JP7372064B2 - Alkali-soluble resin, curable resin composition, and its uses - Google Patents

Description

The present invention relates to an alkali-soluble resin. More specifically, an alkali-soluble resin, a curable resin composition, a laminate, a color filter, and a display that can provide a cured product with excellent solvent resistance and adhesion to a substrate even under low-temperature curing conditions. Regarding equipment.

Curable resin compositions that can be cured by heat or active energy rays can be used in various applications such as color filters, inks, printing plates, printed wiring boards, semiconductor devices, and photoresists used in liquid crystal display devices, solid-state image sensors, etc. Various applications of curable resin compositions to various uses such as optical members and electrical/electronic devices have been investigated, and curable resin compositions with excellent properties required for each use have been developed. Among these applications, color filters are the main components of liquid crystal display devices, solid-state image sensors, etc., and are generally used for substrates and at least three primary colors (red (R), green (G), and blue (B)). In addition to the pixels and the resin black matrix (BM) and black column spacer (BCS) that separate them, the protective film provided to cover and protect the pixels and resin black matrix and flatten their unevenness. It is composed of

Normally, when forming pixels of a color filter using a curable resin composition, for each pixel, (1) a coating step of applying the curable resin composition to the entire surface of the substrate; The resist film is pattern-exposed through a photomask to harden the exposed areas, and then the cured areas are insolubilized; (3) the unexposed areas are removed using a developer, and then exposed by baking. A method is adopted in which a developing and baking process is performed to further harden the part, and the same process is repeated for each color.

Considering the application to such color filter applications, curable resin compositions have various properties such as curability, solvent resistance after curing, adhesion to substrates (substrates), heat resistance, and transparency. It is required to have physical properties. In addition, in recent years, optical components, electrical machinery, electronic devices, and the like have become smaller, thinner, and more energy-saving, and along with this, components such as color filters are required to have high-quality performance.

Various curable resin compositions for use in color filters and the like have been proposed so far.
For example, Patent Document 1 describes a thermosetting or radiation-curing product with excellent heat resistance obtained by copolymerizing a monomer having an oxetanyl group and a double bond in the molecule with a maleimide monomer. High molecular weight compounds have been described.
For example, Patent Document 2 describes a colored photosensitive composition containing a binder polymer which is a copolymer of a monomer having an oxetane skeleton and other monomers, a colorant, a photopolymerizable compound, and a photoinitiator. things are listed.
For example, Patent Document 3 discloses that a copolymer of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, a monomer having a specific oxetanyl group, and another olefinically unsaturated compound, and an ethylenic unsaturated compound. A radiation-sensitive resin composition containing a polymerizable compound having a saturated bond and a radiation-sensitive polymerization initiator is described.
For example, Patent Document 4 describes a radiation-sensitive composition for forming a colored layer containing a polymer having an oxetanyl group and a polymerizable unsaturated bond, a colorant, and a photopolymerization initiator.

Japanese Patent Application Publication No. 2005-330481 Patent No. 3956679 Patent No. 4269480 Patent No. 5417994

However, when a conventional alkali-soluble resin is used as a raw material for a color filter or the like together with a coloring material, there is a problem that the coloring material is eluted from the raw material into a cleaning solvent during the production of the color filter. Therefore, there has been a demand for further improvement in the solvent resistance of alkali-soluble resins.

In addition, in recent years, especially in the use of color filters, as the quality of color liquid crystal display devices and the like has increased and applications have expanded, there has been a strong demand for higher performance such as higher brightness and higher contrast of display panels. However, in the production of color filters, if the baking treatment step (post-curing step) after exposure and development is performed at a high temperature of over 200°C, discoloration such as yellowing occurs in the resulting cured product, resulting in the desired color. There was a problem that high coloring could not be achieved sufficiently. Furthermore, when the firing process is performed at high temperatures, unnecessary reactions proceed and by-products are produced, which causes a problem of deterioration of the properties of the base material and cured film. In order to suppress such unnecessary reactions and efficiently obtain a color filter having desired characteristics, it is desirable that the curing reaction proceed sufficiently even under relatively low temperature conditions. Moreover, if the curable resin composition can be cured at a relatively low temperature, the production efficiency of color filters can also be improved.

The present invention was made in view of the above-mentioned current situation, and can provide a cured product with excellent solvent resistance and adhesion to a substrate even under low-temperature curing conditions, and is suitable for applications such as color filters. It is an object of the present invention to provide an alkali-soluble resin and a curable resin composition that can be used.

The present inventor conducted various studies on alkali-soluble resins useful for applications such as color filters, and found that structural units derived from oxetanyl group-containing monomers, structural units derived from acid anhydride monomers, and hydroxyl group-containing monomers. By using a polymer having a structural unit derived from an adduct of an acid group-containing compound, a cured product with excellent solvent resistance and adhesion to the substrate can be obtained even if the post-curing process is performed at a temperature below about 200°C. The present invention has been completed based on the discovery that it is possible to provide the following properties.

