or more. Moreover, you may combine a pigment and dye. For example, when forming red, blue, and green pixels of a color filter, a method of exerting a desired color characteristic by combining color materials such as blue and purple, green and yellow is preferably used. In addition, when forming a black matrix, it can form using a black color material.

Among the pigments and dyes, for example, in terms of durability, a pigment (for example, an organic pigment or an inorganic pigment) is excellent, and, for example, a dye is excellent in terms of luminance improvement such as a panel. What is necessary is just to select or use these suitably according to a characteristic. Moreover, among pigments, More preferably, it is an organic pigment.

As said pigment, an azo pigment, a phthalocyanine pigment, a polycyclic pigment (for example, a quinacridone system, a perylene system, a perinone system, an isoindolinone system, an isoindolin system, a dioxazine system, a thioindigo system, , Anthraquinones, quinophthalones, metal complexes, diketopyrrolopyrroles and the like), and dye lake pigments; White and constitution pigments (e.g. titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), rapeseed pigments (e.g. sulfur, cadmium, chromium vermilion, nickel titanium, chromium titanium, yellow) Iron oxide, bengal, zinc chromate, podium, ultramarine, blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc., black pigments (e.g. carbon black, bone black, graphite, iron black, titanium Inorganic pigments, such as black), a light piercing pigment (for example, a pearl pigment, an aluminum pigment, a bronze pigment, etc.), and a fluorescent pigment (for example, zinc sulfide, strontium sulfide, strontium aluminate). Moreover, yellow, red, purple, blue, green, brown, black, white etc. are mentioned as a color of the pigment which can be used.

The pigment may further be subjected to surface treatments such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, and wax coating.

Although the specific example of the said pigment is shown by the color index (C.I .; The Society of Dyers and Colourists) number below for each color below, the coloring material of this invention is not limited to these. In addition, these may be used independently and may be used in combination of 2 or more type. The following "C.I." means a color index, and a number means a color index number.

As a yellow pigment, it is C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36 , 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 49, 53, 55, 60, 61, 61: 1, 62, 62: 1, 63, 65, 71, 73, 74 , 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119 , 120, 123, 124, 126, 127, 127: 1, 128, 129, 130, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156 , 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184 , 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 209, 209 : 1, 212, 213, 214, 215, 219 etc. are mentioned.

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

As the purple pigment, for example, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 13, 14, 15, 16, 17, 19, 23, 25, 27, 29 , 31, 32, 36, 37, 38, 39, 42, 44, 47, 49, 50 and the like.

As a red pigment, it is C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 37, 38 , 40, 41, 42, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 49: 1, 49: 2, 50: 1, 52, 52: 1 , 52: 2, 53, 53: 1, 53: 2, 53: 3, 54, 57, 57: 1, 57: 2, 58, 58: 2, 58: 4, 60, 60: 1, 63, 63 : 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 89, 90: 1, 95, 97, 101 , 101: 1, 102, 104, 105, 106, 108, 108: 1, 109, 112, 113, 114, 122, 123, 136, 144, 146, 147, 149, 150, 151, 164, 166, 168 , 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206 , 207, 208, 209, 210, 211, 213, 214, 215, 216, 220, 221, 224, 226, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245 , 247, 248, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273 , 274, 275, 276, 279 and the like.

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

As a green pigment, it is C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like.

As the brown pigment, for example, C.I. Pigment brown 5, 6, 23, 24, 25, 32, 41, 42 and the like.

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

As said dye, the organic dye described in Unexamined-Japanese-Patent No. 2010-9033, Unexamined-Japanese-Patent No. 2010-211198, Unexamined-Japanese-Patent No. 2009-51896, and Unexamined-Japanese-Patent No. 2008-50599, for example. Can be used. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.

Although the content rate (namely, the total ratio of a pigment and dye) of the said color material can be set suitably according to the objective and use, the preferable range of the content rate of the said color material is 3-70 mass with respect to 100 mass% of solid content total amount of curable resin composition. % to be. More preferably, it is 5-60 mass%, More preferably, it is 10-50 mass%.

