JP6495769B2 - Curable resin composition and use thereof - Google Patents

Description

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

Curable resin compositions that can be cured by heat or active energy rays are variously studied for various applications such as optical members, electrical machinery and electronic equipment, and are excellent in characteristics required for each application. Compositions are being developed. A color filter is an example of a specific application. The color filter is a main member that constitutes a liquid crystal display device, a solid-state imaging device, and the like. G) and blue (B)) pixels, and a protective film provided to cover and protect the pixels and the resin black matrix in addition to the resin black matrix (BM) separating them and to flatten the irregularities thereof And the like.

In general, when forming a pixel of a color filter using a curable resin composition, (1) an application process for applying the curable resin composition to the entire surface of the substrate and (2) an application process for each pixel color. The resist film is subjected to pattern exposure through a photomask and the exposed portion is cured, and then the exposed portion is insolubilized, and (3) the unexposed portion is removed with a developer and then baked (baked). A developing and baking (baking) treatment process for further curing the exposed portion is performed, and the same process is repeated for each color. Considering application to such color filter applications, the curable resin composition has various physical properties such as curability, solvent resistance after curing, adhesion to the substrate, heat resistance and transparency. Is required. Therefore, for example, methods described in Patent Documents 1 to 3 have been proposed.

JP 2007-333847 A JP 2012-022048 A JP 2007-034134 A

As described above, the curable resin composition is required to have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (also referred to as a base material), heat resistance, and transparency. Yes. In recent years, optical members, electrical equipment, electronic devices, etc. are becoming smaller, thinner, and energy-saving, and along with this, members such as color filters used are required to have high-grade performance. As a result, new challenges arise. For example, in a color filter application, there is a problem that the coloring material is eluted in the cleaning solvent in the manufacturing process as the concentration of the coloring material such as pigment or dye increases. Therefore, it is required to exhibit a very high solvent resistance after curing. However, in the current situation, conventional resin compositions cannot sufficiently meet these demands. For example, in the resin compositions described in Patent Documents 1 and 2, since the solvent resistance is not sufficient, the coloring material may start to dissolve in the cleaning solvent in the manufacturing process, and the color characteristics may deteriorate. There was room for improvement. Moreover, in the resin composition of patent document 3, although solvent resistance was improved, there existed room for improving comprehensive characteristics, such as adhesiveness and developability, by making further improvement.

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

The present inventor has made various studies on curable resin compositions useful for various uses such as color filters. When the resin composition includes a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, the composition is cured. We paid attention to the fact that it would have sex. The (meth) acrylate polymer has a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer (also referred to as a tertiary carbon-containing (meth) acrylate monomer unit) and a hydroxyl group. A structural unit derived from a monomer (also referred to as a monomer unit having a hydroxyl group) and a structural unit derived from a monomer having an active methylene group (also referred to as a monomer unit having an active methylene group) Assuming that, the resin composition has drastically improved solvent resistance after curing, curing that can stably express various physical properties such as high transparency, adhesion to the substrate, heat resistance and high hardness I found out that it gives things. Further, it has been found that the use of the resin composition can shorten the development time at the time of alkali development, further improve the productivity, and reduce the production cost. Such a curable resin composition is particularly useful for color filter applications, and is particularly suitable as a resin composition for forming pixels for color filters. Therefore, a cured product, a color filter and a display device formed from such a curable resin composition are extremely useful in the optical field, electrical machinery and electronic field, and can sufficiently meet the recent demand for higher performance. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

Here, the (meth) acrylate polymer contained in the curable resin composition of the present invention has a tertiary carbon-containing (meth) acrylate monomer unit, which is easily decomposed by heat. For example, as will be described later, a tertiary carbon-containing (meth) acrylate monomer that provides the monomer unit has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. In this case, the O—C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent to the (meth) acryloyl group is easily cleaved, whereby (meth) acrylic acid and tertiary carbon It is decomposed into a stable compound generated on the atomic side. Therefore, for example, when the curable resin composition of the present invention is used for forming a pixel of a color filter, a tertiary carbon-containing (meth) acrylate is produced by a heating process after development (also referred to as a baking process or a post-baking process). The monomer units are decomposed to produce (meth) acrylic acid and a stable compound generated on the tertiary carbon atom side. And after the curability and curing of the resin composition due to the formation of an ester cross-linking structure between the hydroxyl group in the polymer and the ester group that can be included as necessary, and the (meth) acrylic acid produced It is considered that the solvent resistance of the resin is drastically improved.

That is, the present invention is a curable resin composition comprising a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, wherein the (meth) acrylate polymer is a tertiary carbon-containing (meth) acrylate. A curable resin composition having a monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group.
The present invention is also a cured product obtained by curing the curable resin composition.
The present invention is also a color filter having the above cured product on a substrate.
The present invention is also a display device configured using the color filter.

The curable resin composition of the present invention has extremely good developability and can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to a substrate, heat resistance and transparency. It is also excellent in storage stability and useful for various applications such as color filters. Therefore, a color filter and a display device having a cured product (cured film) formed from such a curable resin composition are very useful in the optical field, the electric machine / electronic field, and the like.

