JP2019081846A - Curable resin composition and application thereof - Google Patents

Abstract

To provide a curable resin composition that can produce a cured product capable of sufficiently suppressing density unevenness through contact with water, being excellent in heat-resistant colorability and capable of being suitably used for an application of a color filter.SOLUTION: A curable resin composition contains an acid group-containing polymer. The acid group-containing polymer has 2 to 30 mass% of an N-alkylmaleimide monomer unit and/or an N-cycloalkylmaleimide monomer unit, 10 to 40 mass% of an alicyclic hydrocarbon group-containing monomer unit and 5 to 25 mass% of an acid group-containing monomer unit.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition capable of obtaining a cured product excellent in water unevenness suppression and heat resistant colorability, the cured product, a color filter using the cured product, and a display device.

The curable resin composition that can be cured by heat or active energy ray is, for example, various kinds of color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used for liquid crystal display devices, solid-state imaging devices, etc. The application to various applications, such as the optical member of this, an electrical machinery, an electronic device, etc. is examined variously, and development of the curable resin composition excellent in the characteristic requested | required by each application is made | formed. Among these applications, the color filter is a main member constituting a liquid crystal display device, a solid-state imaging device, etc., and in general, at least three primary colors (red (R), green (G), blue (B)) of a substrate. In addition to the pixels and the resin black matrix (BM) separating them, the pixel and the resin black matrix are covered and protected, and a protective film or the like provided to planarize the unevenness thereof.

In general, when forming a pixel of a color filter using a curable resin composition, (1) an application step of applying the curable resin composition to the entire surface of the substrate, and (2) an application step After exposing a resist film to a pattern through a photomask and curing the exposed area, an exposure step of insolubilizing the cured area, and (3) removing the unexposed area with a developer, and exposing it by baking (baking) A method is employed in which development and baking (baking) processing steps for further curing the part are performed and the same steps are repeated for each color. Considering the application of such color filters to applications, the curable resin composition has various properties such as curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance and transparency. It is required to have physical properties. Further, in recent years, downsizing, thinning and energy saving of optical members, electric machines, electronic devices and the like are progressing, and along with this, members such as color filters to be used are required to have high quality performance.

As a curable resin composition suitable for color filter applications, for example, N-benzylmaleimide monomer unit, tertiary carbon-containing (meth) acrylate monomer unit, monomer unit having a hydroxyl group, and acrylic acid The curable resin composition (refer patent document 1) containing the (meth) acrylate type polymer which has a unit, a polymeric compound, and a photoinitiator is proposed.

JP, 2015-157909, A

However, in such a conventional curable resin composition, when developing is performed using a developer after the exposure step, when the developer adheres to the exposed and cured portion (cured portion), the adhered portion becomes cloudy. There was a problem that density unevenness (water unevenness) could occur in the cured part, and the transparency and colorability of the cured product would be reduced.
Further, in recent years, from the viewpoint of improving the brightness of a color filter, a curable resin composition applied to a color filter is required to cause as little discoloration as yellowing or the like by heating at the time of production. Such heat-resistant colorability has been studied so far, but as the performance required for color filters etc. increases, further improvement is required.

The present invention provides a curable resin composition that can sufficiently suppress water unevenness, is excellent in heat-resistant colorability, and can obtain a cured product that can be suitably used for applications of color filters in view of the above-mentioned present conditions. The purpose is to

The inventors of the present invention have investigated various curable resin compositions in order to solve the above problems, and N-alkylmaleimide monomer units and / or N-cycloalkylmaleimide monomer units, alicyclic hydrocarbon groups By using a polymer having each of the content-containing monomer units and the acid group-containing monomer units in a specific range amount, it is possible to sufficiently suppress water unevenness and to obtain a cured product which is also excellent in heat-resistant colorability. I found that I could do it. The present inventors have also found that such a curable resin composition is particularly suitable as a resin composition for forming a member for applications such as a color filter, and came to complete the present invention.

That is, the present invention is a curable resin composition containing an acid group-containing polymer, wherein the acid group-containing polymer is an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide monomer unit A curable resin composition comprising: 2 to 30% by mass, 10 to 40% by mass of an alicyclic hydrocarbon group-containing monomer unit, and 5 to 25% by mass of an acid group-containing monomer unit is there.
The present invention is also a cured product characterized in that the above-mentioned curable resin composition is cured.
The present invention is also a color filter characterized by having the cured product on a substrate.
The present invention is also a display device comprising the above color filter.

Since the curable resin composition of the present invention is configured as described above, it is possible to suppress water unevenness and obtain a cured product excellent in heat-resistant colorability. Such a curable resin composition of the present invention can be used as a color filter, an ink, a printing plate, a printed wiring board, a semiconductor element, an optical member such as a photoresist, or an electric / electronic device such as a liquid filter Etc. can be suitably used in various applications such as

The present invention will be described in detail below.
In addition, what combined two or more of each preferable form of this invention described below is also a preferable form of this invention.

1. Curable resin composition The curable resin composition of the present invention contains an acid group-containing polymer, and the above-mentioned acid group-containing polymer is an N-alkylmaleimide monomer unit and / or a single amount of N-cycloalkylmaleimide. It is characterized by having 2 to 30% by mass of a body unit, 10 to 40% by mass of an alicyclic hydrocarbon group-containing monomer unit, and 5 to 25% by mass of an acid group-containing monomer unit.
By containing the above-mentioned acid group-containing polymer, it is possible to suppress water unevenness and obtain a cured product excellent in heat-resistant colorability, because the above-mentioned acid group-containing polymer is composed of N-alkylmaleimide monomer units and / or Or it is guessed that it is because the hydrophobic property of the hardened | cured material obtained becomes high by having a N- cycloalkyl maleimide monomer unit and an alicyclic hydrocarbon group containing monomer unit. Moreover, it is estimated that the discoloration at the time of a heating is suppressed because the said acidic radical containing polymer has an alicyclic hydrocarbon group containing monomeric unit.

In the present specification, “water unevenness” means that the cured product comes in contact with a water-soluble solution such as a developer and the like, and after the water-soluble solution is removed, discoloration occurs such that the contacted portion becomes cloudy. It means that unevenness can be made on objects.
Below, each component of the curable resin composition of this invention is demonstrated.

<1-1. Acid group-containing polymer>
The acid group-containing polymer used in the present invention is an N-alkyl maleimide monomer unit and / or an N-cycloalkyl maleimide unit amount relative to 100% by mass of all monomer units constituting the acid group-containing polymer. It has 2 to 30% by mass of a body unit, 10 to 40% by mass of an alicyclic hydrocarbon group-containing monomer unit, and 5 to 25% by mass of an acid group-containing monomer unit. Therefore, the curable resin composition containing the above-mentioned acid group-containing polymer is unlikely to cause water unevenness and can give a cured product having excellent heat-resistant colorability.
The acid group-containing polymer contains 100% by mass of all the monomer units of the acid group-containing polymer in that the water unevenness is further suppressed and a cured product having more excellent heat-resistant colorability is obtained. Against 5 to 20% by mass of N-alkylmaleimide monomer units and / or N-cycloalkylmaleimide monomer units, 10 to 35% by mass of alicyclic hydrocarbon group-containing monomer units, and an acid group It is preferable to have 10 to 25% by mass of the monomer unit contained, and 5 to 20% by mass of an N-alkylmaleimide monomer unit and / or an N-cycloalkylmaleimide monomer unit, an alicyclic hydrocarbon group-containing unit It is more preferable to have 10 to 33% by mass of the monomer unit and 12 to 25% by mass of the acid group-containing monomer unit.
Below, each monomer unit which comprises the said acidic radical containing polymer is demonstrated.

(N-alkyl maleimide monomer unit and / or N-cycloalkyl maleimide monomer unit)
The acid group-containing polymer has N-alkyl maleimide monomer units and / or N-cycloalkyl maleimide monomer units. When the acid group-containing polymer has an N-alkyl maleimide monomer unit and / or an N-cycloalkyl maleimide monomer unit, the water unevenness of the obtained cured product is suppressed, and the heat-resistant colorability is improved. be able to. Especially, it is preferable to have a N-cycloalkyl maleimide monomer unit from the point which can exhibit the suppression of a further outstanding water nonuniformity, and heat-resistant colorability.