- dispersant -

The dispersant has an interaction site with respect to the colorant and an interaction site with respect to the dispersion medium (for example, a solvent or binder resin), and has a function of stabilizing dispersion of the colorant with respect to the dispersion medium. (For example, a polymeric dispersant), surfactant (for example, a low molecular dispersant), and a pigment derivative. It is preferable that curable resin composition of this invention contains a dispersing agent with a coloring material. In addition, as a dispersing agent (ie, a resinous dispersing agent, surfactant, and / or a pigment derivative), the dispersing agent normally used can be used. In addition, 1 type may be used individually as a dispersing agent, and may be used in combination of 2 or more type.

As said resin type dispersing agent, For example, Polycarboxylic acid esters, such as a polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxyl Amides or salts thereof formed by the reaction of an acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, poly (lower alkyleneimine) and polyester having a free carboxyl group, (meth ) Acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester type, modified polyacrylate, ethylene oxide / poly And propylene oxide adducts.

Moreover, as a structure of the said resin type dispersing agent, a main chain is an anchor chain which has an interaction site with respect to a coloring material, and a graft structure resin or anchor chain whose graft chain is a compatible chain which has an interaction property with respect to a dispersion medium, Particularly preferred are resins in which a highly compatible chain has a block structure.

If the brand name of the said resin type dispersing agent is illustrated, the following are mentioned, for example. However, it is not limited to these.

EFKA-46, 47, 48, 745, 1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4540, 4550, 6750, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE131, 1525070, 5207 (above, manufactured by EFKA ADDITIVES); Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, 160, 161, 162, 163, 164, 166, 182, P-104, P-104S, P105, 220S, 203, 204, 205, 2000, 2001, 9075, 9076, 9077 ); SOLSPERSE3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 22000, 24000, 24000GR, 26000, 28000 (above, manufactured by Nihon Lubrizol); Disperlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 152MS (above, manufactured by Kusumoto Chemical Co., Ltd.); Azisper PB-711, 821, 822, 880, PN-411, PA-111 (above, Ajinomoto Fine Techno Co., Ltd. make); KP series (made by Shin-Etsu Chemical Co., Ltd.); Polyflow series (made by Kyoeisha Chemical Co., Ltd.); Megapak series (made by Daishi (DIC) company); Disperade series (manufactured by Sanofko Co., Ltd.) and the like.

As said surfactant, For example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalin sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, Anionic surfactants such as ammonium lauryl sulfate, sodium stearate and sodium lauryl sulfate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; Amphoteric surfactants, such as alkylbetaines, such as alkyldimethylamino acetate betaine, and alkyl imidazoline, etc. are mentioned.

The said pigment derivative is a compound of the structure which introduce | transduced a functional group into a pigment | dye, As a functional group, a sulfonic acid group, a sulfonamide group, its quaternary salt, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, a phthalimide And the like can be mentioned. As a structure of the pigment | dye used as a mother, For example, an azo system, an anthraquinone system, a quinophthalone system, a phthalocyanine system, a quinacridone system, a benzimidazolone system, an isoindolin system, a dioxazine system, an indanthrene system, Perylene system, diketopyrrolopyrrole system, etc. are mentioned.

What is necessary is just to set the content rate of the said dispersing agent (namely, resin type dispersing agent, surfactant, and / or pigment derivative) suitably according to a purpose or a use, and it is a viewpoint of the balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.), and transparency. For example, it is preferable that it is 0.01-60 mass% with respect to 100 mass% of solid content total amount of curable resin composition. More preferably, it is 0.1-50 mass%, More preferably, it is 0.3-40 mass%.

Heat improver

The heat improver is preferably used for improving heat resistance and strength. As a heat-resistant improving agent, the compound etc. which have an N- (alkoxymethyl) melamine compound, two or more epoxy groups, an oxetanyl group, etc. are preferable, for example. In particular, when the curable resin composition is used as a photospacer resist, a protective film for a protective film, or a resist for an interlayer insulating film, their use is preferable.

Leveling agent

The leveling agent is preferably used for improving the leveling property. As a leveling agent, surfactant of a fluorine type and a silicone type is preferable.

- Coupling agent -

The coupling agent is preferably used for improving the adhesion. As a coupling agent, a silane coupling agent is preferable, and an silane coupling agent of an epoxy type, methacryl type, and an amino type is mentioned, for example. Especially, an epoxy silane coupling agent is preferable.

Developmental Supplements

The development aid is preferably used for improving the developability. As a development aid, For example, Monocarboxylic acids, such as (meth) acrylic acid, acetic acid, a propionic acid; Polycarboxylic acids such as maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid and trimellitic acid; Carboxylic acid anhydrides, such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, etc. are preferable.