The present invention is described in detail below. A form in which two or three or more preferred forms of the present invention described below are combined is also a preferred form of the present invention.
In addition, “A to B” representing a range means “A or more and B or less”.

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

<(Meth) acrylate polymer>
The (meth) acrylate polymer has a tertiary carbon-containing (meth) acrylate monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group. Each structural unit may be one kind or two or more kinds. Further, if necessary, it may further contain one or more structural units derived from other monomers (also referred to as other monomer units).
Hereinafter, the structure of the (meth) acrylate polymer will be further described.

(I) Tertiary carbon-containing (meth) acrylate monomer unit The tertiary carbon-containing (meth) acrylate monomer unit is a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer. Yes, it means a structural unit in which the polymerizable carbon-carbon double bond (C═C) of the monomer is a single bond (C—C). Here, the tertiary carbon-containing (meth) acrylate monomer is a compound having one or more (meth) acryloyl groups and tertiary carbon atoms in the molecule. The tertiary carbon atom means a carbon atom having three other carbon atoms bonded to the carbon atom.

The tertiary carbon-containing (meth) acrylate monomer preferably has a structure in which an oxygen atom adjacent to the (meth) acryloyl group is bonded to a tertiary carbon atom. Thereby, since the tertiary carbon-containing (meth) acrylate monomer unit is more easily decomposed by the heating step after development, the curability of the resin composition and the solvent resistance after curing are dramatically improved as described above. To be improved.

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

In the general formula (1), the organic group represented by A can be represented by, for example, —C (R ¹ ) (R ² ) (R ³ ). In this case, R ¹ , R ² and R ³ are the same or different and are preferably a hydrocarbon group having 1 to 30 carbon atoms. This hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Moreover, it may have a cyclic structure and may further have a substituent. R ¹ , R ^2, and R ³ may be linked to each other at a terminal site to form a cyclic structure. However, from the viewpoint of sufficiently exerting the effect derived from the tertiary carbon-containing (meth) acrylate monomer unit, R ¹ , R ² and R ³ preferably have no cyclic structure, It is preferable that they are not linked to each other at the terminal sites to form a cyclic structure.

Further, in the present invention, as will be described later, a new compound produced by breaking the O—C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom in A adjacent thereto. It is preferable that carbon number of the organic group represented by A is 12 or less in that it is easy to volatilize. Among these, the organic group represented by A is preferably a group derived from t-butyl (meth) acrylate and / or a group derived from t-amyl (meth) acrylate. The organic group represented by A may have a branched structure.

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

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

In the (meth) acrylate polymer, the content ratio of the tertiary carbon-containing (meth) acrylate monomer unit is 100% by mass of all monomer units (that is, “(meth) acrylate polymer It corresponds to “mass 100 mass%”), and is preferably 5 mass% or more. Thereby, the effect of this invention resulting from a tertiary carbon containing (meth) acrylate type monomer unit will be expressed further. More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more. Further, the upper limit of the content ratio may be appropriately set in consideration of the content ratio of other monomer units, for example, from the viewpoint of further improving the pattern characteristics and developability when used for color filter applications. 90% by mass or less is preferable. More preferably, it is 75 mass% or less, More preferably, it is 60 mass% or less.

(Ii) Monomer unit having a hydroxyl group A monomer unit having a hydroxyl group is a structural unit derived from a monomer having a hydroxyl group (hydroxyl group). This means a structural unit in which a double bond (C═C) is a single bond (C—C). By including such a monomer unit, the curability of the curable resin composition is improved, and a cured product having excellent solvent resistance and transparency can be provided.

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

Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. Examples include 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, and the like.

In the (meth) acrylate polymer, the content ratio of the monomer unit having a hydroxyl group is preferably 5 to 50% by mass with respect to 100% by mass of the total amount of all monomer units, for example. When it exists in this range, sclerosis | hardenability will become more sufficient and solvent resistance will improve. In addition, since the hydrophilicity is appropriate, it is possible to more sufficiently reduce the occurrence of defects during development (for example, peeling during development or roughening and whitening of the surface). More preferably, it is 10-40 mass%, More preferably, it is 15-35 mass%.

(Iii) Monomer unit having an active methylene group The monomer unit having an active methylene group is a structural unit derived from a monomer having an active methylene group, and the polymerizable carbon- This means a structural unit in which a carbon double bond (C═C) is a single bond (C—C). By including such a monomer unit, the solvent resistance and developability of the curable resin composition are improved.

The monomer having an active methylene group is a monomer having one or more active methylene groups in one molecule. For example, a compound represented by the following formula (2) is suitable. Thereby, it becomes possible to further improve the sensitivity of the curable resin composition. The form in which the monomer having an active methylene group is represented by the following formula (2) is one of the preferred forms of the present invention.

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

In the above formula, R ¹ and R ⁵ are the same or different and each represents a hydrogen atom, or represents a hydrocarbon group which may 1 to 24 carbon atoms which may contain heteroatoms. Among these, a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group, propoxy group, hexoxy group, cyclohexoxy group, or the following formula (2-9) To (2-11), more preferably a hydrogen atom or a methyl group.