That is, the present invention provides a structural unit (A) derived from an oxetanyl group-containing monomer, a structural unit (B) derived from an acid anhydride monomer, and a structure derived from an acid group-containing compound adduct of a hydroxyl group-containing monomer. It is an alkali-soluble resin characterized by having the unit (C).

The structural unit (B) is preferably a structural unit derived from an unsaturated dicarboxylic anhydride monomer.

The structural unit (C) is preferably a structural unit represented by the following general formula (3).

(In the formula, R ⁸ represents a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are the same or different and are a divalent chain or cyclic group having 1 to 12 carbon atoms which may have a substituent. represents a saturated hydrocarbon group or an unsaturated hydrocarbon group)

It is preferable that the alkali-soluble resin further has a structural unit (D) derived from an aromatic vinyl monomer.

In the alkali-soluble resin, the total content of the structural unit (B) and the structural unit (C) is preferably 30% by mass or more based on 100% by mass of all structural units of the alkali-soluble resin.

The alkali-soluble resin preferably has a theoretical polymer acid value of 40 to 300 mgKOH/g.

The present invention also provides a curable resin composition containing the above-mentioned alkali-soluble resin and a polymerizable compound.

The present invention is also a laminate characterized by having a cured product of the alkali-soluble resin described above or a cured product of the curable resin composition described above on a base material.

The present invention is also a color filter characterized by having a cured product of the alkali-soluble resin described above or a cured product of the curable resin composition described above on a substrate.

The present invention is also a display device characterized by being equipped with the above-mentioned color filter.

The alkali-soluble resin of the present invention can provide a cured product with excellent solvent resistance and adhesion to a substrate even under relatively low-temperature curing conditions. The alkali-soluble resin of the present invention and the curable resin composition containing the above-mentioned alkali-soluble resin can be used for various types of liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state image sensors, touch panel display devices, etc. It can be suitably used as an optical member or a structural member in various applications such as electrical and electronic equipment.

The present invention will be explained in detail below.
Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
Further, "(meth)acrylic acid" includes "acrylic acid" and "methacrylic acid", and "(meth)acrylate" includes "acrylate" and "methacrylate".

1. The alkali-soluble resin of the present invention comprises a structural unit (A) derived from an oxetanyl group-containing monomer, a structural unit (B) derived from an acid anhydride monomer, and an acid group-containing compound adduct of a hydroxyl group-containing monomer. It is an alkali-soluble resin characterized by having the structural unit (C).

Since the alkali-soluble resin of the present invention has the above-mentioned structure, even when the post-curing process is performed at a relatively low temperature condition of 200°C or less, it has good solvent resistance and good adhesion to the base material. can provide excellent cured products. Even when the alkali-soluble resin of the present invention is subjected to a post-curing step at a relatively low temperature, it is possible to provide a cured product with excellent solvent resistance and adhesion to the substrate because of the following: It is assumed that this is due to the following reasons.
That is, when the alkali-soluble resin of the present invention is heated to about 150° C. or higher, the acid group-containing compound that is a part of the structural unit (C) is eliminated as an acid anhydride, and a hydroxyl group is formed at the end. The hydroxyl group formed at the end of the structural unit (C) is bonded to the acid anhydride group of the structural unit (B) through an esterification reaction, and at the same time, a monovalent free acid group is removed from the structural unit (B). It is formed. Furthermore, the formed acid group and the oxetanyl group of the structural unit (A) react and bond together. Through the reaction of the structural units (A), (B), and (C), a high-density crosslinked product is formed, and a cured product with excellent solvent resistance and adhesion to the substrate can be obtained. can.

The structural units constituting the alkali-soluble resin of the present invention will be explained.
<Structural unit (A)>
The alkali-soluble resin of the present invention has a structural unit (A) derived from an oxetanyl group-containing monomer.
The alkali-soluble resin having the above structural unit (A) can be obtained by polymerizing a monomer component containing an oxetanyl group-containing monomer. For example, if an epoxy group-containing monomer is used instead of an oxetanyl group-containing monomer, the epoxy group will react with acid groups under polymerization conditions, resulting in gelation, making it impossible to obtain a sufficient amount of the desired resin. There is a risk. On the other hand, when a monomer having a more stable oxetanyl group is used, gelation is suppressed and the desired resin can be easily obtained.

Examples of the oxetanyl group-containing monomer include compounds having an oxetanyl group and a polymerizable functional group.
Examples of the oxetanyl group include a group represented by the following general formula (1).

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、同一又は異なって、水素原子又は炭素数１～４のアルキル基を表す。）

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

Examples of the polymerizable functional group include groups having a polymerizable double bond, such as a (meth)acryloyl group, a vinyl group, an allyl group, and a methallyl group. Among these, a (meth)acryloyl group is preferred in terms of high polymerizability, versatility, and supply stability.

As the above-mentioned oxetanyl group-containing monomer, for example, a monomer represented by the following general formula (2) is preferably mentioned.

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a single bond or an alkylene group having 1 to 6 carbon atoms. R ⁷ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.)