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

As the dispersing treatment step of the colorant, for example, first, a predetermined amount of each colorant (preferably an organic pigment), a dispersant and a solvent is weighed, and a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homo The disperser, such as a analyzer, a kneader, and a blender, disperse | distributes a coloring material microparticles | fine-particles, and the method of making a liquid coloring material dispersion liquid (also called a mill base) is mentioned. Preferably, after kneading and dispersing treatment with a roll mill, kneader, blender or the like, fine dispersing treatment is performed with a media mill such as a bead mill filled with beads of 0.01 to 1 mm. To the obtained mill base, a composition (preferably transparent liquid) containing a (meth) acrylate polymer, a polymerizable monomer, a photopolymerization initiator, and a solvent, a leveling agent, and the like, which are separately stirred and mixed, are added. And mixing and setting it as a uniform dispersion solution can obtain curable resin composition.

Moreover, it is preferable that the obtained curable resin composition carries out a filtration process with a filter etc., and removes fine dust.

[Cured goods]

As mentioned above, the curable resin composition of this invention is especially excellent in photosensitive property and sclerosis | hardenability, and provides the hardened | cured material which was excellent in basic performance, such as developability, solvent resistance, adhesiveness with a board | substrate (base material), heat resistance, and transparency. will be. Such hardened | cured material is also excellent in image formation property and surface smoothness, for example, there exists no residue of an unexposed part, soil contamination, etc. after image development. The hardened | cured material formed by hardening | curing such said curable resin composition is also one of this invention.

It is preferable that the film thickness (thickness) of the said hardened | cured material (cured film) is 0.1-20 micrometers. Thereby, it can fully respond to the low magnification request | requirements of the member etc. and display apparatus which used the said hardened | cured material. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

The cured product is preferably used for various optical members such as color filters, inks, printed boards, printed wiring boards, semiconductor devices, photoresists, photoresists, and the like used in liquid crystal displays and solid-state imaging devices. Used. Especially, it is preferable to use for a color filter. Thus, the color filter which uses the said curable resin composition, ie, the color filter which has the said hardened | cured material on a board | substrate specifically, is also one of this invention. Hereinafter, the color filter will be further described.

<Color filter>

The color filter of this invention consists of a form which has the said hardened | cured material on a board | substrate.

In the said color filter, the hardened | cured material formed with curable resin composition of this invention is especially preferable as a segment which requires coloring like each pixel, such as a black matrix and red, green, blue, yellow, for example, It is good also as a segment which does not necessarily require coloring, such as a photo spacer, a protective layer, and an orientation control rib.

As a board | substrate used for the said color filter, For example, Glass substrates, such as a white plate glass, a blue plate glass, an alkali strengthened glass, a silica coat blue plate glass; Sheets, films or substrates made of thermoplastic resins such as ring-opening polymers of polyesters, polycarbonates, polyolefins, polysulfones and cyclic olefins and hydrogenated substances thereof; Sheets, films or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates such as aluminum plates, copper plates, nickel plates and stainless steel plates; Ceramic substrate; A semiconductor substrate having a photoelectric conversion element; The member etc. which consist of various materials, such as a glass substrate (for example, color filter for LCD) provided with a color material layer on the surface, are mentioned. Especially, from a heat resistant point, a glass substrate and the sheet | seat, film, or board | substrate which consist of heat resistant resin are preferable. In addition, the substrate is preferably a transparent substrate.

In addition, you may perform chemical processing by a corona discharge treatment, an ozone treatment, a silane coupling agent, etc. to the said base material as needed.

<Manufacturing Method of Color Filter>

In obtaining the said color filter, the process (it is also called a batch process) which arrange | positions the said curable resin composition on a board | substrate with respect to one pixel of a color, for example, and the curable resin composition arrange | positioned on the board | substrate It employs a method including a step (also called a light irradiation step) of irradiating light, a step (also called a developing step) of developing with a developer, and a step of heating (also called a heating step). It is preferable to employ | adopt the manufacturing method which repeats to each color. In addition, the formation order of the pixel of each color is not specifically limited.

Batch process (preferably an application process)

It is preferable to perform the said batch process by application | coating. As a method of apply | coating the said curable resin composition on a board | substrate, spin coating, slit coating, roll coating, casting | flow_spread coating, etc. are mentioned, for example, Any method can be used preferably.