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

Specifically, as the compound represented by the above formula (2), for example, compounds represented by the following formulas (3-1) to (3-16) are preferable.

In the above formulas (3-1) to (3-7) and (3-16), R ⁶ is the same or different and represents a hydrogen atom or a methyl group. That is, a compound that derives a structural unit composed of a methacryl group or a compound that derives a structural unit composed of an acryl group may be used. Among these compounds represented by the formulas (3-1) to (3-16), 2- (methacryloyloxy) ethyl acetoacetate (that is, a compound represented by the above formula (3-1), A compound in which ⁶ represents a methyl group is particularly preferred.
Moreover, you may use together the unsaturated compound which has an active methine group illustrated by Unexamined-Japanese-Patent No. 2007-34134.

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

(Iv) Monomer unit having an acid group The (meth) acrylate polymer preferably further has a monomer unit having an acid group. The monomer unit having an acid group is a structural unit derived from a monomer having an acid group, and a polymerizable carbon-carbon double bond (C = C) in the monomer is a single bond (C -C) means a structural unit. For example, an acrylic acid unit means a structural unit derived from acrylic acid when acrylic acid is copolymerized or graft polymerized.

The monomer having an acid group is a monomer having one or more acid groups in one molecule. Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group. Of these, a carboxyl group or a carboxylic anhydride group is preferable, a carboxyl group is more preferable, and a (meth) acrylic acid group is still more preferable.

Particularly preferred as the monomer having an acid group is (meth) acrylic acid. That is, the monomer unit having an acid group is preferably a (meth) acrylic acid unit. Thus, the form in which the (meth) acrylate polymer further has a (meth) acrylic acid unit is one of the preferred forms of the present invention. In terms of solvent resistance, acrylic acid is more preferable than methacrylic acid.
In this specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

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

The content ratio of the monomer unit having an acid group (preferably a (meth) acrylic acid unit) is preferably set so that the acid value of the (meth) acrylate polymer is within the above-described preferred range. is there. For example, it is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more with respect to the total amount of all monomer units of 100% by mass. Moreover, it is preferable that it is 50 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 25 mass% or less.

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

When the (meth) acrylate polymer has a ring structure in the main chain, the polymer is, for example, a tertiary carbon-containing (meth) acrylate monomer, a monomer having a hydroxyl group, and an active methylene group. It is preferable that the polymer is obtained by copolymerizing a monomer component containing a monomer having a monomer and a monomer capable of forming a ring structure in the main chain. As described above, the monomer component further preferably includes a monomer having an acid group (preferably (meth) acrylic acid).

Examples of the ring structure include an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, and a lactone ring.

Examples of monomers that can form a ring structure in the main chain include N-substituted maleimide monomers, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers, and α- (unsaturated). It is preferable to use an alkoxyalkyl) acrylate monomer (preferably an alkyl- (α-allyloxymethyl) acrylate monomer). Thus, the (meth) acrylate polymer is composed of an N-substituted maleimide monomer unit, a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer unit, and α- (unsaturated alkoxyalkyl). A form containing at least one monomer unit selected from the group consisting of acrylate monomer units is one of the preferred forms of the present invention.

Here, for example, an N-substituted maleimide monomer and / or a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer and / or an α- (unsaturated alkoxyalkyl) acrylate monomer is used. When used, it becomes possible to give a cured product having further improved heat resistance, hardness, colorant dispersibility and the like. In particular, when a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer and / or an α- (unsaturated alkoxyalkyl) acrylate monomer is used, a cured product that is superior in heat-resistant colorability can be obtained. .

The content ratio of the monomer units capable of forming a ring structure in the main chain is preferably 60% by mass or less and more preferably 50% by mass or less in the total amount of 100% by mass of all monomer units. Is preferred. In particular, when an N-substituted maleimide monomer, a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer and / or an α- (unsaturated alkoxyalkyl) acrylate monomer are included, the content ratio Is preferably 2 to 60% by mass, more preferably 2 to 50% by mass, and still more preferably 3 to 40% by mass from the viewpoints of heat resistance, hardness, colorant dispersibility, development speed, transparency, and the like. It is.

Examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, p-methylbenzylmaleimide, p-butylbenzylmaleimide, p-hydroxybenzylmaleimide, o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide, etc. These 1 type (s) or 2 or more types can be used. Among these, N-phenylmaleimide or N-benzylmaleimide is preferable from the viewpoint of transparency, and N-benzylmaleimide is more preferable.

Examples of the dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer include 2,2 ′-[oxybis (methylene)] bisacrylic acid, dialkyl-2,2 ′-[oxybis (methylene). )] Bis-2-propenoate and the like. Among these, it is preferable to use, for example, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate from the viewpoints of transparency, dispersibility, industrial availability, and the like.