As said N-alkyl maleimide monomer unit, the polymer structural unit derived from a N-alkyl maleimide monomer is mentioned.
As said N-alkyl maleimide monomer, The maleimide monomer which preferably has a C1-C20 chain | strand-shaped alkyl group is mentioned, Specifically, For example, N- methyl maleimide, N- ethyl maleimide , N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-t-butylmaleimide, N-n-pentylmaleimide, N-n-hexylmaleimide, N-n- Heptyl maleimide, N-n-octyl maleimide, N-dodecyl maleimide, N-lauryl maleimide, 2-ethylhexyl maleimide, etc. are mentioned.

As said N- cycloalkyl maleimide monomer unit, the polymer structural unit derived from N- cycloalkyl maleimide monomer is mentioned.
As said N- cycloalkyl maleimide monomer, The maleimide monomer which preferably has a C5-C10 cycloalkyl group is mentioned, Specifically, For example, N-cyclohexyl maleimide, N-cyclopentyl maleimide , N-dicyclopentanyl maleimide, N-dicyclopentenyl maleimide, N-tricyclodecanyl maleimide and the like. Among them, N-cyclohexyl maleimide is preferable in that it can exhibit even more excellent suppression of water unevenness and heat resistant colorability.
The above-mentioned acid group-containing polymer may have only one kind of those mentioned above as the above-mentioned N-alkyl maleimide monomer unit and / or N-cycloalkyl maleimide monomer unit, or two of them. You may have the above.

The content ratio of the N-alkyl maleimide monomer unit to the N-cycloalkyl maleimide monomer unit (N-alkyl maleimide monomer unit / N-cycloalkyl maleimide monomer unit) is 0/100 by mass ratio It is preferably 50/50, more preferably 0/100 to 30/70, and still more preferably 0/10 to 10/90.

(Alicyclic hydrocarbon group-containing monomer unit)
The acid group-containing polymer has an alicyclic hydrocarbon group-containing monomer unit. When the acid group-containing polymer contains the alicyclic hydrocarbon group-containing monomer unit, the curable resin composition of the present invention provides a cured product excellent in suppression of water unevenness and heat-resistant colorability. Can.

As said alicyclic hydrocarbon group containing monomer unit, the polymer structural unit derived from the monomer which has an alicyclic hydrocarbon group and has a polymerizable double bond is mentioned.
The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms, more preferably 7 to 10 carbon atoms, and specifically, cyclopropyl, cyclopentyl, cyclohexyl Monocyclic hydrocarbon groups such as cyclooctyl, cyclododecyl, cycloheptyl, cyclobutenyl, cyclopentenyl and cyclohexenyl; and polycyclic carbonization such as dicyclopentanyl, dicyclopentenyl, tricyclodecanyl, adamantyl and isobornyl A hydrogen group is mentioned. Among them, the alicyclic hydrocarbon group is preferably a polycyclic hydrocarbon group in that it can exert even more excellent suppression of water unevenness and heat resistant colorability, and dicyclopentanyl, Dicyclopentenyl and isobornyl are more preferred, and dicyclopentanyl is especially preferred.

As said polymeric double bond, a (meth) acryloyl group, a vinyl group, an allyl group, a methallyl group etc. are mentioned, for example. The monomer having a polymerizable double bond is preferably a (meth) acrylate monomer. That is, it is preferable that the said alicyclic hydrocarbon group containing monomer is an alicyclic hydrocarbon group containing (meth) acrylate type monomer.
In the present specification, "(meth) acrylate" means "acrylate and / or methacrylate".

Specific examples of the alicyclic hydrocarbon group-containing monomer include, for example, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (3 , 4-Epoxycyclohexyl) methyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dimethylol- Tricyclodecane di (meth) acrylate, pentacyclopentadecane dimethanol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, norbornane dimethanol di (meth) acrylate, p-men 1,8-diol di (meth) acrylate, p-menthan-2,8-diol di (meth) acrylate, p-menthan-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 them, as the above-mentioned alicyclic hydrocarbon group-containing monomer, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and isobornyl (meth) acrylate are more preferable, and dicyclopentanyl (meth) Acrylate is more preferred and dicyclopentanyl methacrylate is particularly preferred.
The above-mentioned acid group-containing polymer may have only one kind or two or more kinds of those described above as the above-mentioned alicyclic hydrocarbon group-containing monomer unit.

(Acid group containing monomer unit)
The acid group-containing polymer has an acid group-containing monomer unit. When the acid group-containing polymer has an acid group-containing monomer unit, the curable resin composition of the present invention improves the surface hardness of the cured product at the time of curing, and thus the adhesion to a substrate and alkali solubility It can give excellent cured products. Moreover, when the curable resin composition of this invention is used for a color filter use, the cured film (hardened | cured material) excellent in developability can be formed.
Examples of the acid group-containing monomer unit include polymer structural units derived from the acid group-containing monomer. Examples of the acid group-containing monomer include compounds having an acid group and a polymerizable double bond in the molecule.

Examples of the acid group include a functional group which is neutralized with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, a sulfonic acid group, etc. You may have, and you may have 2 or more types. Among them, a carboxyl group and a carboxylic acid anhydride group are preferable, and a carboxyl group is more preferable.
As said polymeric double bond, a (meth) acryloyl group, a vinyl group, an allyl group, a methallyl group etc. are mentioned, for example.

Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid Unsaturated polyvalent carboxylic acids such as: monounsaturated (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, etc. Unsaturated monobasic in which the chain is extended between the unsaturated group and the carboxyl group Carboxylic acids; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.); and the like. Among these, it is preferable to use a carboxylic acid monomer (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) from the viewpoint of versatility, availability and the like. From the viewpoint of reactivity, suppression of water unevenness, heat-resistant colorability, etc., unsaturated monocarboxylic acids are more preferable, and (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid) is more preferable.
The above-mentioned acid group-containing polymer may have only one type or two or more types among the above-mentioned as the above-mentioned acid group-containing monomer unit.

(--COO ^* R ¹ vinyl group containing vinyl group)
The above-mentioned acid group-containing polymer has the above-mentioned monomer unit as a structural unit, but further, -COO ^* R ¹ (R ¹ is a monovalent organic group and carbon bonded to O ^* The atom preferably has a vinyl-based monomer unit containing a tertiary carbon atom) group (hereinafter also referred to as "vinyl-based monomer unit (A)"). When the acid group-containing polymer further includes the vinyl monomer unit (A) and a hydroxyl group-containing monomer unit described later, the curability of the curable resin composition, the hardness of the cured product, the solvent resistance Properties, heat resistance, transparency, adhesion to a substrate, etc. can be improved. Furthermore, when the curable resin composition of the present invention contains a colorant, the colorant concentration in the obtained cured product can be increased. Therefore, it is possible to realize further thinning of the film, and further to achieve high color purification and a high light blocking ratio of the black matrix.

When the acid group-containing polymer has the vinyl monomer unit (A) and a hydroxyl group-containing monomer unit described later, the curability of the curable resin composition and the characteristics of the cured product described above are improved. When a coating film is formed using a cured resin composition and heated, the tertiary carbon in the vinyl monomer unit (A) is eliminated to form an acid group, and this acid group and It is presumed that the crosslinking occurs with the hydroxyl group of the hydroxyl group-containing monomer unit. Also, as described above, the color material concentration in the cured product can be increased because the crosslinking reaction proceeds due to the elimination of tertiary carbon, while the eliminated components are volatilized and the amount of resin in the cured product is relative Is presumed to be due to the decrease.

In the vinyl-based monomer unit (A), ^{R 1} of -COO ^* R ¹ represents a monovalent organic group, the carbon atom bonded to ^{O *} is a tertiary carbon atom. The tertiary carbon atom means a carbon atom in which three other carbon atoms are bonded to the carbon atom.
As said monovalent organic group, Preferably C1-C90 monovalent | monohydric chain | strand-shaped, branched or cyclic saturated or unsaturated hydrocarbon group is mentioned. The organic group may have a substituent.
The carbon number of R ¹ is more preferably ¹ to 46 carbon atoms, still more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
R ¹ is preferably a monovalent organic group similar to A in general formula (a) described later.

