TWI670570B - Curable resin composition and its use - Google Patents

Abstract

The present invention provides various physical properties such as curable property, solvent resistance after curing, adhesion to a substrate (substrate), heat resistance, and transparency, and is excellent in storage stability, and can be used for a color filter or the like. A curable resin composition for various purposes. Moreover, the present invention also provides a cured product formed from such a curable resin composition, and a color filter and a display device using the cured product.

The present invention is a curable resin composition containing a (meth) acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator, and the (meth) acrylate-based polymer has three stages. A carbon (meth) acrylate monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group.

Description

Curable resin composition and use thereof

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

In the industry, various studies have been made on various applications such as optical members, motors, and electronic devices, which have been cured by heat or active energy rays, and have been developed to have excellent properties required for each application. Resin composition. An example of a specific use is a color filter, which is a main component of a liquid crystal display device or a solid-state image sensor. Generally, it is a substrate, at least three primary colors (red (R), green). (G), blue (B)) pixels, and a resin black matrix (BM) that separates them, and a protective film for covering and protecting the pixels and the resin black matrix and flattening the unevenness thereof. And the constituents.

In general, in the case of forming a pixel of a color filter using a curable resin composition, the following steps are performed for one color of a pixel, and the same steps are repeated for each color: (1) on the entire surface of the substrate a coating step of applying a curable resin composition, and (2) an exposure step of patterning the resist film formed by the coating step by patterning to cure the exposed portion, and then insolubilizing the cured portion, 3) After removing the unexposed portion by the developer, A development and calcination (baking) treatment step of calcining (baking) to further harden the exposed portion. In consideration of the application in the use of such a color filter or the like, the curable resin composition is required to have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate, heat resistance, and transparency. Therefore, for example, the methods described in Patent Documents 1 to 3 have been proposed.

[Previous Technical Literature]

[Patent Literature]

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

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-022048

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-034134

As described above, the curable resin composition is required to have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (also referred to as a substrate), heat resistance, and transparency. In addition, in recent years, the industry is promoting the miniaturization, thinning, and energy saving of optical components, motors, and electronic equipment. In response to this, high-quality performance is required for components such as color filters to be used. . For example, in the case of a color filter, there is a problem in that a colored material is eluted in a cleaning solvent in a manufacturing step as the concentration of a colored material such as a pigment or a dye becomes high. Therefore, it is required to exhibit very high solvent resistance after hardening. However, the current state of the art is that the resin composition does not sufficiently satisfy the requirements. For example, the resin composition described in Patent Documents 1 and 2 is insufficient in solvent resistance, and thus the colored material is eluted in the cleaning solvent in the production step, and the color characteristics are deteriorated. Therefore, there is an improvement in this aspect. room. Also, Patent Document 3 Although the resin composition described above has improved solvent resistance, there is still room for improvement in comprehensive properties such as adhesion and developability by further improvement.

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

The inventors of the present invention conducted various studies on a curable resin composition which can be used for various applications such as a color filter, and as a result, it has been focused on the preparation of a (meth)acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator. The resin composition is curable. Further, it has been found that the (meth) acrylate-based polymer has a constituent unit derived from a (meth) acrylate-based monomer containing tertiary carbon (also referred to as a tertiary carbon-containing (meth) group). An acrylate monomer unit), a constituent unit derived from a monomer having a hydroxyl group (also referred to as a monomer unit having a hydroxyl group), and a constituent unit derived from a monomer having an active methylene group (also referred to as having an activity) In the case of the monomer unit of the methylene group, the resin composition can be provided with a high degree of transparency, a high degree of transparency, a good adhesion to a substrate, heat resistance and high resistance. A cured product of various physical properties such as hardness. Further, it has been found that when the resin composition is used, the development time at the time of alkali development can be shortened, the productivity can be further improved, and the production cost can be reduced. Such a curable resin composition is particularly useful for color filter applications, and among them, it is particularly suitable as a resin composition for forming a pixel for a color filter. Therefore, it has been found that a cured product, a color filter, and a display device formed of such a curable resin composition are required to satisfy the requirements for high performance in recent years, and are in the field of optics. It is extremely useful in the field of motors and electronics, and it is conceived that the above problems can be completely solved, thereby completing the present invention.

Here, the (meth) acrylate type polymer contained in the curable resin composition of the present invention has a (meth) acrylate type monomer unit containing tertiary carbon, but the unit is easily decomposed by heat. For example, the tertiary carbon-containing (meth) acrylate monomer to which the monomer unit is bonded has a structure in which an oxygen atom adjacent to a (meth) fluorenyl group is bonded to a tertiary carbon atom. In the case, the OC bond between the oxygen atom adjacent to the (meth)acryl fluorenyl group and the tertiary carbon atom adjacent thereto is easily cleaved, whereby it is decomposed into (meth)acrylic acid and is produced in the third order. A stable compound on the side of the carbon atom. Therefore, for example, when the curable resin composition of the present invention is used for forming a pixel of a color filter, the third-stage carbon is included by a heating step after development (also referred to as a calcination step or a post-baking step). The (meth) acrylate monomer unit is decomposed to form a (meth)acrylic acid and a compound which is stable on the side of the tertiary carbon atom. Further, it is considered that the ester-crosslinking structure is formed between the hydroxyl group in the polymer and the ester group which may be optionally contained, and the generated (meth)acrylic acid, so that the hardening property of the resin composition and the solvent resistance after curing are drastic. Improve the ground.

In other words, the present invention is a curable resin composition containing a (meth)acrylate polymer, a polymerizable compound, and a photopolymerization initiator, and the (meth)acrylate polymer has: A tertiary carbon (meth) acrylate monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group.

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

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

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

The curable resin composition of the present invention has excellent developability and is stable It exhibits various physical properties such as hardenability, solvent resistance after hardening, adhesion to a substrate, heat resistance, and transparency, and is excellent in storage stability, and can be used for various applications such as color filters. Therefore, a color filter and a display device having a cured product (cured film) formed of such a curable resin composition are very useful in the field of optics, motors, and electronics.

The invention is described in detail below. The preferred embodiments of the present invention described below in combination with two or more (including) or more preferred embodiments are also preferred embodiments of the present invention.

In addition, the "A~B" indicating the range means "A (inclusive) or more and B (inclusive)".

[Curable resin composition]

The curable resin composition of the present invention contains a (meth) acrylate-based polymer, a polymerizable compound, and a photopolymerization initiator, and these components may be used alone or in combination of two or more. Further, one or two or more other components may be further contained as needed.

<(Meth)acrylate type polymer>

The (meth) acrylate-based polymer has a (meth) acrylate monomer unit containing a tertiary carbon, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group. Each of the constituent units may be one type or two or more types. Further, one or two or more constituent units derived from other monomers (also referred to as other monomer units) may be further contained as needed.

Hereinafter, the structure of the (meth) acrylate type polymer will be further described.

(Meth) acrylate monomer unit containing tertiary carbon

The (meth) acrylate-based monomer unit having a tertiary carbon means a constituent unit derived from a (meth) acrylate-based monomer containing a tertiary carbon, and the polymerizable carbon-carbon of the monomer The double bond (C=C) becomes a structural unit of a single bond (CC). Here, the (meth)acrylate-based single-system molecule containing a tertiary carbon has one or two (inclusive) or more (meth)acryloyl group and a tertiary carbon atom. The term "third-order carbon atom" means a carbon atom having three carbon atoms bonded to the carbon atom.

The above-mentioned tertiary carbon-containing (meth) acrylate-based monomer preferably has a structure in which an oxygen atom adjacent to a (meth) acrylonitrile group is bonded to a tertiary carbon atom. Thereby, the (meth) acrylate type monomer unit containing tertiary carbon is more easily decomposed by the heating step after development, and therefore, the hardening property of the resin composition and the solvent resistance swell after hardening as described above Improve the ground.