Examples of the α- (unsaturated alkoxyalkyl) acrylate monomer include α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl. N-propyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, Examples include α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate neopentyl, and the like. In addition, alkyl- (α-methallyloxymethyl) acrylate monomers and the like are also preferable. Of these, alkyl- (α-allyloxymethyl) acrylate monomers are preferred.
In addition, although α- (unsaturated alkoxyalkyl) acrylic acid (for example, α-allyloxymethylacrylic acid) is not an acrylate ester, “α- (unsaturated alkoxyalkyl) acrylate-based simple substance described in this specification is used. Included in “mer”.

As the alkyl- (α-allyloxymethyl) acrylate monomer, for example, methyl- (α-allyloxymethyl) acrylate is preferable from the viewpoint of transparency, dispersibility, industrial availability, and the like. It is.

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

(Vi) Other monomer units The (meth) acrylate polymer is also a (meth) acrylic acid ester that does not fall under the above-mentioned monomers in order to adjust developability, solvent solubility, and the like. A structural unit derived from a monomer (also referred to as a (meth) acrylic acid ester monomer unit), a structural unit derived from an aromatic vinyl monomer (also referred to as an aromatic vinyl monomer unit), In addition, one or more structural units derived from other copolymerizable monomers (also referred to as other copolymerizable monomer units) may be included.

As the (meth) acrylic acid ester monomer, for example, a monomer having an alicyclic skeleton is preferable in consideration of the surface hardness of the cured product. Specifically, for example, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, pentacyclopentadecanedimethanol rudi (meth) acrylate, cyclohexanedimethanol Di (meth) acrylate, norbornane dimethanol di (meth) acrylate, p-menthane-1,8-diol di (meth) acrylate, p-menthane-2,8-diol di ( ) Acrylate, p-menthane-3,8-diol di (meth) acrylate, bicyclo [2.2.2] -octane-1-methyl-4-isopropyl-5,6-dimethylol di (meth) acrylate, and the like. . Among these, it is preferable to use cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate and / or tricyclodecanyl (meth) acrylate from the viewpoints of versatility and availability. . It is also preferable to use an alicyclic epoxy compound such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, or ethyl glycidyl (meth) acrylate.

Examples of the (meth) acrylic acid ester monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, s-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2- (meth) acrylic acid 2- Ethylhexyl, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid phenyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl , Phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, α-hydroxy 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, in addition to t-butyl methyl acrylate, t-amyl α-hydroxymethyl acrylate, etc. 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) ) Acrylyloxymethyl-2-methyl-2-cyclohexyl-1 , 3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, and the like. Among them, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate are easy to balance heat resistance, colorant dispersibility, and solvent resolubility. And aralkyl (meth) acrylate of benzyl (meth) acrylate is preferred.

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

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

The (meth) acrylate polymer includes, for example, a monomer component including a tertiary carbon-containing (meth) acrylate monomer, a monomer having a hydroxyl group, and a monomer having an active methylene group. A polymer obtained by polymerization is preferred. The monomer component may further contain one or more other monomers as required. The monomer component preferably further includes a monomer having an acid group (particularly preferably (meth) acrylic acid) and a monomer capable of forming a ring structure in the main chain as described above. It is. Each monomer may be one type or two or more types.

The blending ratio (mass%) of the monomers to be subjected to the polymerization, that is, the content ratio of each monomer with respect to 100 mass% of the total amount of all monomer components is as follows. It is preferable to set in the same range as the content ratio of the monomer unit. In particular, the monomer component includes a tertiary carbon-containing (meth) acrylate monomer (a), a monomer (b) having a hydroxyl group, and a monomer (c) having an active methylene group. A monomer having an acid group (particularly preferably (meth) acrylic acid) (d), a monomer (e) capable of forming a ring structure in the main chain, and other units other than these if necessary. It is preferable that the monomer (f) (for example, preferably other (meth) acrylic acid ester monomer) is included, and the mass ratio (a / b / c / d / e / f) is 10 It is preferable to set to 40/10 to 40/3 to 40/2 to 50/5 to 20/0 to 20 (however, the sum of a to f is 100% by mass). More preferably, it is 10-40 / 10-40 / 4-3-40 / 2-50 / 5-5-20 / 5-20.
Further, it is preferable to appropriately set the polymerization conditions so that the acid value of the obtained (meth) acrylate polymer is 20 to 300 mgKOH / g.

As a method for polymerizing the monomer component, a commonly used technique such as bulk polymerization, solution polymerization, emulsion polymerization or the like can be used, and it may be appropriately selected according to the purpose and application. Among these, solution polymerization is preferred because it is industrially advantageous and structural adjustments such as molecular weight are easy. The polymerization mechanism of the monomer component may be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, but the polymerization method based on the radical polymerization mechanism is industrial. Is also preferable.

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

Examples of the solvent include monoalcohols; cyclic ethers; glycol monoethers; glycol ethers; esters of glycol monoethers; alkyl esters; ketones; aromatic hydrocarbons; 1 type or 2 types or more, such as amides; are preferable. Specific examples of these solvents include compounds described in paragraph No. 0042 of JP-A-2015-42697. Among these, propylene glycol monomethyl ether, propylene due to solubility of the obtained polymer, surface smoothness when forming a coating film, little influence on human body and environment, and industrial availability. More preferably, glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and / or ethyl lactate are used.