As a vinyl-type monomer, the monomer which has a polymeric carbon-carbon double bond in a molecule | numerator is mentioned, A (meth) acrylate-type monomer is especially preferable. That is, as the vinyl-based monomer unit (A), a tertiary carbon-containing (meth) acrylate-based monomer unit is preferable.

The tertiary carbon-containing (meth) acrylate monomer preferably has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom.

The above-mentioned tertiary carbon-containing (meth) acrylate monomer is a compound having one polymerizable carbon-carbon double bond in the molecule, that is, a (meth) acryloyl group (CH ₂ CC (R ² ) in the molecule. It is preferable that it is a compound which has one -C (= O)-), for example, following General formula (a):
^{_{CH 2 = C (R 2)}} -C (= O) -O-A (a)
(Wherein R ² represents a hydrogen atom or a methyl group. A represents a monovalent organic group containing a structure having a tertiary carbon atom on the oxygen atom side.) Is preferred.

In the general formula (a), the monovalent organic group represented by A can be represented, for example, by —C (R ³ ) (R ⁴ ) (R ⁵ ). In this case, R ³ , R ⁴ and R ⁵ are the same or different and are preferably a hydrocarbon group having 1 to 30 carbon atoms, and the above hydrocarbon group may be a saturated hydrocarbon group It may be an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. In addition, R ³ , R ⁴ and R ⁵ may be linked to each other at terminal portions to form a cyclic structure.

The carbon number of the organic group represented by A is an oxygen atom adjacent to a (meth) acryloyl group (CH ₂ CC (R ² ) -C (CO)-), and the third in A adjacent to it. The number of carbon atoms is preferably 12 or less, more preferably 9 or less, from the viewpoint that new compounds formed by cleavage of the O-C bond with the class carbon atom are easily volatilized. Further, the organic group represented by A may have a branched structure.

Here, in the above-mentioned tertiary carbon-containing (meth) acrylate monomer, at least one of the adjacent carbon atoms of the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group is 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 (a), and A is represented by -C (R ³ ) (R ⁴ ) (R ⁵ ) When it is a group, it is preferable that at least one of R ³ , R ⁴ and R ⁵ contains a carbon atom having one or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom. In such a form, the heating cleaves the O-C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent to it to simultaneously generate (meth) acrylic acid. 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 more stably generated.

Preferably, the new compounds produced as described above are volatile. In this case, at the same time the film thickness of the cured product (cured film) is reduced due to the new compound volatilizing out of the cured product, for example, the curable resin composition further includes a coloring material In the case, the colorant concentration increases after heating. Therefore, it is possible to realize further thinning of the film, and to achieve high color purification and a high light blocking ratio of the black matrix. When this point is considered, it is preferable that said R < ³ >, R < ⁴ > and R < ⁵ > are the same or different, and are a C1-C15 saturated hydrocarbon group. 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.

The (meth) acrylate monomer having a tertiary carbon atom is preferably t-butyl (meth) acrylate or t-amyl (meth) acrylate.
The above-mentioned acid group-containing polymer may have only one kind of those mentioned above as the above-mentioned vinyl monomer unit (A), or may have two or more kinds.

The content of the vinyl-based monomer unit (A) in the acid group-containing polymer is preferably 20 to 60% by mass, based on 100% by mass of all monomer units of the acid group-containing polymer. Preferably it is 25-50 mass%, More preferably, it is 25-40 mass%.

(Hydroxyl group containing monomer unit)
The acid group-containing polymer preferably further contains a hydroxyl group-containing monomer unit. When the acid group-containing polymer further includes a hydroxyl group-containing monomer unit together with the vinyl monomer unit (A), the curability of the curable resin composition of the present invention, the hardness of the cured product, the solvent resistance Properties, heat resistance, transparency, adhesion to a substrate, etc. can be improved. In addition, the thickness of the cured product can be reduced, and the color material concentration can be increased.

The above hydroxyl group-containing monomer is not particularly limited as long as it is a compound having a hydroxyl group and a polymerizable double bond in the molecule, and examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxy (meth) acrylate Propyl, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3 (meth) acrylate Preferred are hydroxyalkyl (meth) acrylates such as -hydroxypropyl, and more preferred is 2-hydroxyethyl (meth) acrylate.
The above-mentioned acid group-containing polymer may have only one kind of those mentioned above as the above-mentioned hydroxyl group-containing monomer unit, or may have two or more kinds.

The content of the hydroxyl group-containing monomer unit in the acid group-containing polymer is preferably 10 to 40 mass%, more preferably 10 with respect to 100 mass% of all monomer units of the acid group-containing polymer. It is -35 mass%, more preferably 10-30 mass%.

The above-mentioned acid group-containing polymer is, as described above, 2 to 30% by mass of N-alkylmaleimide monomer unit and / or N-cycloalkylmaleimide monomer unit, alicyclic hydrocarbon group-containing monomer unit Although it has 10 to 40% by mass and 5 to 25% by mass of acid group-containing monomer units, it further contains 20 to 60% by mass of the above-mentioned vinyl-based monomer unit (A) and the above-mentioned hydroxyl group-containing It is also one of the preferred embodiments to have 10 to 40% by mass of monomer units.

The above-mentioned acid group-containing polymer may contain other polymerizable monomer units in addition to the above-mentioned monomer units.
As the other polymerizable monomer unit, for example, a single amount derived from a (meth) acrylic acid ester monomer, an aromatic hydrocarbon group-containing monomer, another copolymerizable monomer, etc. Body unit is mentioned.

Examples of the (meth) acrylic acid ester-based monomer include 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) acrylate Ethyl hexyl, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid 2 -Methoxyethyl, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) N, N-dimethylaminoethyl acrylate, 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloyl morpholine, 4- (meth) acryloyloxymethyl-2-methyl-2-yl Ethyl 1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane and the like can be mentioned.

Examples of the aromatic hydrocarbon group-containing monomer include aromatic vinyl monomers such as styrene, vinyl toluene, α-methylstyrene and methoxystyrene; N-phenyl maleimide, N-benzyl maleimide and the like N- Aromatic substituted maleimides and the like can be mentioned.

As said other copolymerizable monomer, 1 type (s) or 2 or more types, such as the following compound, are mentioned, for example.
(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, etc .; heavy weight such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam, etc. Macromonomers having (meth) acryloyl group at one end of united molecular chain; Conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether Vinyl ethers such as methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, methoxy ethoxy ethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole N-vinyl compounds such as N-vinyl morpholine and N-vinyl acetamide; Unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate; 2,2 '-[oxybis (methylene)] bis acrylic Acids, dialkyl-2,2 '-[oxybis (methylene)] bis-2-propenoates, dialkyl-2,2'-[oxybis (methylene)] bis-2-propenoates, etc. Dialkyl-2,2 '-(oxydimethylene) diacrylate monomers; α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyloxy N-propyl methyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate Α- (unsaturated alkoxy) such as n-amyl α-allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate Alkyl) acrylate type monomers etc. are mentioned.

The content of the aromatic hydrocarbon group-containing monomer unit in the acid group-containing polymer is 5% by mass or less based on 100% by mass of all monomer units of the acid group-containing polymer preferable. When the content of the aromatic hydrocarbon group-containing monomer unit is 5% by mass or less, the heat resistant colorability is further excellent. The content of the aromatic hydrocarbon group-containing monomer unit is more preferably 3% by mass or less, still more preferably 0% by mass.
As said aromatic hydrocarbon group containing monomer unit, the monomer unit originating in the aromatic hydrocarbon group containing monomer mentioned above is mentioned.

The acid group-containing polymer is also a vinyl-based monomer unit having a —COOR ⁶ (R ⁶ is an alkyl group having 1 to 3 carbon atoms) group (hereinafter referred to as “vinyl-based monomer unit (B The content of “)” is also preferably 5% by mass or less based on 100% by mass of all the monomer units of the acid group-containing polymer. When the content of the vinyl-based monomer unit (B) is 5% by mass or less, the hydrophobicity of the cured product is further enhanced, and the suppression of water unevenness is further excellent. The content of the vinyl-based monomer unit (B) is more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 0% by mass.