In the said arrangement process, after apply | coating the said curable resin composition on a board | substrate, it is preferable to dry a coating film further. Drying of a coating film can be performed using a hotplate, an IR oven, a convection oven, etc., for example. Although dry conditions are suitably selected according to the boiling point of the solvent component contained, the kind of hardening component, the film thickness, the performance of a dryer, etc., it is preferable to carry out normally for 10 second-300 second at the temperature of 50-160 degreeC.

Light irradiation process

As the light source of the active light beam used in the light irradiation step, for example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp Laser light sources such as lamp light sources such as lamps, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. Moreover, although a proximity system, a mirror projection system, and a stepper system are mentioned as a system of an exposure machine, a proximity system is used preferably.

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

Development Process

The said developing process is a process of image-processing with a developing solution after the above-mentioned light irradiation process, and removing an unexposed part and forming a pattern. Thereby, a patterned cured film can be obtained. Developing process can be normally performed by the methods of immersion development, spray image development, brush image development, ultrasonic image development, etc. at the development temperature of 10-50 degreeC.

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

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

In addition to an alkali chemicals, the said alkaline aqueous solution can contain surfactant, an organic solvent, a buffer, a dye, a pigment, etc. as needed. As an organic solvent in this case, the organic solvent etc. which are preferable as a developing solution mentioned above are mentioned.

Examples of the alkali agent include inorganic alkali agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tertiary sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate and sodium hydrogen carbonate; Amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. It may be sufficient or it may combine 2 or more types.

As said surfactant, For example, Nonionic surfactant, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, sorbitanic acid alkyl ester, monoglyceride alkyl ester; Anionic surfactant, such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl sulfonate, and sulfosuccinic acid ester salt; Amphoteric surfactants, such as alkylbetaines and amino acids, etc. are mentioned, These may be individual or it may combine 2 or more types.

Heating process

The said heating process is a process (it is also called a post hardening process) which further hardens an exposure part (hardening part) by baking after the image development process mentioned above. For example, using a light source such as a high-pressure mercury lamp, the post-exposure at a light amount of 0.5 to 5 J / cm 2, for example, or post-heating for 10 seconds to 120 minutes at a temperature of 60 to 260 ° C., for example. The process etc. which are made are mentioned. By carrying out such a post-curing process, it becomes possible to make hardness and adhesiveness of a patterned cured film more firm. In addition, by this heating step, part of the structural unit of the (meth) acrylate polymer contained in the curable resin composition (that is, part derived from a part of the tertiary carbon-containing (meth) acrylate monomer) is decomposed. Therefore, hardenability and solvent resistance can be improved.

It is preferable that the film thickness of the cured film obtained by the said heating process (namely, the cured film obtained by thermosetting the said curable resin composition) is 0.1-20 micrometers. By using curable resin composition of this invention, the cured film by which the film thickness was fully reduced can be provided. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

Moreover, when the film thickness of the coating film (namely cured film) obtained by the said heating process makes the film thickness of the coating film before heating 100%, it is preferable that it is 90% or less. More preferably, it is 80% or less, More preferably, it is 70% or less.

In the said heating process, it is preferable that heating temperature is 150 degreeC or more. Thereby, since the part derived from a part of the said tertiary carbon containing (meth) acrylate type monomer decomposes more effectively, it becomes possible to implement | achieve the improvement of curability and solvent resistance more. More preferably, it is 160 degreeC or more, More preferably, it is 170 degreeC or more, Especially preferably, it is 180 degreeC or more. Moreover, it is preferable to set it as 260 degrees C or less, More preferably, it is 250 degrees C or less.

Although the heating time in the said heating process is not specifically limited, For example, it is preferable to set it as 5 to 60 minutes. Moreover, a heating method is not specifically limited, either, For example, it can carry out using heating apparatuses, such as a hotplate, a convection oven, and a high frequency heater.

[Display device]

The present invention is also a display device constituted by using the color filter.

Moreover, the member for display apparatuses and display apparatus which have hardened | cured material formed with the said curable resin composition are also contained in preferable embodiment of this invention. Since the hardened | cured material (cured film) formed with the said curable resin composition is stable, is excellent in adhesiveness with respect to a base material, etc., and also shows high smoothness and high smoothness and has high transmittance | permeability, it is especially preferable as a transparent member. It is also useful as a protective film or an insulating film in various display devices.