The (meth) acrylate-based monomer having a tertiary carbon is preferably a compound having one polymerizable carbon-carbon double bond in one molecule, that is, one (meth) acrylonitrile group in one molecule. A compound of (CH ₂ =C(R)-C(=O)-). Among them, a compound represented by the following formula (1) is more preferred.

CH ₂ =C(R)-C(=O)-OA (1)

In the formula (1), R represents a hydrogen atom or a methyl group. A represents a monovalent organic group having a structure having a tertiary carbon atom on the oxygen atom side.

In the above formula (1), the organic group represented by A may be represented, for example, by -C(R ¹ )(R ² )(R ³ ). In this case, R ¹ , R ² and R ^{3 are the} same or different, and are preferably a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, it may have a cyclic structure, and may further have a substituent. Further, R ¹ , R ² and R ³ may be bonded to each other at the terminal sites to form a cyclic structure. However, from the viewpoint of giving full play to the effect obtained by the (meth) acrylate monomer unit containing tertiary carbon, R ¹ , R ² and R ³ preferably have no cyclic structure, and Preferably, the ones are joined to each other at the end portions to form a ring structure.

Further, in the present invention, the new compound formed by cutting off the OC bond between the oxygen atom of the (meth) acrylonitrile group and the tertiary carbon atom in the adjacent A is easily volatilized as follows. In terms of the carbon number of the organic group represented by A, it is preferably 12 or less. Among them, the organic group represented by A is preferably a group derived from a group of a third butyl (meth) acrylate and/or a third pentyl (meth) acrylate. Further, the organic group represented by A may have a branched structure.

In the above-mentioned tertiary carbon-containing (meth) acrylate monomer, at least one of the adjacent carbon atoms is preferably a tertiary carbon atom bonded to an oxygen atom adjacent to the (meth) acrylonitrile group. Bonded to a hydrogen atom. For example, the (meth) acrylate monomer having a tertiary carbon is a compound represented by the above formula (1), and wherein A is -C(R ¹ )(R ² )(R ³ ) In the case of the base, at least one of R ¹ , R ² and R ³ preferably 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 OC bond between the oxygen atom adjacent to the (meth) acrylonitrile group and the tertiary carbon atom adjacent thereto is cut by heating to form (meth)acrylic acid, and at the same time, The tertiary carbon atom forms a double bond (C=C) with the carbon atom to which it is adjacent, and a new compound is formed more stably.

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

In the above (meth) acrylate-based polymer, the content ratio of the (meth) acrylate-based monomer unit containing tertiary carbon is 100% by mass based on the total amount of all the monomer units (that is, equivalent to "( The mass of the methyl acrylate polymer is 100% by mass "), preferably 5% by mass or more. Thereby, the effect of the present invention obtained from the (meth) acrylate type monomer unit containing a tertiary carbon is further exhibited. It is more preferably 15% by mass or more, and still more preferably 20% by mass or more. In addition, the upper limit of the content ratio may be appropriately set in consideration of the content ratio of the other monomer units. For example, when used in the case of a color filter, the pattern characteristics or developability are further improved. Good is 90% by mass or less. It is more preferably 75 mass% or less, further preferably 60 mass% or less.

(ii) monomer units having a hydroxyl group

The monomer unit having a hydroxyl group means a constituent unit derived from a monomer having a hydroxyl group, and the polymerizable carbon-carbon double bond (C=C) in the monomer becomes a structural unit of a single bond (CC). . By containing such a monomer unit, the curability of the curable resin composition can be improved, and a cured product excellent in solvent resistance or transparency can be provided.

The monomer having a hydroxyl group is a monomer having one or two or more hydroxyl groups in one molecule, and is preferably, for example, a hydroxyalkyl (meth)acrylate. The number of carbon atoms constituting the hydroxyalkyl group is not particularly limited, and is, for example, preferably from 1 to 20, more preferably from 1 to 12, still more preferably from 2 to 6.

Specific examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxy(meth)acrylate. Propyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (methyl) propyl 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl (meth) acrylate, and the like.

In the above (meth) acrylate-based polymer, the content ratio of the monomer unit having a hydroxyl group is, for example, 100% by mass based on the total amount of all the monomer units, preferably 5 to 50% by mass. When it is in this range, hardenability is more sufficient, and solvent resistance improves. Further, since the hydrophilicity is moderate, it is possible to sufficiently reduce the occurrence of defects during development (for example, peeling during development or roughening of the surface and whitening). More preferably, it is 10 to 40% by mass, and further preferably 15 to 35% by mass.

(iii) monomer units having an active methylene group

The monomer unit having an active methylene group means a constituent unit derived from a monomer having an active methylene group, and the polymerizable carbon-carbon double bond (C=C) in the monomer becomes a single bond (CC) The structural unit. By containing such a monomer unit, the solvent resistance and developability of the curable resin composition are good.

The monomer having an active methylene group is a monomer having one or two or more active methylene groups in one molecule, and is preferably a compound represented by the following formula (2). Thereby, the sensitivity of the curable resin composition can be further improved. Thus, the form of the monomer having an active methylene group represented by the following formula (2) is one of preferred embodiments of the present invention.

R ¹ -XR ² -R ³ -CH ₂ -R ⁴ (2)

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

In the above formula, R ¹ and R ^{5 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may also contain a hetero atom. Among them, preferred are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, a hexyloxy group, a cyclohexyloxy group, or the following formula: The group represented by (2-9) to (2-11) is more preferably a hydrogen atom or a methyl group.

R ² represents a single bond or a hydrocarbon group having a carbon number of from 1 to 20 carbon atoms. Wherein, it is preferably a single bond, a methylene group, an ethylidene group, a propyl group, a butyl group, a propyl group, a hexyl group, a cyclohexyl group, a decyl group, a decyl group or a dodecenyl group. Is a single bond, methylene or ethyl.

Specific examples of the compound represented by the above formula (2) are, for example, compounds represented by the following formulas (3-1) to (3-16).

In the above formulae (3-1) to (3-7) and (3-16), R ^{6 is the} same or different and represents a hydrogen atom or a methyl group. That is, it may be a compound in which a constituent unit composed of a methacrylic acid group is introduced, or a compound in which a constituent unit composed of an acrylonitrile group is introduced. Among the compounds represented by the above formulas (3-1) to (3-16), 2-(methacryloxy)ethyl acetate (i.e., the above formula (3-1) is preferred. A compound represented by R ⁶ represents a methyl group).

Further, it may be used in combination with an unsaturated methyl group-containing unsaturated compound exemplified in JP-A-2007-34134.

In the above (meth) acrylate-based polymer, the content ratio of the monomer unit having an active methylene group is, for example, 100% by mass based on the total amount of all the monomer units, and preferably 3 to 40% by mass. If it is in this range, the effect of solvent resistance is especially exhibited, and developability also becomes it. In addition, when the content ratio is too large, it may become incompatible with the colored material or the polyfunctional polymerizable monomer, and tends to become white when it is made into a cured film, or may be whitened. The heat-resistant coloring property is not sufficiently exhibited, and the brightness at the time of forming a panel does not become more favorable. More preferably, it is 3 to 30% by mass, and further preferably 4 to 20% by mass.

(iv) monomer units having an acid group

The (meth) acrylate-based polymer preferably further contains a monomer unit having an acid group. The monomer unit having an acid group means a constituent unit derived from a monomer having an acid group, and a polymerizable carbon-carbon double bond (C=C) in the monomer becomes a structural unit of a single bond (CC). . For example, the acrylic unit means a constituent unit derived from acrylic acid in the case of copolymerizing or graft-polymerizing acrylic acid.

The monomer having an acid group is a monomer having one or two or more acid groups in one 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, or a sulfonic acid group. Among them, a carboxyl group or a carboxylic anhydride group is preferred, a carboxyl group is more preferred, and a (meth)acryl group is further preferred.