Examples of the vinyl monomer unit (B) include monomer units derived from methyl (meth) acrylate, ethyl (meth) acrylate or propyl (meth) acrylate, and preferably (meth) It is a monomer unit derived from methyl acrylate.

(Method for producing acid group-containing polymer)
As a method for producing the above-mentioned acid group-containing polymer, at least the above-mentioned N-alkylmaleimide monomer unit and / or N-cycloalkylmaleimide monomer unit, alicyclic hydrocarbon group-containing monomer unit, and The method is not particularly limited as long as it is a method that can obtain an acid group-containing polymer having an acid group-containing monomer unit, and, for example, the above-described N-alkylmaleimide monomer and / or N-cycloalkylmaleimide monomer amount Methods of polymerizing monomer components including a monomer, an alicyclic hydrocarbon group-containing monomer, an acid group-containing monomer, and the other monomers described above as needed according to a known method Be

The method for polymerizing the above-mentioned monomer component is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used. Among them, solution polymerization is preferable in that it is industrially advantageous and the structure adjustment such as molecular weight is easy. The polymerization mechanism of the monomer component may be a polymerization method based on mechanisms such as radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, etc., but from the industrially advantageous point of view, the radical polymerization mechanism The polymerization method based on is preferred.

As a compounding quantity of the said monomer component at the time of superposition | polymerization, said N-alkyl maleimide monomer unit and / or N-cycloalkyl maleimide monomer (2-30 mass%), said alicyclic hydrocarbon group containing It is preferable to contain a monomer (10 to 40% by mass) and the above-mentioned acid group-containing monomer (5 to 25% by mass), and the above N-alkyl maleimide monomer unit and / or N-cycloalkyl maleimide Monomer (2 to 30% by mass), Alicyclic hydrocarbon group-containing monomer (10 to 40% by mass), Acid group-containing monomer (5 to 25% by mass), Vinyl monomer unit amount It is more preferable to contain body (A) (20 to 60% by mass) and the above-mentioned hydroxyl group-containing monomer (10 to 40% by mass).

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

When the above monomer components are polymerized by solution polymerization, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction, and the polymerization mechanism, type and amount of monomers used, It may be appropriately set according to the polymerization conditions such as the polymerization temperature and the polymerization concentration. When using a solvent as a diluent etc. when setting it as a curable resin composition later, it is efficient and preferable to use the solvent containing the solvent for solution polymerization of a monomer component.

As said solvent, the thing similar to the solvent as described in Unexamined-Japanese-Patent No. 2015-157909 is mentioned, Those 1 type (s) or 2 or more types can be used. Among these solvents, propylene glycol monomethyl ether, propylene, from the solubility of the obtained polymer, the surface smoothness when forming a coating film, the small influence on the human body and the environment, and the industrial availability. It is more preferable to use glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethyl lactate.

The amount of the solvent used is preferably 50 to 1000 parts by mass, more preferably 100 to 500 parts by mass, with respect to 100 parts by mass of the monomer component.

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

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and t-butyl peroxy- 2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-) Peroxides and azo compounds which are usually used as polymerization initiators such as dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methyl propionate), hydrogen peroxide and persulfate are mentioned. These may be used singly or in combination of two or more.

The amount of the polymerization initiator to be used is not particularly limited, and may be appropriately set according to the kind and amount of monomers to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and molecular weight of the target polymer. Although it is good, for example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the above-mentioned monomer component.

In the above polymerization, if necessary, a chain transfer agent may be used. Preferably, a polymerization initiator and a chain transfer agent are used in combination. The use of a chain transfer agent during polymerization tends to suppress the increase in molecular weight distribution and gelation.

As said chain transfer agent, the thing similar to the solvent as described in Unexamined-Japanese-Patent No. 2015-157909 is mentioned, 1 type (s) or 2 or more types of them can be used. Among them, mercapto carboxylic acids, mercapto carboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercapto are preferable in view of availability, crosslink preventing ability, degree of decrease in polymerization rate and the like. The compound which has mercapto groups, such as isocyanurate, is mentioned, More preferably, alkyl mercaptans, mercapto carboxylic acids, mercapto carboxylic acid esters, More preferably, n-dodecyl mercaptan and mercapto propionic acid are mentioned.

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

The polymerization temperature may be appropriately set according to the type and amount of the monomer used, the type and amount of the polymerization initiator, etc., for example, 50 to 130 ° C. is preferable. 120 ° C. is more preferred.

The acid value of the acid group-containing polymer is preferably 50 to 200 mg KOH / g, more preferably 60 to 180 mg KOH / g, and still more preferably 70 to 170 mg KOH / g.
The said acid value is a value obtained by measuring by the neutralization titration method using a KOH solution.

The weight average molecular weight of the acid group-containing polymer is not particularly limited, but preferably 2,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000.
The weight average molecular weight of the acid group-containing polymer is a value obtained by measurement according to the method described in the examples by gel permeation chromatography (GPC).

In the curable resin composition of the present invention, the content of the acid group-containing polymer is not particularly limited, and may be appropriately set according to the application, the blending of other components, etc. For example, the curable resin composition 10-70 mass% is preferable with respect to 100 mass% of solid content total amount of, 20-60 mass% is more preferable, and 20-50 mass% is still more preferable.
In addition, "solid content total amount" means the total amount of the component (except the solvent etc. which volatilize at the time of formation of hardened | cured material) which forms hardened | cured material.

<1-2. Polymerizable compound>
The curable resin composition of the present invention preferably further contains a polymerizable compound. By further including a polymerizable compound, the curability of the curable resin composition is excellent, and after curing, not only suppression of water unevenness and heat-resistant colorability but also surface hardness is high and adhesion to a substrate is high, It is possible to obtain a cured product which is also excellent in solvent resistance and heat resistance.
The polymerizable compound is a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) which can be polymerized by irradiation of active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. ) Is a low molecular weight compound. For example, monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more are mentioned.

Examples of the monofunctional polymerizable monomer include, for example, N-substituted maleimide monomers; (meth) acrylic esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; Unsaturated monocarboxylic acids in which a chain is extended between a saturated group and a carboxyl group; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated Isocyanates; and the like. Further, a monomer having an active methylene group or an active methine group can also be used.

As said polyfunctional polymerizable monomer, the following compound etc. are mentioned, for example.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexane dimethanol 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, glycerin 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 adducted trimethylolpropane tri (meth) acrylate, ethylene oxide adducted 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 hexamer (Meth) Acrylate, .EPSILON.-caprolactone added trimethylolpropane tri (meth) acrylate, .EPSILON.-caprolactone added ditrimethylolpropane tetra (meth) acrylate, .EPSILON.-caprolactone added pentaerythritol tetra (meth) acrylate, .epsilon.-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, ditriol Methylolpropane tetravinyl ether, glycerine trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide adducted trimethylolpropane trivinyl ether, ethylene oxide adducted ditrimethyene 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 acids such as p-vinyloxymethylphenyl methyl methacrylate, 2- (vinyloxyethoxy) ethyl acrylate, and 2- (vinyloxyethoxyethoxy) ethyl methacrylate 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, glycerine triaryl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide adducted trimethylolpropane triallyl ether, ethylene oxide adducted ditrimethylate 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 allyl (meth) acrylic acid; tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyl oxyethyl) isocyanurate, alkylene Multifunctional (meth) acryloyl group-containing isocyanurates such as oxide-added tri (methacryloyloxyethyl) isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. And (hydroxy) -containing (meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Multifunctional urethane (meth) acrylates obtained by reaction of a; polyfunctional aromatic vinyl compounds such as divinylbenzene; and the like. These polymerizable compounds may be used singly or in combination of two or more.

Among the above-described polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of enhancing the curability of the curable resin composition. The functional number of the polyfunctional polymerizable compound is preferably 3 or more, and more preferably 4 or more. Moreover, ten or less are preferable and, as for the said functional number, eight or less are more preferable.
Further, the molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, for example, 2000 or less is preferable.