As said display apparatus, a liquid crystal display device, a solid-state image sensor, a touch panel display device, etc. are preferable, for example.

In addition, when using the said hardened | cured material (cured film) as a member for display apparatuses, the said member may be a film-form single layer or a multilayer member comprised by the said cured film, and a layer different from the single layer or multilayer member further The combined member may be sufficient, and the member which contains the said cured film in a structure may be sufficient.

Since the curable resin composition of this invention is a structure as mentioned above, it can exhibit various physical properties, such as sclerosis | hardenability, solvent resistance after hardening, adhesiveness with a board | substrate (base material), heat resistance, and transparency, and is excellent in storage stability, It is useful for various uses, such as a color filter. Therefore, the color filter and display apparatus which have hardened | cured material (cured film) formed by such a curable resin composition are very useful in an optical field or an electric / electronic field.

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

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

<Weight average molecular weight>

Using polystyrene as the standard material and tetrahydrofuran as the eluent, HLC-8220GPC (manufactured by Tosoh Corporation) and column: GPC (gel permeation chromatography) method using TSKgel SuperHZM-M (manufactured by Tosoh Corporation) Measured.

<Solid content>

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

<Acid value>

3 g of a resin solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and automatically titrated using a 0.1 N aqueous KOH solution as a titration solution (manufactured by Hiranuma Industries, trade name: COM-555). By this, the acid value of the polymer solution was measured, and the acid value (AV) per solid content of 1 g was determined from the acid value of the solution and the solid content of the solution.

<Absorbance of the curable resin composition>

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

Synthesis Example 1

Synthesis of Resin Solution 1 (BzMI-CHMA-t-BMA-MAA Copolymer Solution)

844.57 g of propylene glycol monomethyl ether acetate was injected | thrown-in to the reaction tank provided with the thermometer, the stirrer, the gas introduction tube, the cooling tube, and the dropping tank inlet, and it heated, and heated up to 90 degreeC. On the other hand, as the dripping tank (A), 50 g of N-benzyl maleimide, 125 g of cyclohexyl methacrylates, 225 g of t-butyl methacrylates, 100 g of methacrylic acid, and t-butylperoxy-2 to a beaker It prepared by stirring and mixing 10 g of ethyl hexanoate ("perbutyl O" by Nippon Oil Holding Co., Ltd.), 21 g of n-dodecyl mercaptans and 84 g of propylene glycol monomethyl ether acetates to a dropping tank (B). It was prepared by stirring and mixing. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

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

Synthesis Example 2

Synthesis of Resin Solution 2 (BzMI-CHMA-HEMA-MAA Copolymer Solution)

844.57 g of propylene glycol monomethyl ether acetate was injected | thrown-in to the reaction tank provided with the thermometer, the stirrer, the gas introduction tube, the cooling tube, and the dropping tank inlet, and it heated, and heated up to 90 degreeC. On the other hand, as the dripping tank (A), 50 g of N-benzyl maleimide, 250 g of cyclohexyl methacrylates, 100 g of methacrylic acid 2-hydroxyethyl, 100 g of methacrylic acid, and t-butylperoxy in a beaker A mixture of 10 g of 2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil Industries Co., Ltd.) was prepared, and 21 g of n-dodecyl mercaptan and propylene glycol monomethyl ether acetate were added to the dropping tank (B). 84 g was prepared by stirring and mixing. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

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

Synthesis Example 3

Synthesis of Resin Solution 3 (Side Chain Double Bond Containing Copolymer; BzMI-t-BA-AA // GMA Copolymer Solution)

1006.67 g of propylene glycol monomethyl ether was injected into the reaction tank provided with the thermometer, the stirrer, the gas introduction pipe, the cooling pipe, and the dropping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as a dripping tank (A), 20 g of N-benzyl maleimide, 250 g of t-butyl acrylates, 230 g of acrylic acid, and t-butyl peroxy-2-ethylhexanoate (the "furnace made by Nippon Oil Industries, Ltd." The thing which stirred and mixed 10 g of butyl O ') was prepared, The thing which mixed 40 g of n-dodecyl mercaptan and 160 g of propylene glycol monomethyl ethers was prepared in the dripping tank (B). After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

Thereafter, the nitrogen of the gas inlet tube was changed to an oxygen / nitrogen mixed gas (oxygen / nitrogen = 5/95 vol%), and 2,2'-methylenebis (4-methyl-6-t-butylphenol) was used as an inhibitor. (Kawaguchi Chemical Co., Ltd., "Anti w-400") 1.34 g and 2.68 g of triethylamine as a catalyst are added, after stirring and mixing, 393.74 g of glycidyl methacrylate is added as an addition compound, 115 The reaction was terminated when the temperature was raised to ° C, and the addition reaction was carried out, and after 8 hours, the amount of remaining GMA by GC (gas chromatography) analysis reached 0.5 mass% or less, and an acid group having a radically polymerizable double bond in the side chain. The polymer solution of the containing copolymer was obtained.