As the above-mentioned monomer having an acid group, (meth)acrylic acid is particularly preferable. That is, the monomer unit having an acid group is preferably a (meth)acrylic unit. As described above, the aspect in which the (meth) acrylate-based polymer further has a (meth)acrylic acid unit is one of preferred embodiments of the present invention. Further, acrylic acid is superior to methacrylic acid in terms of solvent resistance.

In the present specification, (meth)acrylic means acrylic acid and/or methacrylic acid.

Here, the acid value (AV) of the (meth) acrylate-based polymer is preferably from 20 to 300 mgKOH/g. Thereby, a cured product which exhibits more sufficient alkali solubility and is more excellent in developability can be obtained. In particular, when the acid value is within this range, the solvent resistance is further improved, and the development speed is moderate, the adhesion is further improved, or the surface roughness during development can be further suppressed. Further, by setting the content of the monomer unit (preferably (meth)acrylic acid unit) having an acid group so that the acid value is in the range, the solvent resistance is further improved. The acid value is more preferably 60 to 160 mgKOH/g.

The content ratio of the monomer unit having an acid group (preferably a (meth)acrylic acid unit) is preferably set so that the acid value of the (meth) acrylate polymer is within the above preferred range. For example, it is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more based on 100% by mass of the total of all the monomer units. Further, it is preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less.

(v) main chain ring structure

The (meth) acrylate-based polymer preferably has a ring structure as a main chain. When a polymer having a ring structure in the main chain is used as the (meth) acrylate-based polymer, heat resistance, surface hardness, and adhesion are more excellent, and, for example, temporal change after high-temperature exposure is further suppressed. can A more stable hardening property of various physical properties is exhibited. Further, in recent display devices, in order to allow various members to have strength against external impact, there is a case where a tempered glass is used as the substrate, and a polymer having a ring structure in the main chain is used as the (meth) acrylate. The polymer is very suitable because it can obtain a cured product which exhibits excellent adhesion to the tempered glass even after exposure to high temperature.

In the case where the main chain of the above (meth) acrylate-based polymer has a ring structure, the polymer is preferably, for example, a monomer having a hydroxyl group-containing (meth) acrylate monomer and having a hydroxyl group. A polymer obtained by copolymerizing a monomer having an active methylene group and a monomer component which can form a ring structure in the main chain. As described above, the monomer component more preferably further contains a monomer having an acid group (preferably (meth)acrylic acid).

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

As the monomer which can form a ring structure in the main chain, for example, an N-substituted maleimide-imide monomer or a 2,2'-(oxydimethylene) dialkyl diacrylate is preferably used. A monomer or an α-(unsaturated alkoxyalkyl)acrylate monomer (preferably an (α-allyloxymethyl)acrylic acid alkyl ester monomer) or the like. Thus, in one preferred embodiment of the present invention, the (meth) acrylate-based polymer contains a monomer unit selected from N-substituted maleimide-imide monomers, 2,2'-(oxydimethylene group). And a form of at least one monomer unit of the group consisting of a dialkyl acrylate monomer unit and an α-(unsaturated alkoxyalkyl) acrylate monomer unit.

Here, for example, if N is substituted with a maleimide-based monomer and/or a 2,2'-(oxydimethylene) dialkyl acrylate monomer and/or α- (not A saturated alkoxyalkyl) acrylate monomer can further impart heat resistance, hardness, and dispersibility of a colored material. Improve the hardened material. In particular, when a 2,2'-(oxydimethylene) dialkyl acrylate monomer and/or an α-(unsaturated alkoxyalkyl) acrylate monomer is used, heat resistant coloring can be obtained. More excellent hardened material.

The content ratio of the monomer unit which can form a ring structure in the main chain is 100% by mass based on the total amount of all the monomer units, preferably 60% by mass or less, more preferably 50% by mass ( Contains) below. In particular, it contains an N-substituted maleimide-imine monomer, a 2,2'-(oxydimethylene) dialkyl acrylate monomer, and/or an α-(unsaturated alkoxyalkylene). In the case of the acrylate-based monomer, the content ratio is preferably from 2 to 60% by mass, more preferably from 2 to 60% by mass, from the viewpoints of heat resistance, hardness, dispersibility of a colored material, development speed, transparency, and the like. ~50% by mass, further preferably 3 to 40% by mass.

Examples of the N-substituted maleimide-imine-based monomer include N-cyclohexylmethyleneimine, N-phenylmaleimide, and N-methylbutylene. Diimine, N-ethyl maleimide, N-isopropyl maleimide, N-tert-butyl maleimide, N-dodecyl Equinone imine, N-benzyl maleimide, N-naphthyl maleimide, p-methylbenzyl maleimide, p-butylbenzyl Equinone imine, p-hydroxybenzyl maleimide, o-chlorobenzyl maleimide, o-dichlorobenzyl maleimide, p-dichlorobenzyl cis One or two or more kinds of these may be used for the enedilylene imine or the like. Among them, from the viewpoint of transparency, N-phenyl maleimide or N-benzyl maleimide, more preferably N-benzylbutylene amine.

Examples of the dialkyl 2,2′-(oxydimethylidene) diacrylate monomer include 2,2′-[oxybis(methylene)]diacrylic acid and 2,2. '-[Oxy bis(methylene)] di-2-alkyl acrylate or the like. Among these, transparency or dispersion, industrial accessibility, etc. For the time, for example, 2,2'-[oxybis(methylene)]bis-2-acrylic acid dimethyl ester or the like is preferably used.

Examples of the α-(unsaturated alkoxyalkyl)acrylate monomer include α-allyloxymethacrylic acid, α-allyloxymethyl methacrylate, and α-allyloxyl. Ethyl methacrylate, α-allyloxypropyl n-propyl methacrylate, α-allyloxy isopropyl methacrylate, α-allyloxy methacrylate n-butyl ester, α-allyl Dibutyl oxymethacrylate, tert-butyl α-allyloxymethacrylate, n-amyl α-allyloxymethyl methacrylate, second amyl ester of α-allyloxymethyl methacrylate And α-allyloxymethacrylic acid third amyl ester, α-allyloxymethyl methacrylate neopentyl ester and the like. Further, an (α-methacryloxymethyl) acrylate alkyl ester monomer or the like is also preferable. Among them, an (α-allyloxymethyl) acrylate alkyl ester monomer is preferred.

Further, α-(unsaturated alkoxyalkyl)acrylic acid (for example, α-allyloxymethacrylic acid) is not an acrylate, but is included in the “α-(unsaturated alkoxylate) described in the present specification. Among the alkyl group) acrylate monomers.

The (α-allyloxymethyl) acrylate alkyl ester monomer is preferably (α-allyloxymethyl) from the viewpoints of transparency, dispersibility, ease of industrial availability, and the like. Base) methyl acrylate and the like.

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

(vi) other monomer units

Further, for example, in order to adjust developability, solvent solubility, and the like, the (meth) acrylate-based polymer may contain one or two or more kinds of (meth) acrylates derived from the above-mentioned monomers. a constituent unit of a monomer (also referred to as a (meth) acrylate monomer unit), a constituent unit derived from an aromatic vinyl monomer (also referred to as an aromatic vinyl monomer unit), and/or a source Co-aggregation from other The constituent unit of the monomer (also referred to as other copolymerizable monomer units).