Among the above-mentioned polyfunctional polymerizable compounds, from the viewpoint of reactivity, economy, availability, etc., polyfunctional (meth) acrylate compounds, polyfunctional urethane (meth) acrylate compounds, (meth) acryloyl group-containing isocyanates The compound which has a (meth) acryloyl group, such as a nurate compound, is preferable, and is more preferable than a polyfunctional (meth) acrylate compound. By including a compound having a (meth) acryloyl group, the curable resin composition becomes more excellent in photosensitivity and curability, and a cured product with higher hardness and higher transparency can be obtained. It is more preferable to use a trifunctional or higher polyfunctional (meth) acrylate compound as the polyfunctional polymerizable compound.

In the curable resin composition of the present invention, the content of the above-mentioned polymerizable compound is not particularly limited as long as the effects of the present invention can be exhibited, and may be appropriately set, but the curable resin composition is suitably used. The viscosity is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, still more preferably 10% by mass, based on 100% by mass of the total solid content of the curable resin composition of the present invention. It is -55 mass%.

<1-3. Photopolymerization initiator>
The curable resin composition of the present invention preferably further contains a photopolymerization initiator. By including a photopolymerization initiator, the curability of the curable resin composition can be improved, and the performance of the resulting cured product can be improved.
As a photoinitiator in this invention, Preferably a radically polymerizable photoinitiator is mentioned. A radically polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation of an active energy ray such as an electromagnetic wave or an electron beam.

The photopolymerization initiator is not particularly limited. For example, alkylphenone compounds, benzophenone compounds, benzoin compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds Known photopolymerization initiators such as oxime ester compounds, titanocene compounds, benzoate compounds, and acridine compounds can be used.
Among them, as a photopolymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one ("IRGACURE 907", manufactured by BASF), 2-benzyl-2- Alkylphenone compounds such as dimethylamino-1- (4-morpholinophenyl) -butanone-1 ("IRGACURE 369", manufactured by BASF) are preferable.
The said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the photopolymerization initiator is not particularly limited as long as the effects of the present invention can be exhibited, and may be appropriately designed. For example, the total solid content 100 of the curable resin composition of the present invention Preferably it is 2-30 mass% with respect to mass%, More preferably, it is 5-20 mass%, More preferably, it is 5-18 mass%.

Moreover, you may use together 1 type, or 2 or more types of a photosensitizer, an optical radical polymerization accelerator, etc. as needed. By using a photosensitizer and / or a photo radical polymerization accelerator together with the photopolymerization initiator, the sensitivity and the curability are further improved. The photosensitizer and the photoradical polymerization accelerator are not particularly limited, and may be appropriately selected from known ones generally used in curable resin compositions.

Examples of photosensitizers and photoradical polymerization accelerators that may be used in combination with the above-mentioned photopolymerization initiators include, for example, dye-based compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; 4-dimethylamino Examples thereof include dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; and mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole.

In the case of using the photosensitizer and the photoradical polymerization accelerator, the content thereof is 100% by mass of the total solid content of the curable resin composition from the viewpoint of the balance between the curability, the influence of the decomposition product and the economy. The amount is preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.05 to 10% by mass.

<1-4. Other ingredients>
The curable resin composition of the present invention may contain other components as necessary in addition to the (meth) acrylate polymer, the polymerizable compound, and the photopolymerization initiator described above. Other components include, for example, solvents; coloring materials (also referred to as colorants); dispersants; antioxidants; heat resistance improvers; leveling agents; developing assistants; inorganic fine particles such as silica fine particles; silanes, aluminums, Coupling agents such as titanium type; thermosetting resins such as filler, epoxy resin, phenol resin, and polyvinyl phenol; curing assistant such as polyfunctional thiol compound; plasticizer; polymerization inhibitor; ultraviolet absorber; Antifoaming agents, antistatic agents, slip agents, surface modifiers, thixotropic agents, thixotropic assistants, quinone diazide compounds, polyhydric phenol compounds, cationically polymerizable compounds, acid generators, and the like. These may be used alone or in combination of two or more. For example, when using the said curable resin composition for a color filter use, it is preferable that the said curable resin composition contains a coloring material.

(solvent)
As the above-mentioned solvent, one which is usually used in a curable resin composition can be used, and it may be appropriately selected according to the purpose and application, and it is not particularly limited, but for example, it is described in JP-A-2015-157909. The same ones as those described above can be used. These may be used alone or in combination of two or more.

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

(Color material)
Examples of the coloring material include pigments and dyes. Either the pigment or the dye may be used as the coloring material, or the pigment and the dye may be used in combination. For example, when forming red, blue, and green pixels of a color filter, it is preferable to use a known method that exhibits desired color characteristics such as blue and purple, green and yellow, etc. by appropriately combining color materials. In addition, in the case of forming a black matrix, it is preferable to use a black coloring material.

Among the coloring materials, pigments are preferable in terms of durability, and dyes are preferable in terms of improving the brightness of panels and the like. These can be suitably selected according to the characteristic calculated | required. In the curable resin composition of the present invention, a pigment is preferable in that the solvent resistance and heat resistant colorability of the cured product can be further improved. As a pigment, the thing similar to the thing as described in Unexamined-Japanese-Patent No. 2015-157909 can be used.

As the above-mentioned dye, for example, it is possible to use the organic dye described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599. it can. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable.
These colorants may be used alone or in combination of two or more.

The content of the color material is not particularly limited and may be appropriately set depending on the purpose and application, but preferably, it is preferably 0. 0 to 100% by mass of the total solid content of the curable resin composition. 1-20 mass%, More preferably, it is 1-15 mass%, More preferably, 2-12 mass% is mentioned.

(Dispersant)
When the curable resin composition of the present invention contains the above-mentioned colorant, it is preferable to further contain a dispersant.
The dispersant has an interaction site with the color material and an interaction site with the dispersion medium (for example, a solvent and a binder resin), and has a function to stabilize the dispersion of the color material in the dispersion medium. Generally, they are classified into resin type dispersants (for example, high molecular weight dispersants), surfactants (for example, low molecular weight dispersants), and dye derivatives. These may be used alone or in combination of two or more.

Examples of the resin type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, and polysiloxane A long chain polyaminoamide phosphate, a hydrogen group-containing polycarboxylic acid ester, an amide or a salt thereof formed by the reaction of poly (lower alkyleneimine) and a polyester having a free carboxyl group, (meth) acrylic acid-styrene Copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, polyesters, modified polyacrylates, ethylene oxide / polypropylene oxide adducts, etc. E It is. As a commercial item of the said resin type dispersing agent, the thing similar to the thing as described in Unexamined-Japanese-Patent No. 2015-157909 is mentioned.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate, sodium lauryl sulfate, etc .; nonionics such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate etc. Cationic surfactants 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 a dye, and 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 phthalimido groups. Examples of the structure of the base dye include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, and diketopyrrolopyrrole. And the like.

The content of the dispersant may be appropriately set according to the purpose or application, but from the viewpoint of the balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency, for example, curing It is preferable that it is 0.01-60 mass% with respect to 100 mass% of solid content total amount of the transparent resin composition. More preferably, it is 0.1-50 mass%, More preferably, it is 0.3-40 mass%.

(Antioxidant)
The curable resin composition of the present invention can further improve the heat resistant colorability of the cured product by containing the antioxidant.
The antioxidant that can be used in the present invention is not particularly limited, and a known antioxidant may be appropriately selected and used. Among them, hindered phenol-based antioxidants and phosphite ester-based antioxidants are used. Agents are preferred. These may be used alone or in combination of two or more.

As content of the said antioxidant, 0.01-5 mass% is preferable with respect to solid content 100 mass% of the said acidic radical containing polymer, and 0.05-3 mass% is more preferable.

<Preparation of a curable resin composition>
The method for preparing the curable resin composition is not particularly limited, and a known method may be used. For example, a method of mixing and dispersing each of the above-mentioned components using various mixers and dispersers is mentioned. Be The mixing / dispersing step is not particularly limited, and may be performed by a known method. Moreover, you may further include the other process normally performed. In addition, when the said curable resin composition contains a coloring material, it is preferable to prepare through the dispersion | distribution processing process of a coloring material.