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

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

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

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

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

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

Examples of the chain transfer agent include mercaptocarboxylic acids; mercaptocarboxylic esters; alkyl mercaptans; mercapto alcohols; aromatic mercaptans; mercaptoisocyanurates; disulfides; dithiocarbamates; 1 type or 2 types or more, such as alkyl halides; Specific examples of these chain transfer agents include compounds described in paragraph No. 0049 of JP-A-2015-42697. Among these, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercaptoisocyanurates, in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. It is preferable to use a compound having a mercapto group such as More preferred are alkyl mercaptans, mercaptocarboxylic acids, and / or mercaptocarboxylic esters, and still more preferred are n-dodecyl mercaptan and / or mercaptopropionic acid.

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

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

The polystyrene equivalent weight average molecular weight of the (meth) acrylate polymer is preferably 5000 to 100,000. If the weight average molecular weight is within this range, the coating property when applying a curable resin composition containing a (meth) acrylate polymer tends to be good, and film loss is less likely to occur during development. preferable. More preferably, it is 5000 (= 55,000) to 50,000. As a result, better developability can be exhibited, solvent resistance is improved, and development speed is further increased. More preferably, it is 10,000 to 40,000, and particularly preferably 15,000 to 30,000.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the (meth) acrylate polymer is preferably 1.1 to 6.0. A molecular weight distribution within this range is preferred because it tends to be excellent in developability. More preferably, it is 1.2-4.0.

In the present specification, the weight average molecular weight and the number average molecular weight of the polymer can be determined according to the measuring method described in Examples described later.

In the curable resin composition, the content ratio of the (meth) acrylate polymer may be appropriately set according to the use and the blending of other components. For example, the solid content of the (meth) acrylate polymer However, 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 suitable that it is 80 mass% or less. By being in such a range, it becomes possible to show the effect of the present invention more remarkably. More preferably, it is 7-70 mass%, More preferably, it is 10-60 mass%.
The “total amount of solid content of the curable resin composition” means the total amount of components that form a cured product (excluding solvents that volatilize during the formation of the cured product) among the components contained in the curable resin composition. To do.

In the present invention, an acrylic polymer usually used in this field may be used in combination as long as the effects of the present invention are not impaired.

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

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

Examples of the polyfunctional polymerizable monomer include the following compounds.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meth) acrylate compounds such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate;

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Trifunctional or higher polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;

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

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

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

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

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

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

The content ratio of the polymerizable compound may be appropriately set according to the purpose and use in addition to the type of the polymerizable compound to be used and the type of the (meth) acrylate-based polymer. Therefore, it is preferably 2% by mass or more and more preferably 80% by mass or less with respect to 100% by mass of the total solid content of the curable resin composition. The lower limit is more preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 10% by mass or more, and the upper limit is more preferably 70% by mass or less, still more preferably 50% by mass or less, particularly preferably. Is 30% by mass or less, and most preferably 20% by mass or less.

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

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

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and other halomethylated triazine compounds 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4 Halomethylated oxadiazole compounds such as oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 Biimidazole compounds such as' -biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- ( Oxime ester compounds such as 2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); oxime ether compounds; bis (η5-2,4-cyclopentadien-1-yl ) -Bis (2 Titanocene compounds such as 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium; benzoate compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; 9-phenylacridine and the like An acridine compound;

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

The content of the photopolymerization initiator may be appropriately set according to the purpose, use, etc., and is not particularly limited, but is 0 with respect to 100 parts by mass of the total solid content of the curable resin composition excluding the photopolymerization initiator. It is suitable that it is 1 part by mass or more. Thereby, the hardened | cured material excellent by adhesiveness can be obtained, and peeling is suppressed more fully even after high temperature exposure. In consideration of the balance between the influence of the decomposition product of the photopolymerization initiator, economy, and the like, the amount is preferably 30 parts by mass or less. The lower limit is more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, and the upper limit is more preferably 25 parts by mass or less, and still more preferably 20 parts by mass or less. is there.

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

The photosensitizer and the photo radical polymerization accelerator do not have to be used as described above. It is preferable that it is 0.001-20 mass% with respect to 100 mass% of solid content total amount of a composition. More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

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

As the solvent, one or two kinds of commonly used solvents can be used, and the solvent is not particularly limited as long as it is appropriately selected according to the purpose and application. For example, monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; esters of glycol monoethers; alkyl esters; ketones; aromatic hydrocarbons; Water; etc. are preferred. Specific examples of these solvents include compounds described in paragraph No. 0042 of JP-A-2015-42697. For example, glycol monoether esters include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl Le acetate and the like.

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

The curable resin composition further includes, for example, a coloring material (also referred to as a colorant); a dispersant; a heat resistance improver; a leveling agent; a development aid; Inorganic fine particles such as silane, aluminum and titanium coupling agents; thermosetting resins such as fillers, epoxy resins, phenolic resins and polyvinylphenol; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization Inhibitors; UV absorbers; antioxidants; matting agents; antifoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic agents; quinonediazide compounds; 1 type (s) or 2 or more types, such as an acidic compound; acid generator; For example, when using the said curable resin composition for a color filter use, it is preferable that a coloring material is included. Thus, the form in which the curable resin composition further contains a color material is also one of the preferred forms of the present invention. A form containing at least one selected from the group consisting of a colorant, a dispersant, a heat resistance improver, a leveling agent, a coupling agent, and a development aid is also suitable. Hereinafter, these contained components will be described.