In the above general formula (2), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ⁵ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ⁶ represents a single bond or an alkylene group having 1 to 6 carbon atoms, and is preferably a single bond or an alkylene group having 1 to 3 carbon atoms.

R ⁷ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.
Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group.
Examples of the monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n- Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2 -Methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3 , 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, etc. linear or branched alkyl The following groups can be mentioned.

Examples of the monovalent alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl group.

Among these, R ⁷ is preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and even more preferably an ethyl group. .

Specific examples of the above-mentioned oxetanyl group-containing monomers include (meth)acrylic acid (3-ethyl-3-oxetanyl)methyl, (meth)acrylic acid (3-methyl-3-oxetanyl)methyl, (meth) 3-oxetanylmethyl acrylate, (3-ethyl-3-oxetanyl)ethyl (meth)acrylate, (3-methyl-3-oxetanyl)ethyl (meth)acrylate, 3-oxetanylethyl (meth)acrylate, ( (3-ethyl-3-oxetanyl)propyl (meth)acrylate, (3-methyl-3-oxetanyl)propyl (meth)acrylate, 3-oxetanylpropyl (meth)acrylate, (3-ethyl (meth)acrylate) -3-oxetanyl)butyl, (3-methyl-3-oxetanyl)butyl (meth)acrylate, 3-oxetanylbutyl (meth)acrylate, (3-ethyl-3-oxetanyl)hexyl (meth)acrylate, ( (3-Methyl-3-oxetanyl)hexyl (meth)acrylate, 3-oxetanylhexyl (meth)acrylate, (2-ethyl-3-oxetanyl)methyl (meth)acrylate, (2-methyl (meth)acrylate) -3-oxetanyl)methyl, (2-ethyl-3-oxetanyl)ethyl (meth)acrylate, (2-methyl-3-oxetanyl)ethyl (meth)acrylate, (2,2-dimethyl (meth)acrylate) -3-oxetanyl)methyl, (meth)acrylic acid (2,3-dimethyl-3-oxetanyl)methyl, (meth)acrylic acid (2,4-dimethyl-3-oxetanyl)methyl, (meth)acrylic acid (2 ,2-dimethyl-3-oxetanyl)ethyl, (meth)acrylic acid (2,3-dimethyl-3-oxetanyl)ethyl, (meth)acrylic acid (2,4-dimethyl-3-oxetanyl)ethyl, (meth) (3-ethyl-2-oxetanyl)methyl acrylate, (meth)acrylate (3-methyl-2-oxetanyl)methyl, (meth)acrylate 2-oxetanylmethyl, (meth)acrylate (3-ethyl-2) -oxetanyl)ethyl, (meth)acrylate (3-methyl-2-oxetanyl)ethyl, (meth)acrylate 2-oxetanylethyl, (meth)acrylate (2-ethyl-2-oxetanyl)methyl, (meth) (2-Methyl-2-oxetanyl)methyl acrylate, (meth)acrylic acid (2-ethyl-2-oxetanyl)ethyl, (meth)acrylic acid (2-methyl-2-oxetanyl)ethyl, (meth)acrylic acid (4-ethyl-2-oxetanyl)methyl, (4-methyl-2-oxetanyl)methyl (meth)acrylate, (4-ethyl-2-oxetanyl)ethyl (meth)acrylate, (meth)acrylic acid (4 -Methyl-2-oxetanyl)ethyl, (meth)acrylic acid (2,3-dimethyl-2-oxetanyl)methyl, (meth)acrylic acid (2,4-dimethyl-2-oxetanyl)methyl, (meth)acrylic acid (3,3-dimethyl-2-oxetanyl)methyl, (meth)acrylate (3,4-dimethyl-2-oxetanyl)methyl, (meth)acrylate (2,3-dimethyl-2-oxetanyl)ethyl, ( (2,4-dimethyl-2-oxetanyl)ethyl (meth)acrylate, (3,3-dimethyl-2-oxetanyl)ethyl (meth)acrylate, (3,4-dimethyl-2-oxetanyl (meth)acrylate) ) Ethyl etc. Among them, (meth)acrylic acid (3-ethyl-3-oxetanyl)methyl, (meth)acrylic acid (3-methyl-3-oxetanyl)methyl, and (meth)acrylic acid 3 are highly stable in supply. -Oxetanylmethyl, (3-ethyl-3-oxetanyl)ethyl (meth)acrylate, (3-methyl-3-oxetanyl)ethyl (meth)acrylate, and 3-oxetanylethyl (meth)acrylate are preferred, and the structural unit In terms of high copolymerizability with (B) and (D), (3-ethyl-3-oxetanyl)methyl methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, 3-oxetanylmethyl methacrylate , (3-ethyl-3-oxetanyl)ethyl methacrylate, (3-methyl-3-oxetanyl)ethyl methacrylate, and 3-oxetanylethyl methacrylate are more preferred.

A commercially available product may be used as the oxetanyl group-containing monomer. Examples of the above-mentioned commercial products include OXE-10 and OXE-30 (both product names, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The above-mentioned alkali-soluble resin may have only one type of the above-mentioned structural unit (A), and may have two or more types.