In the dispersion processing step of the color material, for example, a predetermined amount of each of the color material (preferably an organic pigment), a dispersant and a solvent are weighed, and the color material is dispersed in fine particles using a disperser to make a liquid color material A method of obtaining a dispersion (also called mill base) may be mentioned. Examples of the disperser include a paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender and the like. As the above-mentioned dispersion treatment process, preferably, a method of carrying out fine dispersion treatment with a media mill such as a bead mill filled with beads of 0.01 to 1 mm after kneading and dispersion treatment with a roll mill, a kneader, a blender or the like is preferable. . Composition containing (meth) acrylate polymer, polymerizable monomer, photopolymerization initiator, and, if necessary, solvent, leveling agent, etc. separately stirred and mixed in the obtained mill base It is possible to add (preferably, a transparent liquid), mix and make a uniform dispersion solution to obtain a curable resin composition.
In addition, it is preferable to filter the obtained curable resin composition with a filter etc., and to remove fine refuse.

2. Cured Product As described above, the curable resin composition of the present invention suppresses water unevenness and gives a cured product excellent in heat-resistant colorability. Moreover, the said hardened | cured material is excellent also in basic performances, such as hardenability, developability, adhesiveness with a base material, heat resistance, and transparency. A cured product obtained by curing such a curable resin composition is also one of the present invention.

As for the film thickness, when the said hardened | cured material is a cured film, Preferably 0.1-20 micrometers is mentioned. When the film thickness is in the above-mentioned range, in addition to the suppression of water unevenness and the heat-resistant colorability, the image forming property and the surface smoothness can be excellent. The film thickness is more preferably 1 to 15 μm, and still more preferably 1 to 10 μm.

The method for obtaining a cured product using the curable resin composition of the present invention is not particularly limited, and a known method may be used. For example, the curable resin composition of the present invention is coated on a substrate, There is a method of curing the applied product by drying, heating or irradiation with energy rays such as ultraviolet rays to obtain a cured product.

The above-mentioned cured product is used, for example, for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used in liquid crystal display devices and solid-state imaging devices, electric machines and electronic devices Are preferably used. Especially, it is preferable to use for a color filter. Thus, the color filter which comprises the said hardened | cured material is also one of this invention. The color filters will be described below.

3. Color Filter The color filter of the present invention is in a form having the above-mentioned cured product on a substrate.
In the above-mentioned color filter, the cured product formed by the curable resin composition of the present invention is particularly suitable as a segment which needs coloring such as black matrix and each pixel such as red, green, blue and yellow. However, it is also suitable as a segment that does not necessarily require coloring, such as photo spacers, protective layers, orientation control ribs and the like.

Examples of the substrate used for the color filter include glass substrates such as white plate glass, blue plate glass, alkali tempered glass, silica coated blue plate glass, etc .; ring-opened polymers of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin and hydrogen thereof Sheet or film made of thermoplastic resin such as additive, film or substrate; Sheet or film made of thermosetting resin such as epoxy resin or unsaturated polyester resin, film or substrate; 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 composed of various materials such as a glass substrate (for example, a color filter for LCD) having a color material layer on the surface; and the like. Among them, in terms of heat resistance, a glass substrate, a sheet made of a heat resistant resin, a film or a substrate is preferable. The substrate is preferably a transparent substrate.
Further, if necessary, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, and the like.

4. Method of Manufacturing Color Filter In order to obtain the color filter, for example, a step (also referred to as a placement step) of placing the curable resin composition on a substrate per pixel color (that is, for each pixel of one color); A step of irradiating the curable resin composition disposed on the substrate with light (also referred to as a light irradiation step), a step of developing treatment with a developer (also referred to as a developing step), and a step of heating (also referred to as a heating step) It is preferable to adopt a manufacturing method in which the same method is repeated for each color. In addition, the formation order of the pixel of each color is not specifically limited.

4-1. Placement step (preferably coating step)
The placement step is preferably performed by coating. Examples of the method for applying the curable resin composition on a substrate include spin application, slit application, roll application, and cast application, and any method can be preferably used.
In the disposing step, it is also preferable to dry the coating film after applying the curable resin composition on the substrate. Drying of the coating can be performed using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected depending on the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the drier, etc., but it is usually carried out at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. It is suitable.

4-2. Light irradiation process As a light source of the actinic light used in the light irradiation process, for example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, A lamp light source such as a fluorescent lamp, a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, a semiconductor laser or the like is used. Further, as a method of the exposure machine, a proximity method, a mirror projection method, a stepper method may be mentioned, but a proximity method is preferably used.
In the irradiation step of the active energy ray, depending on the application, the active energy ray may be irradiated through a predetermined mask pattern. In this case, the exposed portion is cured, and the cured portion is insolubilized or poorly dissolved in the developer.

4-3. Development Step The above-mentioned development step is a step of developing with a developer after the above-mentioned light irradiation step to remove an unexposed area to form a pattern. Thereby, a patterned cured film can be obtained. The development processing can be carried out usually at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, ultrasonic development and the like.

The developer used in the development step is not particularly limited as long as it dissolves the curable resin composition of the present invention, but generally, an organic solvent or an alkaline aqueous solution is used, and a mixture of these may be used. . When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development.

As an organic solvent suitable as said developing solution, an ether solvent, alcohol solvent, etc. are mentioned, for example. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkylphenyl ethers, aralkyl phenyl ethers, diaromatic ethers And isopropanol, benzyl alcohol and the like.

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

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, sodium hydrogencarbonate and the like. Alkaline agents; amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like, which may be used alone And two or more may be used in combination.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, etc .; alkyl benzene sulfonates, alkyl naphthalene sulfonic acid Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid esters salts; amphoteric surfactants such as alkyl betaines and amino acids, etc., which may be used alone or in combination of two You may use combining the above.

4-4. Heating Step The heating step is a step (also referred to as a post-curing step) of further curing the exposed portion (cured portion) by firing after the above-described developing step. For example, using a light source such as a high pressure mercury lamp, a step of post-exposure with an amount of light of, for example, 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, It can be mentioned. By performing such a post-curing step, it is possible to make the hardness and adhesion of the patterned cured film even stronger. In addition, as described above, the carboxyl group generated by the elimination of the tertiary carbon-containing portion of the structural unit of the (meth) acrylate polymer contained in the curable resin composition as described above (the heating step described above) The cured product of the curable resin composition of the present invention obtained by reacting with the hydroxyl group of the hydroxyl group-containing monomer unit possessed by the meta) acrylate polymer to form a crosslinked structure is further excellent in the solvent resistance and the curability. It becomes a thing.

It is preferable that the film thickness of the cured film obtained by the said heating process (namely, cured film obtained by thermosetting the said curable resin composition) is 0.1-20 micrometers. By using the curable resin composition of the present invention, a cured film with a sufficiently reduced film thickness can be provided. In addition, since the film thickness is reduced, the concentration of the coloring material per unit volume of the cured film can be increased, and the luminance of the color filter can be improved. The film thickness is more preferably 1 to 15 μm, and still more preferably 1 to 10 μm.
In addition, it is preferable that the film thickness of the coating film (namely, cured film) obtained by the said heating process is 90% or less, if the film thickness of the coating film before a heating is made into 100%. More preferably, it is 80% or less, more preferably 70% or less.

In the heating step, the heating temperature is preferably 150 ° C. or more. As a result, the part derived from a part of the tertiary carbon-containing (meth) acrylate monomer is more effectively decomposed, and the above-mentioned curability and solvent resistance can be further improved. The heating temperature is more preferably 160 ° C. or more, still more preferably 170 ° C. or more, particularly preferably 180 ° C. or more. Further, the temperature is preferably 260 ° C. or less, more preferably 250 ° C. or less, and still more preferably 240 ° 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, but can be performed using, for example, a heating device such as a hot plate, a convection oven, or a high frequency heater.

5. Display Device The present invention is also a display device configured using the color filter.
In addition, the member for display apparatuses which has a hardened | cured material formed by hardening | curing the said curable resin composition, and a display apparatus are also contained in the suitable embodiment of this invention. A cured product (cured film) formed of the above-mentioned curable resin composition is stably excellent in adhesion to a base material and the like, has high hardness, exhibits high smoothness, and has high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or an 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 (hardened film) as a member for display apparatuses, the said member may be a film-like single layer or multilayer member comprised from the said cured film, or this single layer or multilayer The member may be a member in which another layer is further combined with the member described above, or a member including the above-mentioned cured film in the construction.