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

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

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

Specific examples of the pigment include C.I. described in paragraph numbers 0103 to 0107 of JP-A-2015-42697. I. Yellow pigments such as CI Pigment Yellow 1 and 138; I. Orange pigments such as CI Pigment Orange 1; I. A purple pigment such as CI Pigment Violet 1; I. Red pigments such as CI Pigment Red 1; I. Blue pigments such as CI Pigment Blue 1; I. Green pigments such as CI Pigment Green 1 and 58; I. Brown pigments such as CI Pigment Brown 5; aniline black, carbon black, lamp black, bone black, black iron, titanium black, C.I. I. Black pigments such as CI Pigment Black 1; I. And white pigments such as CI Pigment White 1. However, the color material of the present invention is not limited to these. Moreover, a pigment may be used independently and may be used in combination of 2 or more types. “CI” means a color index (CI; issued by The Society of Dyers and Colorists), and a number means a color index number.

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

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

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

Examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , Long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, or a salt thereof, (meth) acrylic acid-styrene Copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide adduct, etc. All It is.

The resin-type dispersant has a graft structure in which the main chain is an anchor chain having an interaction site with a coloring material, and the graft chain is a compatible chain having an interaction property with a dispersion medium. In addition, a resin in which an anchor chain and a compatible chain have a block structure is particularly preferably used.

Specific examples of the resin-type dispersant include products described in paragraph No. 0112 of JP-A-2015-42697. However, it is not limited to these.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate Surfactants; cationic boundaries such as alkyl quaternary ammonium salts and their ethylene oxide adducts Alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazolines; active agents.

The dye derivative is a compound having a structure in which a functional group is introduced into the dye. Examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, and an amide group. And phthalimide groups. Examples of the structure of the base dye include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, diketopyrrolopyrrole. And the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

-Placement step (preferably coating step)-
The arrangement step is preferably performed by coating. Examples of the method of applying the curable resin composition on the substrate include spin coating, slit coating, roll coating, and cast coating, and any method can be preferably used.

In the arranging step, it is preferable that the coating film is dried after the curable resin composition is applied onto the substrate. The coating film can be dried using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected depending on the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc. Is preferred.

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

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

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

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

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Examples of the organic solvent in this case include organic solvents suitable as the developer described above.

Examples of the alkali agent include inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. Alkali agents: Examples include amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and these may be used alone or in combination of two or more. May be combined.

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

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

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

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

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

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

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

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass”.
In the following synthesis examples and the like, various physical properties and the like were measured as follows.

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

<Solid content>
About 1 g of a polymer solution (also referred to as a resin solution or a polymer solution) was weighed into an aluminum cup, dissolved by adding about 3 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by Espec Corp.), after drying at 140 ° C. for 1.5 hours under vacuum, the mixture was allowed to cool in a desiccator and the mass was measured. From the mass reduction amount, the solid content (% by mass) of the polymer solution was calculated.

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

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

Synthesis example 1
Propylene glycol was added to a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dripping vessel introduction port for a resin solution 1 (BzMI-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 1). After charging 156.3 parts of monomethyl ether acetate and replacing with nitrogen, the mixture was heated to 90 ° C. On the other hand, as a dropping tank (A), 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, 17.1 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate are placed in a beaker. 5 parts, 12.9 parts of acrylic acid, and 2 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) were prepared and mixed in a dropping tank (B). A mixture obtained by stirring and mixing 0.6 parts of n-dodecyl mercaptan and 29.4 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction vessel reached 90 ° C., dropping was started over 3 hours from the dropping vessel while maintaining the same temperature, and polymerization was performed. After maintaining the temperature at 90 ° C. for 30 minutes after completion of the dropping, the temperature was raised to 115 ° C. and aging was performed for 90 minutes.
When the obtained polymer solution was analyzed, the weight average molecular weight was 19,500, the acid value was 100 mgKOH / g, and the resin solid content was 34.7% by mass.

Synthesis example 2
The amount of the synthetic monomer charged in the resin solution 2 (BzMI-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 2) is 10 parts of N-benzylmaleimide, 32.1 parts of t-butyl methacrylate, The same polymer solution as obtained in Synthesis Example 1 except that 10 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 15 parts of 2-acetoacetoxyethyl methacrylate and 12.9 parts of acrylic acid were used. The weight average molecular weight was 20000, the acid value was 100 mgKOH / g, and the resin solid content was 34.6% by mass.

Synthesis example 3
Synthetic monomer charge amount of resin solution 3 (BzMI-t-BMA-MMA-HEMA-AAEM-AA copolymer solution 3) is 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, methacrylic acid. The same polymer solution as obtained in Synthesis Example 1 except that 7.1 parts of methyl, 30 parts of 2-hydroxyethyl methacrylate, 5 parts of 2-acetoacetoxyethyl methacrylate, and 12.9 parts of acrylic acid were used. The weight average molecular weight was 20,500, the acid value was 100 mgKOH / g, and the resin solid content was 34.7% by mass.