The content of the structural unit (A) is preferably 5 to 80% by mass, more preferably 10% by mass or more, and more preferably 15% by mass or more based on 100% by mass of the total structural units of the alkali-soluble resin. It is more preferably 75% by mass or less, even more preferably 70% by mass or less.

<Structural unit (B)>
The alkali-soluble resin of the present invention further has a structural unit (B) derived from an acid anhydride monomer.
When the above-mentioned structural unit (B) is present, it does not become an acid during development, so that the coating film formed using the alkali-soluble resin is not dissolved by the developer, and development can be suitably performed. In addition, since the ring is opened by reaction with hydroxyl groups and acid is formed when heated to about 150 to 200°C, post-curing can be performed at a lower temperature than conventional methods, and a crosslinked product with high crosslink density is formed. can do.
The alkali-soluble resin having the above structural unit (B) can be obtained by polymerizing a monomer component containing an acid anhydride monomer.

Examples of the acid anhydride monomer include maleic anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, allylsuccinic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, bicyclo[2.2.2]oct-7- Unsaturated dicarboxylic anhydride such as ene-2,3,5,6-tetracarboxylic dianhydride, 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride Monomers are preferred. Among these, maleic anhydride is more preferable as the acid anhydride monomer because it has high copolymerizability with acrylate and high supply stability.

The above-mentioned alkali-soluble resin may have only one type of the above-mentioned structural unit (B), and may have two or more types.

The content of the structural unit (B) is preferably 1 to 50% by mass, more preferably 3% by mass or more, and 5% by mass or more based on 100% by mass of the total structural units of the alkali-soluble resin. It is more preferably 40% by mass or less, even more preferably 30% by mass or less.

<Structural unit (C)>
The alkali-soluble resin of the present invention further has a structural unit (C) derived from an acid group-containing compound adduct of a hydroxyl group-containing monomer.
The alkali-soluble resin having the above structural unit (C) can be obtained by polymerizing a monomer component containing an acid group-containing compound adduct of a hydroxyl group-containing monomer.
The acid group-containing compound adduct of the hydroxyl group-containing monomer is one in which the hydroxyl group of the hydroxyl group-containing monomer is, so to speak, capped with the acid group-containing compound. Therefore, during polymerization of the monomer components, the acid group-containing compound adduct of the hydroxyl group-containing monomer does not crosslink with the acid anhydride monomer described above, and the predetermined structural units (A), (B) and An alkali-soluble resin having (C) can be obtained efficiently. In addition, in the curing process of the alkali-soluble resin, the acid group-containing compound corresponding to the cap is removed by heating to form a hydroxyl group, and this hydroxyl group reacts with the acid anhydride group of the structural unit (B) and is crosslinked. Ru.

The hydroxyl group-containing monomer is not particularly limited as long as it has a hydroxyl group and a polymerizable double bond in its molecule, but examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. Hydroxypropyl, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Preferred examples include hydroxyalkyl (meth)acrylates such as 3-hydroxypropyl, and more preferred example is 2-hydroxyethyl (meth)acrylate.

Examples of the acid group-containing compound include compounds having an acid group. Examples of the above-mentioned acid groups include functional groups that neutralize with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group. or two or more types. Among these, the acid group is preferably a carboxyl group or a carboxylic anhydride group, and more preferably a carboxylic anhydride group.

Specifically, examples of the acid group-containing compounds include carboxylic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and trimellitic acid; succinic anhydride, maleic anhydride, phthalic anhydride, and tetrahydrophthalic acid; Examples include acid anhydrides, carboxylic acid anhydrides such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, and trimellitic anhydride. Among these, carboxylic acid anhydrides are preferred.

The acid group-containing compound adduct of the hydroxyl group-containing monomer can be obtained by reacting the hydroxyl group-containing monomer with the acid group-containing compound. The above reaction is not particularly limited and can be performed by any known reaction.

Moreover, a commercially available product can also be used as the acid group-containing compound adduct of the above-mentioned hydroxyl group-containing monomer. Examples of the above-mentioned commercial products include HOA-MS (N) and Light Ester HO-MS (N) (both product names, manufactured by Kyoeisha Chemical Co., Ltd.).

As the structural unit (C), for example, a structural unit represented by the following general formula (3) is preferably mentioned.

(In the formula, R ⁸ represents a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are the same or different and are a divalent chain or cyclic group having 1 to 12 carbon atoms which may have a substituent. represents a saturated hydrocarbon group or an unsaturated hydrocarbon group)

In general formula (3), R ⁸ represents a hydrogen atom or a methyl group. From the viewpoint of copolymerizability with the structural unit (B), a methyl group is preferred.
R ⁹ and R ¹⁰ are the same or different and represent a divalent chain or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 12 carbon atoms and which may have a substituent.
Examples of the divalent chain or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group include an alkylene group, a cycloalkylene group, an arylene group, and the like.
Among these, the above-mentioned divalent chain or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group is preferable because the acid anhydride-derived unit is difficult to remove when producing an alkali-soluble resin. Alternatively, it is preferably a cyclic saturated hydrocarbon group, and more preferably a divalent chain saturated hydrocarbon group.