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

Synthesis Example 4

Synthesis of Resin Solution 4 (Side Chain Double Bond-Containing Copolymer; BzMI-CHA-HEA-AA // GMA Copolymer Solution)

1006.67 g of propylene glycol monomethyl ether was injected into the reaction tank provided with the thermometer, the stirrer, the gas introduction pipe, the cooling pipe, and the dropping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dripping tank (A), 20 g of N-benzyl maleimide, 150 g of cyclohexyl acrylate, 100 g of 2-hydroxyethyl acrylate, 230 g of acrylic acid, and t-butylperoxy-2-ethylhexano in a beaker What prepared by stirring and mixing 10 g of eight ("perbutyl O" by Nippon Oil Industries, Ltd.), and stirring-mixing 40 g of n-dodecyl mercaptans and 160 g of propylene glycol monomethyl ethers to the dripping tank (B) Ready. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

Thereafter, the nitrogen of the gas inlet tube was changed to an oxygen / nitrogen mixed gas (oxygen / nitrogen = 5/95 vol%), and 2,2'-methylenebis (4-methyl-6-t-butylphenol) was used as an inhibitor. (Kawaguchi Chemical Co., Ltd., "Anti w-400") 1.34 g and 2.68 g of triethylamine as a catalyst are added, after stirring and mixing, 393.74 g of glycidyl methacrylate is added as an addition compound, 115 The reaction was terminated when the temperature was raised to ° C, and the addition reaction was carried out, and after 8 hours, the amount of remaining GMA by GC (gas chromatography) analysis reached 0.5 mass% or less, and an acid group having a radically polymerizable double bond in the side chain. The polymer solution of the containing copolymer was obtained.

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

Synthesis Example 5

Synthesis of Resin Solution 5 (BzMI-CHMA-t-BMA-HEMA-MAA Copolymer Solution)

844.57 g of propylene glycol monomethyl ether acetate was injected | thrown-in to the reaction tank provided with the thermometer, the stirrer, the gas introduction tube, the cooling tube, and the dropping tank inlet, and it heated, and heated up to 90 degreeC. On the other hand, as a dripping tank (A), 50 g of N-benzyl maleimide, 125 g of cyclohexyl methacrylates, 125 g of t-butyl methacrylates, 100 g of methacrylic acid 2-hydroxyethyl, metalllic acid in a beaker 100 g and 10 g of t-butylperoxy-2-ethylhexanoate ("perbutyl O" by Nippon Oil Industries, Ltd.) were prepared by stirring, and n-dodecyl mercaptan 21 was added to the dripping tank (B). The thing which stirred and mixed g and propylene glycol monomethyl ether acetate 84g was prepared. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 7700, the acid value was 133 mgKOH / g, and resin solid content was 35.0 mass%.

Synthesis Example 6

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

1006.67 g of propylene glycol monomethyl ether was injected into the reaction tank provided with the thermometer, the stirrer, the gas introduction pipe, the cooling pipe, and the dropping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dripping tank (A), 20 g of N-benzyl maleimide, 150 g of t-butyl acrylates, 100 g of 2-hydroxyethyl acrylates, 230 g of acrylic acids, and t-butylperoxy-2-ethyl hexa were added to a beaker. The thing which mixed 10 g of noates ("perbutyl O" by Nippon Oil Holdings) was prepared, and 40 g of n-dodecyl mercaptans and 160 g of propylene glycol monomethyl ether were stirred and mixed with the dripping tank (B). To prepare. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

Thereafter, the nitrogen of the gas inlet tube was changed to an oxygen / nitrogen mixed gas (oxygen / nitrogen = 5/95 vol%), and 2,2'-methylenebis (4-methyl-6-t-butylphenol) was used as an inhibitor. (Kawaguchi Chemical Co., Ltd., "Anti w-400") 1.34 g and 2.68 g of triethylamine as a catalyst are added, after stirring and mixing, 393.74 g of glycidyl methacrylate is added as an addition compound, 115 The reaction was terminated when the temperature was raised to ° C, and the addition reaction was carried out, and after 8 hours, the amount of remaining GMA by GC (gas chromatography) analysis reached 0.5 mass% or less, and an acid group having a radically polymerizable double bond in the side chain. The polymer solution of the containing copolymer was obtained.