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

Further, examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. N-butyl (meth)acrylate, second butyl (meth)acrylate, n-amyl (meth)acrylate, second amyl (meth)acrylate, n-hexyl (meth)acrylate, (methyl) 2-ethylhexyl acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid Lauryl ester, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- ethoxy (meth) acrylate Ethyl ethyl ester, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethyl (meth)acrylate Aminoethyl ester, α-hydroxymethyl methacrylate, α-hydroxyethyl methacrylate, α-hydroxy methacrylate tert-butyl ester, α-hydroxy methacrylic acid third amyl ester, etc. Listed: 1,4-dioxaspiro[4,5]indole-2-ester, (meth)propenyl fluorenylmorphine, tetrahydrofurfuryl acrylate, 4-(methyl) propylene oxime Methyl-2-methyl-2-ethyl-1,3-dioxopentane, 4-(methyl)propenyloxymethyl-2-methyl-2-isobutyl-1, 3-dioxopentacyclohexane, 4-(meth)acryloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxopentane, 4-(methyl)propene oxime Methyl-2,2-dimethyl-1,3-dioxopentane and the like. Among them, methyl (meth) acrylate, ethyl (meth) acrylate or (meth) acrylate is preferred in terms of easily obtaining heat resistance, dispersibility of colored material, and balance of solvent resolubility. An alkyl (meth)acrylate such as an ester such as an ester or an aralkyl (meth)acrylate such as benzyl (meth)acrylate.

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

The other copolymerizable monomer is not particularly limited, and examples thereof include N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and the like (methyl). Acrylamide; polystyrene, poly(methyl) methacrylate, polyethylene oxide, polypropylene oxide, polyoxyalkylene, polycaprolactone, polycaprolactam equal to polymer molecular chain Giant monomers having a (meth)acryl fluorenyl group at one end; conjugated dienes such as 1,3-butadiene, isoprene, chloroprene, etc.; vinyl acetate, vinyl propionate, butyl Vinyl esters such as vinyl acetate and vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-decyl vinyl ether, lauryl ethylene Ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl ethylene Ether, 4-hydroxybutyrate Vinyl ethers such as vinyl ether; N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinylimidazole, N-vinylmorphine, N-vinylacetamide, etc. Base compound; unsaturated isocyanate such as (meth)acrylic acid isocyanate ethyl ester or allyl isocyanate.

The (meth) acrylate-based polymer is preferably, for example, a monomer component containing a (meth) acrylate-based monomer having a tertiary carbon, a monomer having a hydroxyl group, and a monomer having an active methylene group. A polymer obtained by carrying out polymerization. The monomer component may further contain one or two or more other monomers as needed. The monomer component preferably further contains a monomer having an acid group (particularly (meth)acrylic acid) and a monomer capable of forming a ring structure in the main chain as described above. Each of the monomers may be used alone or in combination of two or more.

The blending ratio (% by mass) of the monomer to be polymerized, that is, the content ratio of each monomer to 100% by mass based on the total of all the monomer components is preferably set to be relative to all the monomer units described above. The content ratio of each monomer unit in a total amount of 100% by mass is the same. In particular, the monomer component is preferably a (meth)acrylate monomer (a) having a tertiary carbon, a monomer having a hydroxyl group (b), and a monomer (c) having an active methylene group. An acid group monomer (particularly (meth)acrylic acid) (d), a monomer (e) which can form a ring structure in the main chain, and other monomers (f) other than those as needed (for example, Preferably, the other (meth) acrylate monomer) is preferably such that the mass ratio (a/b/c/d/e/f) is 10 to 40/10 to 40/3 to 40/ 2~50/5~20/0~20 (where the total of a~f is set to 100% by mass). More preferably 10~40/10~40/3~40/2~50/5~20/5~20.

In addition, the polymerization conditions are appropriately set so that the acid value of the obtained (meth)acrylate polymer is 20 to 300 mgKOH/g.

As a method of polymerizing the above monomer components, block polymerization or solution polymerization can be used. A method generally used, such as a combination and an emulsion polymerization, may be appropriately selected depending on the purpose and use. Among them, solution polymerization is preferred because it is industrially advantageous and it is easy to adjust the structure such as molecular weight. Further, the polymerization mechanism of the above monomer component can be carried out by a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, and a polymerization method based on a radical polymerization mechanism is preferable because it is industrially advantageous.

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

The solvent is preferably, for example, a monoalcohol, a cyclic ether, a glycol monoether, a glycol ether, an ester of a glycol monoether, an alkyl ester, a ketone, an aromatic hydrocarbon, or a fat. One or two or more kinds of hydrocarbons and guanamines. Specific examples of such a solvent include the compounds described in Paragraph No. 0044 of JP-A-2015-42697. Among these, it is more preferable to use the polymer obtained, the surface smoothness at the time of forming a coating film, the influence on the human body and the environment, and the ease of industrial acquisition. Propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and/or ethyl lactate.

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

The polymerization starting method in the above polymerization reaction is only required to be self-heating, electromagnetic waves (for example, red An active energy source such as an external line, an ultraviolet ray, an X-ray or the like, or an electron beam may supply the monomer component with energy required for starting polymerization. Further, when a polymerization initiator is used in combination, the energy required for the start of polymerization can be greatly reduced, and the reaction can be easily controlled, which is preferable.

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

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

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, lauric acid peroxide, benzammonium peroxide, and peroxidation. Tert-butyl propylene carbonate, tert-butyl peroxy 2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2-azobis (2,4-Dimethylvaleronitrile), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, hydrogen peroxide, persulfate, etc., commonly used as a polymerization initiator for peroxidation The azo compound or the like may be used singly or in combination of two or more.

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

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

As the chain transfer agent, for example, a mercaptocarboxylic acid, a mercaptocarboxylic acid ester, an alkyl mercaptan, a mercapto alcohol, an aromatic mercaptan, a mercapto isocyanurate, a disulfide, a disulfide is preferable. One or two or more kinds of dithiocarbamate, monomeric dimer, and halogenated alkyl group. Specific examples of the chain transfer agent include the compounds described in Paragraph No. 0049 of JP-A-2015-42697. Among these, in terms of availability, resistance to crosslinking, and a small degree of reduction in polymerization rate, it is preferred to use mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercapto alcohols, A compound having a mercapto group such as an aromatic mercaptan or a mercapto isocyanurate. More preferred are alkyl mercaptans, mercaptocarboxylic acids and/or mercaptocarboxylic acid esters, and further preferably n-dodecyl mercaptan and/or mercaptopropionic acid.

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

The polymerization temperature may be appropriately set depending on the type or amount of the monomer to be used, the type or amount of the polymerization initiator, and the like, and is preferably, for example, 50 to 150 ° C, more preferably 70. ~120 °C. Further, the polymerization time can be appropriately set in the same manner, and is, for example, preferably 1 to 6 hours, more preferably 2 to 5 hours.

The average weight of the above (meth) acrylate polymer in terms of polystyrene The molecular weight is preferably from 5,000 to 100,000. When the weight average molecular weight is within this range, the coating property in the case of applying a curable resin composition containing a (meth)acrylate polymer tends to be good, and the film formation is less likely to occur during development. Therefore, it is better. More preferably 5000 (= 0.5 million) ~ 50,000. Thereby, better developability can be exhibited, and in addition, solvent resistance is improved and development speed is further improved. Further preferably, it is 10,000 to 40,000, and particularly preferably 15,000 to 30,000.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the above (meth) acrylate-based polymer is preferably from 1.1 to 6.0. When the molecular weight distribution is within this range, the developability is preferred, which is preferable. More preferably 1.2~4.0.

In the present specification, the weight average molecular weight and the number average molecular weight of the polymer can be determined by the measurement methods described in the following examples.

In the curable resin composition, the content of the (meth) acrylate-based polymer may be appropriately set according to the use or the blending of other components, for example, the solid content of the (meth) acrylate-based polymer. The total solid content of the curable resin composition is 100% by mass, preferably 5% by mass or more. Further, it is preferably 80% by mass or less. By being within such a range, the effects of the present invention can be exhibited more remarkably. More preferably, it is 7 to 70% by mass, and further preferably 10 to 60% by mass.

In addition, the total amount of the solid content of the curable resin composition means the total amount of the component forming the cured product (excluding the solvent which volatilizes when the cured product is formed) among the components of the curable resin composition.