The divalent chain or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and preferably 2 to 6 carbon atoms. More preferred.

The divalent chain or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group may have a substituent. Examples of the above-mentioned substituents include alkyl groups having 1 to 8 carbon atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, and the like.

Among these, R ⁹ is preferably a divalent chain or cyclic saturated hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; It is more preferably a divalent chain or cyclic saturated hydrocarbon group having 1 to 8 carbon atoms, and a divalent chain saturated hydrocarbon group having 1 to 8 carbon atoms which may have a substituent. It is even more preferable that there be.

R ¹⁰ is preferably a divalent chain or cyclic saturated hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; It is more preferably a divalent chain-like or cyclic saturated hydrocarbon group having 8 carbon atoms, and more preferably a divalent chain-like saturated hydrocarbon group having 1 to 8 carbon atoms which may have a substituent. More preferred.

The above-mentioned alkali-soluble resin may have only one type of the above-mentioned structural unit (C), and may have two or more types.

The content of the structural unit (C) is preferably 1 to 60% by mass, more preferably 5% by mass or more, and 10% by mass or more based on 100% by mass of the total structural units of the alkali-soluble resin. It is more preferably 55% by mass or less, even more preferably 50% by mass or less.

In the alkali-soluble resin, the total content of the structural unit (B) and the structural unit (C) is preferably 30% by mass or more based on 100% by mass of all structural units. When the total content ratio of the structural unit (B) and the structural unit (C) is within the above range, a cured product with even better solvent resistance and adhesion to the substrate can be obtained. can.
The total content ratio of the structural unit (B) and the structural unit (C) is more preferably 35% by mass or more, and even more preferably 40% by mass or more based on 100% by mass of all structural units. .
Further, the upper limit of the total content ratio of the structural unit (B) and the structural unit (C) is preferably 70% by mass or less, and 65% by mass or less based on 100% by mass of the total structural units. It is more preferable that the amount is 60% by mass or less, and even more preferably 60% by mass or less.

<Structural unit (D)>
It is preferable that the alkali-soluble resin further has a structural unit (D) derived from an aromatic vinyl monomer. By further including the structural unit (D), heat coloring resistance, developability, water unevenness suppressing effect, etc. can be improved.
Furthermore, when producing the alkali-soluble resin of the present invention, when an aromatic vinyl monomer is used, the acid group anhydride monomer is more easily polymerized than when the acid anhydride monomer is used alone. Become. Further, since the aromatic vinyl monomer and the acid anhydride monomer have high copolymerizability, a polymer having a more uniform composition distribution of each structural unit can be obtained.

Preferred examples of the aromatic vinyl monomer include compounds having an aromatic group and a vinyl group.

Examples of the aromatic group include groups containing a benzene ring, a naphthalene ring, etc., and groups containing a benzene ring are particularly preferred. The above aromatic group may have a substituent. Examples of the above substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and the like.

Specific examples of the aromatic vinyl monomer include styrene, vinyltoluene, α-methylstyrene, xylene, methoxystyrene, ethoxystyrene, etc. Among them, the aromatic vinyl monomer is said to improve heat decomposition resistance. In this respect, styrene and vinyltoluene are preferable, and vinyltoluene is more preferable because it has a higher dissolution rate in organic solvents and alkalis.

The alkali-soluble resin may have only one type of the structural unit (D), or may have two or more types of the structural unit (D).

The content of the structural unit (D) is preferably 1 to 40% by mass, more preferably 3% by mass or more, and 5% by mass or more based on 100% by mass of the total structural units of the alkali-soluble resin. It is more preferably 35% by mass or less, even more preferably 30% by mass or less.

<Structural unit (E)>
The alkali-soluble resin of the present invention may further have another structural unit (E). Examples of the other structural units (E) include acid group-containing monomers other than the monomers into which the above-mentioned structural units (B) or (C) can be introduced, and (meth)acrylic acid ester monomers. , and structural units derived from other copolymerizable monomers.

Examples of acid group-containing monomers other than the monomers capable of introducing the above-mentioned structural units (B) or (C) include unsaturated acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid. Monocarboxylic acids; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; phosphoric acid group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical); etc. It will be done. Among these, from the viewpoint of versatility, availability, etc., the above-mentioned unsaturated monocarboxylic acids are preferred, and (meth)acrylic acid (that is, acrylic acid and/or methacrylic acid) is more preferred.

Examples of the (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, and ) n-butyl acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, t-(meth)acrylate Amyl, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate ) lauryl acrylate, stearyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N- (meth)acrylate Dimethylaminoethyl, 1,4-dioxaspiro[4,5]dec-2-ylmethacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3- Dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- Examples include (meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane.