As described above, the curable resin composition of the present invention is less likely to cause water unevenness, and can give a cured product excellent in heat-resistant colorability. In addition, a cured product obtained by using the curable resin composition of the present invention is excellent in adhesion to a substrate, transparency and the like. Such a curable resin composition of the present invention is useful for various applications such as color filters. Moreover, the color filter and display apparatus which have a cured | curing material formed with such a curable resin composition are very useful in an optical field | area, an electric_machine | electrical_electronics field | area.

EXAMPLES The present invention will be described in more detail by way of the following examples, but the present invention is not limited to these examples. In addition, "part" shall mean "mass part" and "%" shall mean "mass%" unless there is particular notice.
Various physical properties were measured as follows in the following synthesis examples and the like.

(1) Weight average molecular weight (Mw)
Weight average molecular weight of polymer by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corp.) and column: TSKgel Super HZM-M (manufactured by Tosoh Corp.) using polystyrene as a standard substance and tetrahydrofuran as an eluent. Was measured.

(2) Solid content concentration About 1 g of a polymer solution was weighed into an aluminum cup, and about 3 g of acetone was added and dissolved, followed by natural drying at normal temperature. And after drying at 140 degreeC under vacuum for 1.5 hours using a vacuum dryer (made by EYELA, brand name: VOS-301SD), it left-to-cool in a desiccator and measured mass. The mass (solid content concentration, mass%) of the solid content (polymer) of the polymer solution was calculated from the mass loss.

(3) Accurately weigh 3 g of the acid value polymer solution, dissolve it in a mixed solvent of 90 g of acetone and 10 g of water, and use a 0.1 N KOH aqueous solution as a titration solution to make an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd. The acid value of the polymer solution was measured according to trade name: COM-555), and the acid value (mg KOH / g) per 1 g of solid content was determined from the acid value of the solution and the solid content of the solution.

Synthesis Example 1
Preparation of Polymer Solution 1 In a reaction vessel equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet, 508 parts of propylene glycol monomethyl ether acetate (PGMEA) was charged and purged with nitrogen, and then stirred. The temperature was raised to 90 ° C.
On the other hand, as a dropping tank (A), 35 parts of N-cyclohexyl maleimide (CHMI), 123 parts of t-butyl methacrylate (t-BMA), dicyclopentanyl methacrylate ("funcryl FA-513M" manufactured by Hitachi Chemical Co., Ltd.) (Hereinafter, also referred to as DCPMA) 68 parts, 70 parts of 2-hydroxyethyl methacrylate (HEMA), 54 parts of acrylic acid (AA) and t-amylperoxy-2-ethylhexanoate ("Ruperox 575" manufactured by Arkema Yoshitomi Co., Ltd.) A stirred mixture of 8 parts of L575 and 35 parts of PGMEA was prepared, and a mixed solution of 2 parts of n-dodecyl mercaptan (n-DM) and 106 parts of PGMEA was prepared in a dropping tank (B). After the temperature of the reaction tank reached 90 ° C., the dropwise addition was started over 3 hours from the dropping tank while maintaining the same temperature to carry out polymerization. Then, after maintaining at 90 ° C. for 30 minutes, 1.4 parts of L575 was added. Further, after holding at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and aging was carried out for 90 minutes to obtain a polymer solution 1.
When the obtained polymer solution 1 was analyzed, the weight average molecular weight was 21,500, the acid value was 122 mg KOH / g, and the resin solid content was 34.8 mass%.

(Composition example 2)
Preparation of Polymer Solution 2 Synthesis Example except that CHMI 25 parts, t-BMA 73 parts, DCPMA 79 parts, HDC 35 parts, HEMA 35 parts, AA 39 parts, PGMEA 25 parts, and the preparation amount of n-DM was 2 parts The same operation as in 1 was carried out to obtain a polymer solution 2.
When the obtained polymer solution 2 was analyzed, the weight average molecular weight was 20700, the acid value was 122 mg KOH / g, and the resin solid content was 34.5 mass%.

(Composition example 3)
Preparation of Polymer Solution 3 Synthesis Example except that CHMI 25 parts, t-BMA 66 parts, DCPMA 80 parts, HPMA 30 parts, AA 49 parts, PGMEA 25 parts, and the preparation amount of n-DM was 2 parts The same operation as in 1 was carried out to obtain a polymer solution 3.
When the obtained polymer solution 3 was analyzed, the weight average molecular weight was 21,600, the acid value was 155 mg KOH / g, and the resin solid content was 34.8 mass%.

(Composition example 4)
Preparation of polymer solution 4 Charged amount of monomer: CHMI 25 parts, t-BMA 88 parts, dicyclopentanyl acrylate ("Funkry FA-513AS" manufactured by Hitachi Chemical Co., Ltd., hereinafter referred to as DCPA) 49 parts, HEMA 50 A polymer solution 4 was obtained by the same operation as in Synthesis Example 1 except that 39 parts of AA, 25 parts of PGMEA, and 2 parts of n-DM were used. When the obtained polymer solution 4 was analyzed, the weight average molecular weight was 22000, the acid value was 122 mg KOH / g, and the resin solid content was 34.4 mass%.

(Composition example 5)
Preparation of polymer solution 5 The charged amount of monomers is CHMI 35 parts, t-BMA 88 parts, DCPMA 112 parts, HEMA 35 parts, HEMA 35 parts, methacrylic acid (MAA) 81 parts, PGMEA 35 parts, and the prepared amount of n-DM is 2 parts. A polymer solution 5 was obtained in the same manner as in Synthesis Example 1 except that 250 parts of PGMEA was added after ripening. When the obtained polymer solution 5 was analyzed, the weight average molecular weight was 19,900, the acid value was 145 mg KOH / g, and the resin solid content was 29.1 mass%.

Synthesis Example 6
Preparation of polymer solution 6 The charged amount of monomer is 25 parts of CHMI, 88 parts of t-BMA, 30 parts of DCPMA, 50 parts of HEMA, 58 parts of MAA, 25 parts of PGMEA, 2 parts of n-DM, and 119 parts of PGMEA after aging. A polymer solution 6 was obtained in the same manner as in Synthesis Example 1 with the exception of adding. When the obtained polymer solution 6 was analyzed, the weight average molecular weight was 19500, the acid value was 152 mg KOH / g, and the resin solid content was 30.1% by mass.

Synthesis Example 7
Preparation of polymer solution 7 The charged amounts of monomers were 25 parts of N-benzylmaleimide (BzMI), 88 parts of t-BMA, 49 parts of methyl methacrylate (MMA), 50 parts of HEMA, 39 parts of AA, 25 parts of PGMEA, A polymer solution 7 was obtained by the same operation as in Synthesis Example 1 except that the preparation amount of DM was changed to 2 parts. When the obtained polymer solution 7 was analyzed, the weight average molecular weight was 19,500, the acid value was 120 mg KOH / g, and the resin solid content was 34.5 mass%.

Synthesis Example 8
Preparation of polymer solution 8 Preparation examples of monomers except that CHMI 25 parts, t-BMA 88 parts, MMA 49 parts, HMA 50 parts, HEMA 50 parts, AA 39 parts, and PGMEA 25 parts, the n-DM preparation amount is 2 parts The same operation as in 1 was carried out to obtain a polymer solution 8. When the obtained polymer solution 8 was analyzed, the weight average molecular weight was 21100, the acid value was 121 mg KOH / g, and the resin solid content was 35.0 mass%.

Synthesis Example 9
Preparation of polymer solution 9 The prepared amount of monomer is 25 parts of BzMI, 88 parts of t-BMA, 30 parts of DCPMA, 50 parts of HEMA, 58 parts of MAA, 25 parts of PGMEA, 2 parts of n-DM, and 119 parts of PGMEA after aging. A polymer solution 9 was obtained in the same manner as in Synthesis Example 1 with the exception of adding. When the obtained polymer solution 9 was analyzed, the weight average molecular weight was 20100, the acid value was 151 mg KOH / g, and the resin solid content was 30.1% by mass.