Further, in the present invention, an acrylic polymer which is generally used in the field may be used in combination as long as the effects of the present invention are not impaired.

<Polymerizable compound>

Further, the curable resin composition contains a polymerizable compound.

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

The monofunctional polymerizable monomer is, for example, an N-substituted maleicene in a compound exemplified as another monomer which is preferably contained in the monomer component of the (meth)acrylate polymer. Amine monomer or (meth) acrylate, (meth) acrylamide, unsaturated monocarboxylic acid, unsaturated polycarboxylic acid, chain extended unsaturated monocarboxylic acid between unsaturated group and carboxyl group Examples of unsaturated anhydrides, aromatic vinyls, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, and unsaturated isocyanates. Further, a monomer having an active methylene group or an active methine group or the like can also be used.

Examples of the polyfunctional polymerizable monomer include the following compounds. Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(a) Acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide a bifunctional (meth) acrylate compound such as (meth) acrylate; trimethylolpropane tri(meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, glycerol tris(methyl) Acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (methyl) Acrylate, tricrostitol hepta (meth) acrylate, tripentenol octa (meth) acrylate, epoxy Ethane addition trimethylolpropane tri(meth) acrylate, ethylene oxide addition di-trimethylolpropane tetra(meth) acrylate, ethylene oxide addition neopentyl alcohol tetra Methyl) acrylate, ethylene oxide addition dipentaerythritol hexa(meth) acrylate, propylene oxide addition trimethylolpropane tri(meth) acrylate, propylene oxide addition two - Trimethylolpropane tetra(meth)acrylate, propylene oxide addition neopentyl alcohol tetra(meth)acrylate, propylene oxide addition dipentaerythritol hexa(meth) acrylate, ε- Caprolactone addition trimethylolpropane tri(meth) acrylate, ε-caprolactone addition di-trimethylolpropane tetra(meth) acrylate, ε-caprolactone addition neopentyl a trifunctional or higher polyfunctional (meth) acrylate compound such as an alcohol tetra(meth) acrylate or ε-caprolactone plus dipentaerythritol hexa(meth) acrylate; Vinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, three Hydroxymethylpropane trivinyl ether, di-trimethylolpropane tetravinyl ether, glycerol trivinyl ether, neopentyl alcohol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, Ethylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition di-trimethylolpropane tetravinyl ether, ethylene oxide addition neopentyl alcohol tetravinyl ether, ethylene oxide Addition of polyfunctional vinyl ethers such as dipentaerythritol hexavinyl ether; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-(meth)acrylate Methyl-2-vinyloxyethyl ester, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate , 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, (meth)acrylic acid Vinyloxymethylphenylmethyl ester, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)(meth)acrylate (Ethylene ether group-containing (meth) acrylates such as ethyl ester; ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, dibutyl Alcohol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, di-trishydroxyl Methylpropane tetraallyl ether, glyceryl triallyl ether, neopentyltetramethylene ether, dipentaerythritol pentamethicone, dipentaerythritol hexene propylene ether, ethylene oxide addition three Hydroxymethylpropane triallyl ether, ethylene oxide addition di-trimethylolpropane tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, ethylene oxide addition two new Polyfunctional allyl ethers such as pentaerythritol hexene ether; allyl group-containing (meth) acrylates such as allyl (meth) acrylate; tris(propylene oxy oxyethyl) isocyanurate , tris(methacryloxyethyl)isocyanurate, alkylene oxide addition of tris(propylene oxyethyl) isocyanurate, alkylene oxide addition isocyanuric acid tris(methacryl oxime) Polyfunctional (meth) acrylonitrile-containing isocyanuric acid such as oxyethyl) ester a polyfunctional allyl-containing isocyanurate such as an ester or a triallyl isocyanurate; a polyfunctional isocyanate such as toluene diisocyanate, isophorone diisocyanate or benzene dimethylene diisocyanate; a polyfunctional (meth) acrylate amine obtained by the reaction of a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl (meth) acrylate; divinyl A polyfunctional aromatic vinyl such as benzene.

Among the above-mentioned polymerizable compounds, from the viewpoint of further improving the curability of the curable resin composition of the present invention, it is preferred to use a polyfunctional polymerizable compound. When a polyfunctional polymerizable compound is used as the polymerizable compound, the number of the functional groups is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more. Further, from the viewpoint of further suppressing the curing shrinkage, the number of functional groups is preferably 10 or less, more preferably 8 or less.

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

When a polyfunctional polymerizable compound is used as the polymerizable compound, it is preferred to use a polyfunctional (meth) acrylate compound from the viewpoints of reactivity, economy, availability, and the like in the polymerizable compound. A compound having a (meth) acrylonitrile group such as a polyfunctional (meth) acrylate compound or a (meth) acrylonitrile-containing isocyanurate compound. More preferably, the curable resin composition is more excellent in photosensitivity and curability, and a cured product having higher hardness and high transparency can be obtained. Further, it is preferred to use a trifunctional or higher polyfunctional (meth) acrylate compound.

The content ratio of the polymerizable compound is preferably set according to the type, purpose, use, and the like of the polymerizable compound or the (meth)acrylate polymer to be used, and is excellent in developability or plate-making property. In view of the solid content of the curable resin composition, the total amount of the solid content is preferably 100% by mass or more, and more preferably 80% by mass or less. The lower limit value is more preferably 5% by mass or more, further preferably 8% by mass or more, more preferably 10% by mass or more, and the upper limit is more preferably 70% by mass. It is more preferably 50% by mass or less, more preferably 30% by mass or less, and most preferably 20% by mass or less.

<Photopolymerization initiator>

The curable resin composition further contains a photopolymerization initiator.

As the photopolymerization initiator, a radical polymerizable photopolymerization initiator is preferred.

The photopolymerization initiator which is a radical polymerizable property means a polymerization initiation radical which can be generated by irradiation of an active energy ray such as an electromagnetic wave or an electron beam, and one or two or more types can be used. Often users. Further, one or two or more kinds of photosensitizers or photoradical polymerization accelerators may be used in combination as needed. The photosensitizer and/or photoradical polymerization accelerator may also be used together with the photopolymerization initiator, or may not be used. Even if the photosensitizer and/or the photoradical polymerization accelerator are not used in combination, the effects of the present invention are fully exerted, but when used in combination, the sensitivity or the curability is further improved.

Specific examples of the photopolymerization initiator include the following compounds.

2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-benzene Propane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4- [4-(2-Hydroxy-2-methylpropenyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)- 2-morpholinylpropan 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)- An alkylphenone compound such as 2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone, 4, a benzophenone compound such as 4'-bis(dimethylamino)benzophenone or 2-carboxybenzophenone; benzoin such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether Compound; 9-oxygen sulfur 2-ethyl 9-oxosulfur 2-isopropyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 9-oxosulfur Compound; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric three , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric three , 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric three , 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-symmetric three Isohalomethylated tri-line compound; 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- Diazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- Diazole, 4- Diazole, 2-trichloromethyl-5-furanyl-1,3,4- Halogenation of oxadiazole Diazole compound; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, 4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4 , 4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O -benzimidoxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-B Anthracene ester compound; an oxime ether compound; bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole- a titanocene compound such as 1-yl)-phenyl)titanium; a benzoate compound such as p-dimethylaminobenzoic acid or p-diethylaminobenzoic acid; and acridine such as 9-phenyl acridine; A compound or the like.

Among the above photopolymerization initiators, an alkylphenone compound, an oxime ester compound, and/or an oxime ether compound are preferably used. The oxime ester compound and the oxime ether compound are collectively referred to as "anthraquinone compound", and when the oxime compound is used, the curability of the curable resin composition is remarkably improved, and the solvent resistance of the obtained cured product is drastically improved. . Such an effect obtained by using a lanthanoid compound is particularly effective in the case of being used in combination with a (meth) acrylate-based polymer containing a monomer unit having an active methylene group. Thus, the form in which the photopolymerization initiator contains at least an anthraquinone compound is one of preferred embodiments of the invention. Among the lanthanoid compounds, an oxime ester compound is particularly preferred.