Also, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, dicyclopentenyl (meth)acrylate , dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, pentacyclopentadecane dimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate , norbornane dimethanol di(meth)acrylate, p-menthane-1,8-diol di(meth)acrylate, p-menthane-2,8-diol di(meth)acrylate, p-menthane-3,8-diol di(meth)acrylate Acrylate, alicyclic (meth)acrylate such as bicyclo[2.2.2]-octane-1-methyl-4-isopropyl-5,6-dimethyloldi(meth)acrylate, glycidyl (meth)acrylate, methylglycidyl ( Examples include alicyclic epoxy compounds such as meth)acrylate, ethylglycidyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate.

Examples of the other copolymerizable monomers include one or more of the following compounds.
(Meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N-methylol(meth)acrylamide; Macromonomers having a (meth)acryloyl group at one end of the combined molecular chain; Conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate. Class: Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2- Vinyl ethers such as hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide; (meth) Unsaturated isocyanates such as isocyanatoethyl acrylate and allyl isocyanate; N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-t-butylmaleimide, N-dodecyl N-substituted maleimides such as maleimide, N-benzylmaleimide, and N-naphthylmaleimide; dialkyl-2,2'-(oxydimethylene) such as dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate;Diacrylates; alkyl-(α-allyloxymethyl)acrylates such as α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, alkoxyalkyl-(α-) such as methoxyethyl α-allyloxymethyl acrylate; α-(unsaturated alkoxyalkyl)acrylates such as allyloxymethyl)acrylate; and the like.

The above-mentioned alkali-soluble resin may have only one type of the above-mentioned structural unit (E), or may have two or more types.

In the alkali-soluble resin, the content ratio of the structural unit (E) can be appropriately set depending on the use of the alkali-soluble resin, but based on 100% by mass of the total structural units of the alkali-soluble resin, It is preferably 1 to 50% by mass, more preferably 5% by mass or more, even more preferably 10% by mass or more, more preferably 45% by mass or less, and 40% by mass or less. More preferably.

The theoretical polymer acid value of the alkali-soluble resin is preferably 40 to 300 mgKOH/g, more preferably 50 to 250 mgKOH/g, and even more preferably 60 to 200 mgKOH/g.
In this specification, the above-mentioned "theoretical polymer acid value" means a calculated acid value that does not include the divalent carboxylic acid derived from the unsaturated dicarboxylic anhydride monomer of the above-mentioned structural unit (B). In other words, it is the theoretical acid value of the total of acid groups derived from the above structural unit (C) (when the above structural unit (E) is included, the above structural units (C) and (E)), and the acid value per polymer. It is. Specifically, it can be calculated based on the following formula.
Theoretical polymer acid value (mgKOH/g) = [number of moles of acid groups derived from structural units (C) and (E) (mmol)] x 56.11/[monomer charge amount (g)]
Here, the above-mentioned "monomer charge amount" is the total amount of monomer components.

In addition to the above-mentioned theoretical polymer acid value, a value obtained by measurement by a neutralization titration method using a KOH solution is referred to as a "solution acid value." The difference between the above solution acid value and the above theoretical polymer acid value is that the solution acid value includes the acid value of divalent carboxylic acid due to ring opening of the structural unit (B) derived from the acid anhydride monomer. be. Specifically, the solution acid value can be determined by measuring by the method described in Examples.
The solution acid value of the alkali-soluble resin is preferably 20 to 250 mgKOH/g, more preferably 30 to 200 mgKOH/g, and even more preferably 40 to 150 mgKOH/g.

Further, the above solution acid value is an actually measured acid value calculated by a neutralization titration method using a KOH solution, but it can be approximately estimated by the following formula.
Solution acid value (mgKOH/g) ≒ [total number of moles (mmol) of divalent acid groups derived from structural unit (B) and acid groups derived from structural units (C) and (E)] x 56.11/[ Total amount of preparation (g)]
Here, the above-mentioned "total charge amount" is the amount of the polymerization solution including monomer components, initiator, solvent, etc.

The weight average molecular weight of the alkali-soluble resin is not particularly limited, but is preferably from 2,000 to 100,000, more preferably from 3,000 to 70,000, even more preferably from 4,000 to 40,000.
The weight average molecular weight is a value determined by gel permeation chromatography (GPC), and specifically, it can be determined by the method described in Examples.

The alkali-soluble resin may have a double bond in its side chain. When the alkali-soluble resin has a double bond in the side chain, developability and curability can be improved.
The double bond equivalent of the alkali-soluble resin is preferably 350 to 4,500 g/equivalent, more preferably 400 to 4,000 g/equivalent, and even more preferably 450 to 3,500 g/equivalent.

In this specification, the double bond equivalent is a measure of the amount of double bonds contained in a molecule, and means the molecular weight per double bond of a polymer. For compounds with the same molecular weight, the larger the double bond equivalent value, the smaller the amount of double bonds introduced.
The double bond equivalent can be calculated from the amount of raw materials charged, and can be determined by dividing the mass (g) of the solid content of the polymer by the amount (mol) of double bonds in the polymer. Moreover, it can also be measured using various analyzes such as titration, elemental analysis, NMR, and IR, and differential scanning calorimetry.