A curable resin composition was prepared by the following method using the obtained polymer solutions 1 to 9 to evaluate the heat resistance colorability and the water unevenness.

Example 1
60 parts of polymer solution 1, 30 parts of dipentaerythritol hexaacrylate as a radically polymerizable compound, 9.8 parts of Irgacure 907 (manufactured by BASF) as a radically polymerizable photoinitiator, in terms of solid content 0.2 parts of Irganox 1010 (manufactured by BASF Corp.) as a curing agent, and a dilution solvent (PGMEA) to a solid content concentration of 20% by mass, followed by stirring to harden the curable resin composition (1-1) Obtained.

<Evaluation of heat-resistant colorability>
The thickness of the coating film after drying on an alkali free glass plate (5 cm × 5 cm, manufactured by Toshin Riko Co., Ltd.) using a spin coater is 3 μm of the curable resin composition (1-1) obtained above The solution was applied as follows, dried at 100 ° C. for 3 minutes on a hot plate, and then irradiated with ultraviolet light using an extra-high pressure mercury lamp so that the irradiation amount was 100 mJ / cm ² . After irradiation, it was further dried at 230 ° C. for 30 minutes on a hot plate to prepare a test piece. The obtained test piece is heated on a hot plate at 250 ° C. for 3 hours and cooled to room temperature, and then the b ^* value of the coated surface is measured using a spectrocolorimeter (“ZE-6000” manufactured by Nippon Denshoku Kogyo Co., Ltd.) Was measured. The results are shown in Table 2.

(Examples 2 to 6, Comparative Examples 1 to 3)
As shown in Table 2, curable resin compositions (2-1) to (9-) were operated in the same manner as in Example 1 except that polymer solutions 2 to 9 were used instead of polymer solution 1. 1) was obtained, and the heat-resistant colorability of the coating was evaluated. The results are shown in Table 2.

(Example 7)
In terms of solid content, 45 parts of polymer solution 1, 20 parts of coloring material composition (b-1), 25 parts of dipentaerythritol hexaacrylate as a radically polymerizable compound, Irgacure 907 as a radically polymerizable photopolymerization initiator Add 9.8 parts (manufactured by BASF), 0.2 parts of Irganox 1010 (manufactured by BASF) as an antioxidant, and a dilution solvent (PGMEA) to a solid concentration of 20% by mass, and stir. Thus, a curable resin composition (1-2) was obtained.
In addition, the color material composition (b-1) used here was prepared by the following method.
(Preparation of Colorant Composition (b-1))
Resin solution for dispersion (monomer composition of resin: BzMI / cyclohexyl methacrylate / methyl methacrylate / methacrylic acid = 30/30/30/10 (mass ratio), Mw: 10000, acid value: 65 mg KOH / g, in resin solution 8.3 parts by mass of solid content: 42%), 2.9 parts by mass of a dispersant (trade name "DISPERBYK-2001" manufactured by BIC Chemie Japan Ltd., non-volatile matter 1.3 g), pigment (C.I. 8.0 parts by weight of Pygmene Blue 15: 6) was weighed in a 225 ml container, and diluted with PGMEA so that the concentration of non-volatile components (solid content concentration) would be 20% by mass. To this, 64 g of zirconia beads having a diameter of 1.0 mm was added and the mixture was shaken for 3 hours with a paint shaker for dispersion treatment, and then the zirconia beads were removed by decantation to obtain a color material composition (b-1).

<Evaluation of water unevenness>
The curable resin composition (1-2) obtained above is applied on an alkali-free glass plate (10 cm × 10 cm, manufactured by Geomatec Co., Ltd.) using a spin coater so that the thickness of the coating film after drying is 3 μm. And dried at 100 ° C. for 3 minutes on a hot plate, and then irradiated with ultraviolet light using an extra-high pressure mercury lamp so that the irradiation dose would be 100 mJ / cm ² . After the exposure, the coating film was subjected to shower development by dispersing an aqueous solution of 0.04 mass% potassium hydroxide for 60 seconds with a spin developing machine. Next, the exposed area was rinsed with pure water for 10 seconds, and then the air on the glass plate surface was used to remove water on the surface of the glass plate.
The water non-uniformity (density non-uniformity) of the coating film was observed using an optical microscope (magnification: 100 times), and evaluated according to the following criteria. In the following criteria, ○ to を were considered to be practically acceptable. The results are shown in Table 3.
○: No unevenness in density is observed on the surface of the coating.
Fair: slight unevenness in density is observed on the surface of the coating film.
X: Clear unevenness in density and peeling are observed on the coating film surface.

(Examples 8 to 12 and Comparative Examples 4 to 6)
As shown in Table 3, curable resin compositions (2-2) to (9-) were prepared in the same manner as in Example 7, except that polymer solutions 2 to 9 were used instead of polymer solution 1. 2) was obtained, and the water unevenness of the coating film was evaluated. The results are shown in Table 3.

In Table 1, each component is as follows. In addition, the value of the monomer composition shown in Table 1 is the mass% of each unit amount with respect to 100 mass% of all unit units of a polymer.
BzMI: N-benzylmaleimide CHMI: N-cyclohexylmaleimide TBMA: t-butyl methacrylate MMA: methyl methacrylate DCPMA: dicyclopentanyl methacrylate DCPA: dicyclopentanyl acrylate HEMA: 2-hydroxyethyl methacrylate MAA: Methacrylic acid AA: acrylic acid

According to Tables 2 and 3, 10% by mass of N-cyclohexylmaleimide, 12 to 32% by mass of dicyclopentanyl methacrylate or dicyclopentanyl acrylate as monomeric units, and methacrylic acid or acrylic acid 15 Curable resin composition (Examples 1 to 12) containing a polymer having 5 to 23% by mass of N-cyclohexyl maleimide and dicyclopentanyl methacrylate or dicyclopentaacrylate as monomer units As compared with a curable resin composition (comparative examples 1 to 6) including a polymer having only one or both of Nil, the resulting cured product has sufficiently suppressed water unevenness, and is heat resistant It was also recognized that the coloring properties were very excellent.
As described above, the curable resin composition of the present invention has very little discoloration in heat treatment at a high temperature of 250 ° C., is extremely excellent in heat-resistant colorability, and can sufficiently suppress water unevenness. It is clear that there is.

Claims (11)

It is a curable resin composition containing an acid group containing polymer,
The acid group-containing polymer comprises 2 to 30% by mass of an N-alkylmaleimide monomer unit and / or 2 to 30% by mass of an N-cycloalkylmaleimide monomer unit, and 10 to 40% by mass of an alicyclic hydrocarbon group-containing monomer unit And a curable resin composition having 5 to 25% by mass of acid group-containing monomer units. The acid group-containing polymer is, furthermore, -COO ^* R ¹ (R ¹ is a monovalent organic group, and the carbon atom bonded to O ^* is a tertiary carbon atom.) Vinyl containing a group The curable resin composition according to claim 1, having 20 to 60% by mass of a monomer unit and 10 to 40% by mass of a hydroxyl group-containing monomer unit. 3. The curable resin composition according to claim 1, wherein the alicyclic hydrocarbon group contained in the alicyclic hydrocarbon group-containing monomer unit is a polycyclic hydrocarbon group. The vinyl-based monomer unit is a tertiary carbon-containing (meth) acrylate-based monomer unit, and 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 according to any one of claims 1 to 3, in which The curable resin composition according to any one of claims 1 to 4, wherein the content of the aromatic hydrocarbon group-containing monomer unit is 5% by mass or less in the acid group-containing polymer. In the acid group-containing polymer, the content of the vinyl-based monomer unit containing —COOR ⁶ (R ⁶ is an alkyl group having 1 to 3 carbon atoms) group is 5% by mass or less The curable resin composition according to any one of claims 1 to 5, characterized in that The curable resin composition according to any one of claims 1 to 6, wherein the N-cycloalkylmaleimide monomer unit is an N-cyclohexylmaleimide monomer unit. Furthermore, a polymerizable compound and a photoinitiator are contained, The curable resin composition in any one of the Claims 1-7 characterized by the above-mentioned. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 8. A color filter comprising the cured product according to claim 9 on a substrate. A display device comprising the color filter according to claim 10.