Synthesis example 4
Synthetic monomer charge amount of resin solution 4 (BzMI-t-BMA-HEMA-AAEM-AA copolymer solution 4) is 10 parts of N-benzylmaleimide, 32.1 parts of t-butyl methacrylate, methacrylic acid. The polymer solution was analyzed in the same manner as in Synthesis Example 1 except that 30 parts of 2-hydroxyethyl, 15 parts of 2-acetoacetoxyethyl methacrylate, and 12.9 parts of acrylic acid were used. Was 21,000, the acid value was 100 mgKOH / g, and the resin solid content was 34.6% by mass.

Synthesis example 5
Synthetic monomer charge amount of resin solution 5 (BzMI-t-BMA-MMA-HEMA-AAEM-MAA copolymer solution 5) is 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, methacrylic acid. The same polymer solution was obtained as in Synthesis Example 1 except that 20 parts of 2-hydroxyethyl, 14.6 parts of methyl methacrylate, 5 parts of 2-acetoacetoxyethyl methacrylate, and 15.4 parts of methacrylic acid were used. The weight average molecular weight was 19,300, the acid value was 100 mgKOH / g, and the resin solid content was 34.7% by mass.

Synthesis Example 6
Synthesis of Resin Solution 6 (MD-t-BMA-MMA-HEMA-AAEM-AA Copolymer Solution 6) Instead of N-benzylmaleimide, dimethyl-2,2 ′-[oxybis (methylene)] bis-2- Except that propenoate (MD) was used, the same operation as in Synthesis Example 1 was performed, and the obtained polymer solution was analyzed. As a result, the weight average molecular weight was 20000, the acid value was 100 mgKOH / g, and the resin solid content was 34.7 mass. %Met.

Synthesis example 7
Synthesis of Resin Solution 7 (AMA-t-BMA-MMA-HEMA-AAEM-AA Copolymer Solution 7) Methyl (α-allyloxymethyl) acrylate (AMA) was used in place of N-benzylmaleimide Was the same as in Synthesis Example 1, and the obtained polymer solution was analyzed. As a result, the weight average molecular weight was 19000, the acid value was 100 mgKOH / g, and the resin solid content was 34.7% by mass.

Synthesis Example 8
The amount of the synthetic monomer of the resin solution 8 (BzMI-t-BMA-MMA-HEMA-AA copolymer solution 8) was changed to 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, methyl methacrylate 22 .1 part, 20 parts of 2-hydroxyethyl methacrylate, 12.9 parts of acrylic acid, and the same operation as in Synthesis Example 1 was performed, and the resulting polymer solution was analyzed. The weight average molecular weight was 19000, acid The value was 100 mgKOH / g, and the resin solid content was 34.7% by mass.

Synthesis Example 9
The amount of the synthetic monomer of resin solution 9 (BzMI-MMA-HEMA-AAEM-AA copolymer solution 9) was changed to 10 parts of N-benzylmaleimide, 52.1 parts of methyl methacrylate, 2-hydroxyethyl methacrylate. The obtained polymer solution was analyzed except that 20 parts, 2-acetoacetoxyethyl methacrylate 5 parts, and 12.9 parts acrylic acid were used, and the obtained polymer solution was analyzed. The weight average molecular weight was 19500, acid The value was 100 mgKOH / g, and the resin solid content was 34.7% by mass.

Synthesis Example 10
The amount of the synthetic monomer of the resin solution 10 (BzMI-t-BMA-MMA-AAEM-AA copolymer solution 10) was changed to 10 parts of N-benzylmaleimide, 35 parts of t-butyl methacrylate, and 37 of methyl methacrylate. .1 part, 5 parts of 2-acetoacetoxyethyl methacrylate and 12.9 parts of acrylic acid were subjected to the same operation as in Synthesis Example 1, and the obtained polymer solution was analyzed. The weight average molecular weight was 19000, The acid value was 100 mgKOH / g, and the resin solid content was 34.6% by mass.

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

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

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

Example 1
2.0 parts of resin solution 1, 0.70 parts of dipentaerythritol hexaacrylate as a radical polymerizable compound, 0.35 parts of Irgacure 369 (manufactured by Ciba Specialty Chemicals) as a radical polymerizable photopolymerization initiator, 8.5 parts of pigment dispersion 1 and 6.57 parts of propylene glycol monomethyl ether acetate as a solvent were mixed to obtain curable resin composition 1. This curable resin composition was spin-coated on a glass substrate, a cured product was prepared under the above conditions, and an NMP elution test was performed. The absorbance of NMP was measured and found to be 4 × 10 ⁻² .

Examples 2-7, Comparative Examples 1-3
Except having set it as the mixing | blending shown in Table 2 and 3, after obtaining the curable resin composition 2-7 and the curable resin composition 9-11 like Example 1, respectively, after NMP elution test of NMP, Absorbance was measured for each. The results are shown in Tables 2 and 3.