<Method for producing alkali-soluble resin>
The method for producing the alkali-soluble resin of the present invention is not particularly limited as long as it can obtain a polymer having at least the above-mentioned structural units (A), (B), and (C), and for example, A monomer component containing a monomer capable of introducing the above-mentioned structural units (A), (B) and (C) and a monomer capable of introducing any other structural unit is polymerized by a known method. One method is to do so. The amount of the monomer can be adjusted as appropriate so that the content of each structural unit in the polymer falls within a desired range.

The method of polymerizing the above monomer components is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Among these, solution polymerization is preferred because it is industrially advantageous and allows easy structural adjustment such as molecular weight. Furthermore, as the polymerization mechanism of the above monomer components, polymerization methods based on mechanisms such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization can be used; Polymerization methods based on are preferred.
Furthermore, the molecular weight of the polymer obtained by polymerizing the above monomer components can be controlled by adjusting the amount and type of polymerization initiator, the polymerization temperature, the type and amount of chain transfer agent, and the like.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy- 2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis( Examples include peroxides and azo compounds commonly used as polymerization initiators, such as 2-methylpropionate), hydrogen peroxide, and persulfates. These may be used alone or in combination of two or more.
The amount of the polymerization initiator added can be appropriately determined by a known method.

Examples of the chain transfer agent include those similar to the solvents described in JP-A-2015-157909, and among them, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkylmercaptans, and mercaptoalcohols are preferable. , aromatic mercaptans, mercaptoisocyanurates, and other mercapto group-containing compounds, more preferably alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, still more preferably n-dodecylmercaptan, mercaptopropion. Examples include acids. These may be used alone or in combination of two or more.
The amount of the chain transfer agent added can be appropriately determined by a known method.

Regarding the above polymerization conditions, the polymerization temperature may be appropriately set depending on the type and amount of the monomer used, the type and amount of the polymerization initiator, etc., but for example, 50 to 130°C is preferable, and 60 to 60°C. 120°C is more preferred. Further, the polymerization time can be similarly set appropriately, and for example, 1 to 5 hours is preferable, and 2 to 4 hours is more preferable.

As a method for producing an alkali-soluble resin having a double bond in a side chain, for example, (1) an epoxy group-containing monomer is added to a polymer (base polymer 1) obtained by polymerizing the above-mentioned monomer components. (2) adding an acid group-containing monomer to a polymer (base polymer 2) obtained by polymerizing a monomer component other than the acid group-containing monomer and an epoxy group-containing monomer; Examples include a method of causing a reaction. Among these, method (1) in which an epoxy group-containing monomer is added to the base polymer 1 is preferred from the viewpoint of production efficiency with respect to introduction of acid groups.

In the above method (1), part of the acid groups contained in the base polymer 1 is subjected to an addition reaction with an epoxy group-containing monomer. The reaction method is not particularly limited, and any known method may be adopted as appropriate, but it is preferable, for example, to set the reaction temperature to 60 to 140°C. Further, it is preferable to use known catalysts such as amine compounds such as triethylamine and dimethylbenzylamine; ammonium salts such as tetraethylammonium chloride; phosphonium salts such as tetraphenylphosphonium bromide; and amide compounds such as dimethylformamide.

Examples of the above-mentioned epoxy group-containing monomers include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (meth) ) (3,4-epoxycyclohexyl)methyl acrylate, vinylcyclohexene oxide, etc., among which glycidyl (meth)acrylate is preferred.

The amount of the epoxy group-containing monomer used in the above addition reaction is preferably set appropriately so that the acid value and double bond equivalent fall within the desired range. The amount is preferably 1 to 60 parts by weight, more preferably 2 to 55 parts by weight, and still more preferably 3 to 50 parts by weight, based on a total of 100 parts by weight.

The method for producing the alkali-soluble resin may include steps other than the polymerization reaction step. Examples include an aging step, a neutralization step, a deactivation step of a polymerization initiator or a chain transfer agent, a dilution step, a drying step, a concentration step, a purification step, and the like. These steps can be performed by known methods.

2. Curable resin composition A curable resin composition can be obtained by containing the above-mentioned alkali-soluble resin and polymerizable compound. Since the above-mentioned curable resin composition contains the above-mentioned alkali-soluble resin, it has excellent solvent resistance and adhesion to the substrate even when the post-curing step is performed at a relatively low temperature of 200°C or less. A cured product can be obtained. Further, by further containing a polymerizable compound, the curability of the resin composition can be improved, and a cured product having better various physical properties such as mechanical strength and heat resistance can be provided. Such a curable resin composition containing the above-mentioned alkali-soluble resin and a polymerizable compound is also part of the present invention.

In the curable resin composition of the present invention, the content of the alkali-soluble resin is not particularly limited and may be set appropriately depending on the use and the combination of other components. The amount is preferably 5 to 60% by weight, more preferably 10 to 55% by weight, and even more preferably 10 to 50% by weight, based on the total amount of 100% by weight.
Note that the "total solid content" means the total amount of components forming the cured product (excluding solvents etc. that volatilize during formation of the cured product).