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

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

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

<Other ingredients>

- solvent -

Moreover, it is preferable that the said curable resin composition contains a solvent. The solvent can be preferably used as a diluent or the like. Specifically, it is preferably used for reducing the viscosity and improving workability, forming a coating film by drying, dispersing a medium as a colored material, and the like, and dissolving or dispersing each component in the curable resin composition. Low viscosity organic solvent or water.

As the above-mentioned solvent, one type or two types of ordinary users can be used, and it is not particularly limited as long as it is appropriately selected depending on the purpose and use. For example, preferred are monools, glycols, cyclic ethers, glycol monoethers, glycol ethers, esters of glycol monoethers, alkyl esters, ketones, aromatic hydrocarbons, and fats. Hydrocarbons, guanamines, water, and the like. Specific examples of such a solvent include the compounds described in Paragraph No. 0044 of JP-A-2015-42697. For example, as the ester of the glycol monoether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether B Acid ester, diethylene glycol monoethyl ether Acid ester, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Acetate, dipropylene glycol monobutyl ether acetate, 3-methoxyacetic acid butyl ester, and the like.

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

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

- colored materials -

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

In the above-mentioned pigments and dyes, for example, in terms of durability, pigments (for example, organic pigments or inorganic pigments) are excellent, and, for example, in terms of improvement in brightness of a panel or the like, the dye is excellent, and therefore, The required characteristics may be appropriately selected or used in combination. Further, among the pigments, organic pigments are more preferred.

Examples of the pigment include an azo pigment, a phthalocyanine pigment, and a polycyclic pigment (for example, quinacridone, anthraquinone, perinone, or isoindolinone). Isoporphyrin system, two Organic pigments such as phthalic acid, thioindigo, lanthanide, quinoxaline, metal complex, diketopyrrolopyrrole, etc., dye lake pigments; white-physical pigments (eg titanium oxide, oxidation) Zinc, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (such as chrome yellow, cadmium, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, iron colcothar) , zinc chromate, lead dan, ultramarine blue, iron blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), black pigments (such as carbon black, bone black, graphite, iron black, titanium black, etc.), flash materials Inorganic pigments such as pigments (for example, pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (for example, zinc sulfide, barium sulfide, barium aluminate, etc.). Further, examples of the color of the pigment that can be used include yellow, red, purple, blue, green, brown, black, white, and the like.

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

Specific examples of the pigment include, for example, C.I. Pigment Yellow 1, 138 and the like yellow pigments described in paragraphs 0103 to 0107 of JP-A-2015-42697; C.I. Orange pigment such as pigment orange 1; purple pigment such as CI pigment violet 1; red pigment such as CI pigment red 1; blue pigment such as CI pigment blue 1; green pigment such as CI pigment green 1, 58; brown pigment such as CI pigment brown 5; Black pigment such as aniline black, carbon black, lamp black, bone black, black iron, titanium black, CI pigment black 1, etc.; white pigment such as CI pigment white 1. However, the colored materials of the present invention are not limited to these. Further, the pigments may be used singly or in combination of two or more. "C.I." means the color index (C.I.; The Society of Dyers and Colourists), and the number means the color index number.

For the dyes, for example, the organic dyes described in JP-A-2010-103833, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599 can be used. Among them, an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone imine dye, a quinoline dye, a nitrate dye, a carbonyl dye, a methine dye, or the like is preferable.

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

-Dispersant-

The dispersant has a function of interacting with a dispersing medium (for example, a solvent or a binder resin) and a function of stabilizing the dispersion of the colored material with respect to the dispersion medium, and is generally classified as A resin type dispersant (for example, a polymer dispersant), a surfactant (for example, a low molecular dispersant), and a dye derivative. The curable resin composition of the present invention preferably contains a colored material and a dispersing agent. Further, as a dispersing agent (that is, a resin type dispersing agent, a surfactant, and/or a dye derivative), a commonly used dispersing agent can be used. Again, as a dispersion The agent may be used alone or in combination of two or more.

Examples of the resin-type dispersant include polycarboxylates such as polyurethanes and polyacrylates, unsaturated polyamines, polycarboxylic acids, polycarboxylates, polycarboxylates, and polycarboxyalkylamines. Salt, polyoxyalkylene, long-chain polyamine phthalamide phosphate, hydrogen-containing polycarboxylate, formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group Amine or a salt thereof, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidine Ketones, polyesters, modified polyacrylates, ethylene oxide/polypropylene oxide adducts, and the like.

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

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

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

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

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

- Heat resistance improver -

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

- Leveling agent -

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

- coupling agent -

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

-Development aids -

The above development aid can be preferably used for improving developability. As the developing assistant, for example, monocarboxylic acids such as (meth)acrylic acid, acetic acid, and propionic acid; maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, and trimellitic acid are preferable. A polycarboxylic acid, a carboxylic acid anhydride such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride or trimellitic anhydride.

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

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

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

[hardened material]

The curable resin composition of the present invention can provide a cured product excellent in basic properties such as excellent photosensitivity and curability, developability, solvent resistance, adhesion to a substrate, heat resistance and transparency. Moreover, such cured product is also excellent in image formability and surface smoothness, and for example, there is no residue or light in the unexposed portion after development. The cured product obtained by hardening the above-mentioned curable resin composition is one of the inventions.

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

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

[Color Filter]

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

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

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

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

[Manufacturing method of color filter]

In order to obtain the color filter described above, for example, a method of performing the following steps on a color of a pixel (that is, each pixel of one color) is performed, and a method of repeating the same steps is repeated for each color: the above configuration is performed on the substrate. a step of the curable resin composition (also referred to as a disposing step), a step of irradiating light to the curable resin composition disposed on the substrate (also referred to as a light irradiation step), and a step of developing treatment by the developer ( Also referred to as a development step), and a step of performing a heat treatment (also referred to as a heating step). Furthermore, the order in which the pixels of the respective colors are formed is not particularly limited.

- configuration step (preferably coating step) -

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

Moreover, in the above arrangement step, it is preferred to apply the curable resin composition onto the substrate and then dry the coating film. Drying of the coating film can be carried out, for example, using a hot plate, an IR oven, a convection oven, or the like. The drying conditions can be appropriately selected depending on the boiling point of the solvent component contained, the kind of the hardening component, the film thickness, the performance of the dryer, and the like, and it is usually preferably carried out at a temperature of 50 to 160 ° C for 10 seconds to 300 seconds.

- Light irradiation step -

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

Further, in the step of irradiating the active energy light, the active energy ray may be irradiated through a predetermined mask pattern according to the use. In this case, the exposed portion is hardened to make the hardened portion insoluble or poorly soluble in the developer.

- development step -

The developing step is a step of forming a pattern by removing the unexposed portion by performing development processing by the developing solution after the light irradiation step. Thereby, a patterned cured film can be obtained. Development treatment can usually be carried out by immersion development, spray development, brush development, super at a development temperature of 10 to 50 ° C Method such as sound wave development is performed.

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

The organic solvent which is preferable as the developer is, for example, an ether solvent or an alcohol solvent. Specific examples thereof include dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, and triethylene glycol dialkyl ethers. Classes, alkylphenyl ethers, aralkyl phenyl ethers, diaromatic ethers, isopropanol, benzyl alcohol, and the like.

In addition to the alkali agent, the alkaline aqueous solution may optionally contain a surfactant, an organic solvent, a buffer, a dye, a pigment, or the like. As the organic solvent in this case, an organic solvent or the like which is preferable as the above developing solution can be mentioned.