Example 8, Comparative Example 4
After obtaining the curable resin composition 8 and the curable resin composition 12 in the same manner as in Example 1 except that the radical polymerizable initiator was changed to Irgacure OXE01 (manufactured by Ciba Specialty Chemicals), The absorbance of NMP after the NMP dissolution test was measured. The results are shown in Tables 2 and 3.

From the results in Tables 2 and 3, the following was confirmed.
The curable resin compositions obtained in Examples 1 to 7 contain, as resin solutions 1 to 7, tertiary carbon-containing (meth) acrylate monomer units, monomer units having hydroxyl groups, and active methylene groups. The polymer which the curable resin composition obtained in Comparative Examples 1 to 3 does not have any of these monomer units, while the polymer having the monomer units to be included is included. In this respect, Examples 1 to 7 and Comparative Examples 1 to 3 are mainly different. Under this difference, when the result of obtaining the cured product under the same conditions and measuring the absorbance was compared, the curable resin composition of Comparative Examples 1 to 3 was compared with the curable resin composition of Examples 1 to 7. Then, it turns out that the light absorbency of hardened | cured material is remarkably large and the coloring material has eluted from hardened | cured material. If the curability and solvent resistance of the curable composition are insufficient, the absorbance of the eluate increases due to the elution of the coloring material. It turns out that the curable resin composition of an example was inadequate in sclerosis | hardenability and solvent resistance. Moreover, it is clear from the comparison between Examples 1, 3, 5 to 7 and Examples 2 and 4 that the more AAEM units and / or HEMA units, the more the solvent resistance is improved.

Example 8 (using resin solution 4 containing AAEM units and using Irgacure OXE01 as a radical polymerizable photoinitiator) and Example 4 (using resin solution 4 containing AAEM units and using Irgacure 369), When Example 8 is compared, it can be seen that the solvent resistance is greatly improved in Example 8 because the absorbance is remarkably low. On the other hand, Comparative Example 4 (using resin solution 8 containing no AAEM units and using Irgacure OXE01 as a radical polymerizable photoinitiator) and Comparative Example 1 (using resin solution 8 containing no AAEM units and radical polymerization) Comparing with Irgacure 369 as the photoinitiator, it can be seen that in Comparative Example 4, the absorbance is slightly low and the solvent resistance is hardly improved. From these results, it is clear that when the oxime compound (preferably oxime ester compound) is used as the radical polymerizable photoinitiator, the resin solution containing the AAEM unit has further improved solvent resistance. That is, the effect that the solvent resistance is remarkably improved by using an oxime compound (preferably an oxime ester compound) is that a polymer containing a monomer unit having an active methylene group such as an AAEM unit is used. It turned out to be a peculiar effect.

Further, Example 1 (using resin solution 1 using acrylic acid as a raw material) has lower absorbance than Example 5 (using resin solution 5 using methacrylic acid as a raw material). From this, the superiority of using an acrylic acid polymer over a methacrylic acid polymer in solvent resistance was confirmed. In addition, although not shown in the table, all the cured products obtained in the examples were excellent in various physical properties such as developability, adhesion to the substrate, and heat resistance.

A member for a display device and a display device including a cured product formed from the curable resin composition of the present invention can be suitably used in the optical field, the electric / electronic field, and the like.

Claims (10)

A curable resin composition comprising a (meth) acrylate polymer, a polymerizable compound and a photopolymerization initiator,
The (meth) acrylate polymer has a tertiary carbon-containing (meth) acrylate monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group. Curable resin composition. In the (meth) acrylate polymer, the content ratio of the tertiary carbon-containing (meth) acrylate monomer unit is 5 to 90% by mass with respect to 100% by mass of the total amount of all monomer units, The content ratio of the monomer units having a ratio of 5 to 50% by mass with respect to 100% by mass of the total amount of all monomer units, and the content ratio of the monomer units having an active methylene group is It is 3-40 mass% with respect to 100 mass% of total amounts of a unit, The curable resin composition of Claim 1 characterized by the above-mentioned. The (meth) acrylate-based polymer, further, (meth) curable resin composition according to claim 1 or 2, characterized in that having an acrylic acid unit. The tertiary carbon-containing (meth) acrylate monomer has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom . The curable resin composition described in 1. The curable resin composition according to any one of claims 1 to 4 , wherein the monomer having an active methylene group is represented by the following formula (2).

In formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom. X represents a divalent group represented by any of the following formulas (2-1) to (2-3). R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a divalent group represented by any of the following formulas (2-4) to (2-6). R ⁴ represents a cyano group (—CN), a nitro group (—NO ₂ ), or a group represented by the following formula (2-7) or (2-8). R5 represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom.

The (meth) acrylate polymer, the curable resin composition according to any one of claims 1 to 5, characterized by having a ring structure in its main chain. The curable resin composition according to claim 1, further comprising a coloring material. Cured product characterized by being obtained by curing the curable resin composition according to any one of claims 1-7. A color filter comprising the cured product according to claim 8 on a substrate. A display device comprising the color filter according to claim 9 .