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

Synthesis Example 7

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

844.57 g of propylene glycol monomethyl ether acetate was injected | thrown-in to the reaction tank provided with the thermometer, the stirrer, the gas introduction tube, the cooling tube, and the dropping tank inlet, and it heated, and heated up to 90 degreeC. On the other hand, as a dripping tank (A), 400 g of methyl methacrylate, 100 g of metalllic acid, and 10 g of t-butylperoxy-2-ethylhexanoate ("perbutyl O" by Nippon Oil Holdings) were put into a beaker. The thing which stirred and mixed was prepared, The thing which stirred-mixed 21 g of n-dodecyl mercaptans and 84 g of propylene glycol monomethyl ether acetates to the dripping tank (B) was prepared. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 7700, the acid value was 133 mgKOH / g, and resin solid content was 35.0 mass%.

Synthesis Example 8

Synthesis of Resin Solution 8 (BzMI-t-BMA-HEMA-MAA Copolymer Solution)

874.57 g of propylene glycol monomethyl ether acetate was injected | thrown-in to the reaction tank provided with the thermometer, the stirrer, the gas introduction pipe, the cooling pipe, and the dropping tank inlet, and it heated, and heated up to 90 degreeC. On the other hand, as the dripping tank (A), 50 g of N-benzyl maleimide, 235 g of t-butyl methacrylic acid, 100 g of 2-hydroxyethyl methacrylic acid, 115 g of metalllic acid, and t-butylperoxy in a beaker 10 g of 2-ethylhexanoate ("perbutyl O" manufactured by Nippon Oil Industries, Ltd.) was prepared by stirring, and 6 g of n-dodecyl mercaptan and propylene glycol monomethyl ether acetate were added to the dropping tank (B). 54 g was prepared by stirring and mixing. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

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

Synthesis Example 9

Synthesis of Resin Solution 9 (MD-t-BMA-HEMA-MAA Copolymer Solution)

844.57 g of propylene glycol monomethyl ether acetate was injected | thrown-in to the reaction tank provided with the thermometer, the stirrer, the gas introduction tube, the cooling tube, and the dropping tank inlet, and it heated, and heated up to 90 degreeC. On the other hand, as a dripping tank (A), 50 g of dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate (MD) in a beaker, 250 g of t-butyl methacrylates, methacryl A mixture of 100 g of acid 2-hydroxyethyl, 100 g of metalllic acid, and 10 g of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil Industries, Ltd.) was prepared by stirring, and a dropping tank ( 15 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetates were stirred and mixed in B). After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

As a result of analyzing the obtained polymer solution, the weight average molecular weight was 12000, the acid value was 133 mgKOH / g, and resin solid content was 35.0 mass%.

Synthesis Example 10

Synthesis of Resin Solution 10 (AMA-t-BMA-HEMA-MAA Copolymer Solution)

844.57 g of propylene glycol monomethyl ether acetate was injected | thrown-in to the reaction tank provided with the thermometer, the stirrer, the gas introduction tube, the cooling tube, and the dropping tank inlet, and it heated, and heated up to 90 degreeC. On the other hand, as a dripping tank (A), 50 g of methyl-((alpha) -allyloxymethyl) acrylates (AMA), 250 g of t-butyl methacrylates, 100 g of 2-hydroxyethyl methacrylates, a metal in a beaker A mixture of 100 g of lrylic acid and 10 g of t-butylperoxy-2-ethylhexanoate ("perbutyl O" manufactured by Nippon Oil Industries, Ltd.) was prepared, and n-dodecyl mercaptan was added to the dropping tank (B). 15 g and propylene glycol monomethyl ether acetate (84 g) were prepared by stirring and mixing. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition | polymerization was performed. After holding dripping at 90 degreeC for 30 minutes after completion | finish of dripping, it heated up to 115 degreeC and aged for 90 minutes.