Examples of the alkaline agent include inorganic bases such as sodium citrate, potassium citrate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, disodium hydrogen phosphate, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate. Amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. They may be used alone or in combination of two or more.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as benzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinates; alkyl betaines, amines An amphoteric surfactant such as an acid may be used alone or in combination of two or more.

- heating step -

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

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

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

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

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

[display device]

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

Furthermore, in a preferred embodiment of the present invention, a member for a display device and a display device having a cured product formed of the curable resin composition are also included. The cured product (cured film) formed of the curable resin composition is stable, has excellent adhesion to a substrate or the like, has high hardness, exhibits high smoothness, and has high transmittance, and is therefore particularly suitable. As a transparent member, it can also be used 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, or the like is preferable.

In the case where the cured product (cured film) is used as a member for a display device, the member may be a film-shaped single layer or a plurality of layers composed of the cured film, or may be a single layer or multiple layers. Further, members of the other members may be combined with each other, or may be members having the cured film in the configuration.

[Examples]

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

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

<weight average molecular weight>

Polystyrene as a standard material, tetrahydrofuran as a solution, and HLC-8220GPC (manufactured by Tosoh Corporation), column: TSK gel Super HZM-M (Tosoh Corporation) The GPC (gel permeation chromatography) method was carried out to determine the weight average molecular weight.

<solid content>

About 1 g of a polymer solution (also referred to as a resin solution or a polymer solution) was weighed in an aluminum cup, and about 3 g of acetone was added thereto for dissolution, followed by natural drying at normal temperature. Further, a hot air dryer (manufactured by Espec Co., Ltd., trade name: PHH-101) was used, and dried under vacuum at 140 ° C for 1.5 hours, and then placed in a desiccator to cool, and the mass was measured. The solid content (% by mass) of the polymer solution was calculated based on the amount of mass reduction.

<acid value>

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

<Absorbance of a curable resin composition>

The curable resin composition was spin-coated on a glass substrate of 5 cm square, dried at 100 ° C for 3 minutes, exposed to light at 100 mJ using a high pressure mercury lamp, and heat-treated at 230 ° C for 30 minutes to obtain a film having a film thickness of 5 μm. Thereafter, it was immersed in 20 g of 1-methyl-2-pyrrolidone at 85 ° C for 10 minutes, and 1-methyl-2-pyrrolidine which was eluted from the coating film by a spectrophotometer UV 3100 (manufactured by Shimadzu Corporation) was used. The hue of the ketone was measured, and the absorbance at 450 nm was determined.

Synthesis Example 1

Synthesis of Resin Solution 1 (BzMI-t-BMA-MMA-HEMA-AAEM-AA Copolymer Solution 1)

The reaction with a thermometer, a mixer, a gas introduction tube, a cooling tube, and a drip channel introduction port Into the tank, 156.3 parts of propylene glycol monomethyl ether acetate was added, and after nitrogen substitution, the mixture was heated and heated to 90 °C. On the other hand, 10 parts of N-benzyl maleimide, 35 parts of butyl methacrylate, and 17.1 parts of methyl methacrylate were mixed and stirred in a beaker as a dropping tank (A). 20 parts of 2-hydroxyethyl methacrylate, 5 parts of 2-ethyl acetoxyethyl methacrylate, 12.9 parts of acrylic acid and tert-butyl 2-ethylhexanoate peroxide (manufactured by Nippon Oil & Fats Co., Ltd.) "Perbutyl O") was prepared in two parts, and was prepared by mixing and mixing 0.6 parts of n-dodecyl mercaptan and 29.4 parts of propylene glycol monomethyl ether acetate in a dropping tank (B). After the temperature of the reaction tank became 90 ° C, the polymerization was carried out by dropwise addition from the dropping tank for 3 hours while maintaining the same temperature. After completion of the dropwise addition, the mixture was kept at 90 ° C for 30 minutes, and then heated to 115 ° C, and aged for 90 minutes.

The polymer solution obtained was analyzed, and as a result, the weight average molecular weight was 19,500, the acid value was 100 mgKOH/g, and the resin solid content was 34.7% by mass.

Synthesis Example 2

Synthesis of Resin Solution 2 (BzMI-t-BMA-MMA-HEMA-AAEM-AA Copolymer Solution 2)

The amount of the monomer added was 10 parts of N-benzyl maleimide, 32.1 parts of butyl methacrylate, 10 parts of methyl methacrylate, and 20 parts of 2-hydroxyethyl methacrylate. The same procedure as in Synthesis Example 1 was carried out to obtain a polymer solution, and the obtained polymer solution was analyzed, and the obtained polymer solution was analyzed. The weight average molecular weight was 20,000, the acid value was 100 mgKOH/g, and the resin solid content was 34.6% by mass.

Synthesis Example 3

Synthesis of Resin Solution 3 (BzMI-t-BMA-MMA-HEMA-AAEM-AA Copolymer Solution 3)

The amount of the monomer added was 10 parts of N-benzyl maleimide, 35 parts of butyl methacrylate, 7.1 parts of methyl methacrylate, and 30 parts of 2-hydroxyethyl methacrylate. The same procedure as in Synthesis Example 1 was carried out to obtain a polymer solution, and the obtained polymer solution was analyzed, and the obtained polymer solution was analyzed. The weight average molecular weight was 20,500, the acid value was 100 mgKOH/g, and the resin solid content was 34.7% by mass.

Synthesis Example 4

Synthesis of Resin Solution 4 (BzMI-t-BMA-HEMA-AAEM-AA Copolymer Solution 4)

The amount of the monomer added was 10 parts of N-benzyl maleimide, 32.1 parts of butyl methacrylate, 30 parts of 2-hydroxyethyl methacrylate, and 2-ethyl methacrylate. A polymer solution was obtained by the same operation as in Synthesis Example 1 except that 15 parts of ethoxyethyl ester and 12.9 parts of acrylic acid were used, and the obtained polymer solution was analyzed, and the weight average molecular weight was 21,000, and the acid value was obtained. The resin solid content was 34.6 mass%, which was 100 mgKOH/g.

Synthesis Example 5

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

The amount of the monomer added was 10 parts of N-benzyl maleimide, 35 parts of butyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, and 14.6 parts of methyl methacrylate. A polymer solution was obtained by the same operation as in Synthesis Example 1 except that 5 parts of 2-ethyl acetoxyethyl methacrylate and 15.4 parts of methacrylic acid were used, and the obtained polymer solution was analyzed. As a result, the weight average molecular weight was 19,300, the acid value was 100 mgKOH/g, and the resin solid content was 34.7 mass%.

Synthesis Example 6

Synthesis of Resin Solution 6 (MD-t-BMA-MMA-HEMA-AAEM-AA Copolymer Solution 6)

The same procedure as in Synthesis Example 1 except that 2,2'-[oxybis(methylene)]bis-2-methyl acrylate (MD) was used instead of N-benzyl maleimide. The polymer solution was obtained by the operation, and the obtained polymer solution was analyzed, and as a result, the weight average molecular weight was 20,000, the acid value was 100 mgKOH/g, and the resin solid content was 34.7% by mass.

Synthesis Example 7

Synthesis of Resin Solution 7 (AMA-t-BMA-MMA-HEMA-AAEM-AA Copolymer Solution 7)

A polymer solution was obtained by the same operation as in Synthesis Example 1, except that (α-allyloxymethyl) acrylate (AMA) was used instead of N-benzyl succinimide. The polymer solution was analyzed and found to have a weight average molecular weight of 19,000, an acid value of 100 mgKOH/g, and a resin solid content of 34.7% by mass.

Synthesis Example 8

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

The amount of the monomer added was 10 parts of N-benzyl maleimide, 35 parts of butyl methacrylate, 22.1 parts of methyl methacrylate, and 20 parts of 2-hydroxyethyl methacrylate. In the same manner as in Synthesis Example 1, except that the polymer solution was obtained, the obtained polymer solution was analyzed, and the weight average molecular weight was 19,000, and the acid value was 100 mgKOH/g. It is 34.7 mass%.

Synthesis Example 9

Synthesis of Resin Solution 9 (BzMI-MMA-HEMA-AAEM-AA Copolymer Solution 9)

The amount of monomer added is 10 parts of N-benzyl maleimide, methyl methacrylate The same procedure as in Synthesis Example 1 was carried out to obtain a polymer, except that 52.1 parts, 20 parts of 2-hydroxyethyl methacrylate, 2 parts of 2-ethyl acetoxyethyl methacrylate, and 12.9 parts of acrylic acid were used. The solution was analyzed for the obtained polymer solution, and as a result, the weight average molecular weight was 19,500, the acid value was 100 mgKOH/g, and the resin solid content was 34.7% by mass.

Synthesis Example 10

Synthesis of Resin Solution 10 (BzMI-t-BMA-MMA-AAEM-AA Copolymer Solution 10)

The amount of the monomer added is 10 parts of N-benzyl maleimide, 35 parts of butyl methacrylate, 37.1 parts of methyl methacrylate, 2-ethyl oxime methacrylate A polymer solution was obtained by the same operation as in Synthesis Example 1 except that 5 parts of ethyl ester and 12.9 parts of acrylic acid were used. The obtained polymer solution was analyzed, and the weight average molecular weight was 19,000, and the acid value was 100 mgKOH/ g, the resin solid content was 34.6% by mass.

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

The symbols in Table 1 are as follows.

BzMI: N-benzyl maleimide

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

AMA: (α-allyloxymethyl) acrylate

MMA: Methyl methacrylate

t-BMA: tert-butyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

AAEM: 2-Ethyl ethoxyethyl methacrylate

AA: Acrylic

MAA: Methacrylic acid

Production example 1

Production of Pigment Dispersion 1

12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a dispersing agent, 2.25 parts of CI Pigment Green 58 as a colored material, and 1.5 parts of CI Pigment Yellow 138 were mixed, and a coating oscillating machine was used. Dispersion was carried out for 3 hours, whereby Pigment Dispersion 1 was obtained.

Example 1

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

Examples 2 to 7, Comparative Examples 1 to 3

The curable resin compositions 2 to 7 and the curable resin compositions 9 to 11 were obtained in the same manner as in Example 1 except that the blending shown in Tables 2 and 3 was carried out, and then the NMP dissolution test was separately measured. The absorbance of the NMP afterwards. The results are shown in Tables 2 and 3.

Example 8 and Comparative Example 4

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

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

The curable resin composition obtained in Examples 1 to 7 contains a (meth) acrylate monomer unit having a tertiary carbon, a monomer unit having a hydroxyl group, and a monomer having an active methylene group. The polymer of the unit was used as the resin solution 1 to 7. On the other hand, the polymer of the curable resin composition obtained in Comparative Examples 1 to 3 did not have any of the monomer units. In this respect, Examples 1 to 7 are mostly different from Comparative Examples 1 to 3. In the background of the difference, the results obtained by obtaining the cured product under the same conditions and measuring the absorbance were compared, and it was found that the hardening of Comparative Examples 1 to 3 was compared with the curable resin compositions of Examples 1 to 7. The absorbance of the cured product of the resin composition is significantly larger, and the colored material is eluted from the hardened material. When the hardenability or solvent resistance of the curable composition is insufficient, the absorbance of the eluate increases due to the elution of the colored material. Therefore, according to the results of Table 2, the curable resin composition of the comparative example is compared with the examples. The hardenability and solvent resistance of the material are insufficient. Moreover, according to the comparison of Examples 1, 3, and 5 to 7 and Examples 2 and 4, it is clear that The more the AAEM unit and/or the HEMA unit is known, the more solvent resistance is improved.

If Example 8 (using the resin solution 4 containing the AAEM unit, using Irgacure OXE01 as the radical polymerizable photoinitiator) and Example 4 (using the resin solution 4 containing the AAEM unit, using Irgacure 369), In the case of Example 8, since the absorbance was remarkably low, the solvent resistance was greatly improved. On the other hand, in Comparative Example 4 (using the resin solution 8 containing no AAEM unit, Irgacure OXE01 was used as the radical polymerizable photoinitiator) and Comparative Example 1 (using the resin solution 8 containing no AAEM unit, Irgacure was used). When 369 was used as a radically polymerizable photoinitiator, it was found that the absorbance in Comparative Example 4 was slightly lower, and the solvent resistance was hardly improved. According to these results, it is clear that when a resin solution containing an AAEM unit is a fluorene-based compound (preferably an oxime ester-based compound) as a radical polymerizable photoinitiator, solvent resistance is further improved. In other words, it is known that the effect of significantly improving the solvent resistance by using an anthraquinone compound (preferably an oxime ester compound) is when a polymer containing a monomer unit having an active methylene group such as an AAEM unit is used. Unique effect.

Further, the absorbance of Example 1 (using the resin solution 1 using acrylic acid as a raw material) was lower than that of Example 5 (using a resin solution 5 using methacrylic acid as a raw material). From this, it was confirmed that the use of an acrylic polymer is more advantageous than a methacrylic polymer in terms of solvent resistance. Further, although not disclosed in the table, the cured product obtained in the examples is excellent in various physical properties such as developability, adhesion to a substrate, and heat resistance.

[Industrial availability]

The member for a display device and the display device containing the cured product formed of the curable resin composition of the present invention can be preferably used in the field of optics, motors, and electronics.

Claims (11)

A curable resin composition containing a (meth) acrylate polymer, a polymerizable compound, and a photopolymerization initiator, wherein the (meth) acrylate polymer has three stages A carbon (meth) acrylate monomer unit, a monomer unit having a hydroxyl group, and a monomer unit having an active methylene group. The curable resin composition of the first aspect of the invention, wherein the (meth) acrylate-based polymer contains a ratio of a tertiary carbon-containing (meth) acrylate monomer unit to all 100% by mass of the total amount of the monomer units is 5 to 90% by mass, and the content ratio of the monomer unit having a hydroxyl group is 5 to 50% by mass based on 100% by mass of the total of all the monomer units, and has an active methylene group. The content ratio of the monomer unit is from 3 to 40% by mass based on 100% by mass of the total of all the monomer units. The curable resin composition according to claim 1, wherein the (meth) acrylate-based polymer further has a (meth)acrylic acid unit. The sclerosing resin composition of claim 1, wherein the tertiary carbon-containing (meth) acrylate monomer has an oxygen atom adjacent to a (meth) acryl fluorenyl group and a tertiary carbon atom. Bonded structure. The curable resin composition of claim 3, wherein the tertiary carbon-containing (meth) acrylate monomer has an oxygen atom adjacent to a (meth) acryl fluorenyl group and a tertiary carbon atom. Bonded structure. The curable resin composition according to any one of claims 1 to 5, wherein the single system having an active methylene group is represented by the following formula (2), R ¹ -XR ² -R ³ -CH _{2 -} R ⁴ (2) In the formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may also contain a hetero atom; and X represents a formula (2-1) to (2-3) below. A divalent group represented by any one of them; R ² represents a single bond or a hydrocarbon group having a carbon number of 1 to 20; and R ³ represents a formula (2-4) to (2-6) a divalent group represented by either; R ⁴ represents a cyano group (-CN), a nitro group (-NO ₂ ), or a group represented by the following formula (2-7) or (2-8); ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may also contain a hetero atom; The curable resin composition according to any one of claims 1 to 5, wherein the (meth) acrylate-based polymer has a ring structure in the main chain. The curable resin composition of claim 6, wherein the (meth) acrylate-based polymer has a ring structure in the main chain. A cured product obtained by hardening a curable resin composition according to any one of claims 1 to 8. A color filter having a cured product of claim 9 on a substrate. A display device is constructed using a color filter of claim 10 of the patent application.