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

In Table 1, the detail of resin solution 1-10 is shown.

In addition, with respect to the compounding quantity of the monomer which comprises resin of Table 1, the numerical value of each monomer which comprises a base polymer described each compounding ratio (mass%) when these total amounts were 100 mass%. In addition, in the synthesis examples 4 and 6, the numerical value of GMA (a compound which has a functional group which can couple | bond with an acidic group, and a polymerizable double bond) added to the said base polymer is a monomer which has an acidic radical and a polymerizable double bond (in this case, It is described as GMA ratio added to the carboxylic acid content of AA), and "GMA compounding ratio (AA compounding ratio (mass%) which added GMA) = (molar amount (mol) of GMA / mol amount of AA (mol) )} × AA compounding ratio (mass%) ”. For example, in the synthesis example 4, AA in a base polymer (100 mass%) is comprised by 46 mass%, and 2769 mmol GMA was added to this 46 mass% (3191 mmol) AA, The compounding ratio (mass%) of the said GMA was prescribed | regulated as "40."

Symbols in Table 1 are as follows.

BzMI: N-benzylmaleimide

MD: dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate

AMA: Methyl- (α-allyloxymethyl) acrylate

MMA: Methyl methacrylate

CHMA: cyclohexyl methacrylate

CHA: Cyclohexyl acrylate

t-BMA: t-butyl methacrylate

t-BA: t-butyl acrylate

HEMA: 2-hydroxyethyl methacrylate

HEA: 2-hydroxyethyl acrylate

MAA: methacrylic acid

AA: Acrylic acid

GMA: glycidyl methacrylate

Production Example 1

Preparation of Pigment Dispersion 1

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

Example 1

1.0 part of resin solution 1, 1.0 part of resin solution 2, 0.70 part of dipentaerythritol hexaacrylate as a radically polymerizable compound, Irgacure 369 (made by Chiba Specialty Chemicals) as a radically polymerizable photoinitiator 0.35 part, 7.88 parts of pigment dispersion 1 and 6.57 parts of propylene glycol monomethyl ether acetate were mixed as a solvent, and the curable resin composition 1 was obtained. When measuring the absorbance with respect to the curable resin composition 1, 1.6 × 10 ^{- 2} it was.

Examples 2-8, Comparative Examples 1-7

Except having set it as the mixture shown in Table 2 and 3, it carried out similarly to Example 1, and obtained curable resin compositions 2-15, respectively, and measured absorbance, respectively. The results are shown in Tables 2 and 3.

From the results of Tables 2 and 3, the followings were confirmed.

Example 1 and Comparative Examples 1, 2, 5 and 6; Example 2 and Comparative Examples 3 and 4; Examples 3, 6, 7, and 8 and Comparative Example 7; Example 4 and Comparative Examples 3 and 4 are examples in which the cured products were obtained under the same conditions and the absorbances were measured. You can see that it is inferior. Here, when the curability and solvent resistance of curable resin composition are inadequate, since the absorbance of hardened | cured material becomes large because a color material elutes, from the result of Table 2 and 3, the curable resin composition of a comparative example compared with an Example has curability and content. It can be seen that the castle was inadequate. In addition, although not shown in the table, all the hardened | cured material obtained by the Example was excellent also in various physical properties, such as developability, adhesiveness with a board | substrate, and heat resistance.

Claims (6)

As curable resin composition containing a (meth) acrylate type polymer, a polymeric compound, and a photoinitiator,
The (meth) acrylate polymer is a polymer having a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer,
The curable resin composition is a form containing a polymer which further has a hydroxyl group, and the (meth) acrylate type polymer is at least 1 type chosen from the group which consists of a form which has a hydroxyl group further, Curable characterized by the above-mentioned. Resin composition. The method of claim 1,
The said tertiary carbon containing (meth) acrylate type monomer has the structure which the oxygen atom adjacent to the (meth) acryloyl group couple | bonded with the tertiary carbon atom, The curable resin composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The said (meth) acrylate type polymer and / or the polymer which has a hydroxyl group are curable resin compositions characterized by the polymer which has a polymerizable double bond in a side chain. Hardened | cured material formed by hardening | curing curable resin composition of any one of Claims 1-3. It has the hardened | cured material of Claim 4 on a board | substrate, The color filter characterized by the above-mentioned. It is comprised using the color filter of Claim 5, The display apparatus characterized by the above-mentioned.