<Polymerizable compound>
The above polymerizable compound has a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by free radicals, electromagnetic waves (e.g. infrared rays, ultraviolet rays, X-rays, etc.), irradiation with active energy rays such as electron beams, etc. It is a low-molecular compound with Examples include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.

Examples of the above-mentioned monofunctional compounds include N-substituted maleimide monomers; (meth)acrylic esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated groups and carboxyl Unsaturated monocarboxylic acids with chain extension between groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; etc. can be mentioned. These include, for example, the same compounds as the monomer components of the alkali-soluble resin described above. Furthermore, monomers having an active methylene group or an active methine group can also be used.

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

Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide trimethylolpropane tri(meth)acrylate, ethylene oxide ditrimethylolpropane tetra(meth)acrylate, ethylene oxide Added pentaerythritol tetra(meth)acrylate, ethylene oxide added dipentaerythritol hexa(meth)acrylate, propylene oxide added trimethylolpropane tri(meth)acrylate, propylene oxide added ditrimethylolpropane tetra(meth)acrylate, propylene oxide added pentaerythritol tetra(meth)acrylate (meth)acrylate, propylene oxide added dipentaerythritol hexa(meth)acrylate, ε-caprolactone added trimethylolpropane tri(meth)acrylate, ε-caprolactone added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone added pentaerythritol tetra (meth)acrylate, ε-caprolactone added dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid modified product, pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol triacrylate Acrylate phthalic acid modified product, the following formula:

Trifunctional or higher functional polyfunctional (meth)acrylate compounds such as modified dipentaerythritol hexaacrylate represented by;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditri Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide trimethylolpropane trivinyl ether, ethylene oxide ditrimethylolpropane tetravinyl ether, ethylene oxide pentaerythritol tetravinyl ether, ethylene oxide Polyfunctional vinyl ethers such as added dipentaerythritol hexavinyl ether;

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

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide added trimethylolpropane triallyl ether, ethylene oxide added ditrimethylolpropane tetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether;

Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide addition tri(acryloyloxyethyl)isocyanurate, alkylene Polyfunctional (meth)acryloyl group-containing isocyanurates such as oxidized tri(methacryloyloxyethyl) isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. Polyfunctional urethane (meth)acrylates obtained by the reaction of polyfunctional isocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc.

Among the above polymerizable compounds, it is preferable to use polyfunctional polymerizable compounds from the viewpoint of further improving the curability of the curable resin composition. The functional number of the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more. Further, the functional number is preferably 10 or less, more preferably 8 or less.
Further, the molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, it is preferably less than 4,000, and more preferably less than 2,000.

Among the above polyfunctional polymerizable compounds, from the viewpoint of reactivity, economy, availability, etc., preferred are polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and (meth)acryloyl groups. Examples include compounds having a (meth)acryloyl group, such as isocyanurate compounds, and more preferably polyfunctional (meth)acrylate compounds. By including a compound having a (meth)acryloyl group, the resin composition becomes more excellent in photosensitivity and curability, and a cured product with even higher hardness and higher transparency can be obtained. As the polyfunctional polymerizable compound, it is more preferable to use a trifunctional or more polyfunctional (meth)acrylate compound.

In the curable resin composition of the present invention, the content of the polymerizable compound is not particularly limited and may be set as appropriate as long as the effects of the present invention are exhibited. In terms of viscosity, it is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on 100% by mass of the total solid content of the curable resin composition of the present invention.

<Photopolymerization initiator>
It is preferable that the above-mentioned curable resin composition further contains a photopolymerization initiator. By including a photopolymerization initiator, the curability of the curable resin composition can be improved, and the performance of the resulting cured product can be improved.
The photopolymerization initiator is preferably a radically polymerizable photopolymerization initiator. A radically polymerizable photopolymerization initiator is one that generates polymerization initiation radicals by irradiation with active energy rays such as electromagnetic waves and electron beams.

Specific examples of the photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907", manufactured by BASF), 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE369", manufactured by BASF), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholinophenyl)-1 Aminoketone compounds such as phosphorus-4-yl-phenyl)-butan-1-one ("IRGACURE379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE651", Benzyl ketal compounds such as phenylglyoxylic acid methyl ester (“DAROCUR MBF”, manufactured by BASF); 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, manufactured by BASF), 2- Hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR1173”, manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1- Propan-1-one ("IRGACURE2959", manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane In addition to hydroketone compounds such as -1-one ("IRGACURE127", manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE500", manufactured by BASF); etc., JP-A-2013 Alkylphenone compounds exemplified in paragraphs [0084] to [0086] of Publication No.-227485; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime)] ("OXE01", manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) ("OXE02") , manufactured by BASF), 1,2-octanedione, 1-[4-(phenylthio)-,2-,(O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), 1-[9- Oxime ester compounds such as ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ("OXE04", manufactured by BASF); benzophenone compounds; Benzoin-based compounds; thioxanthone-based compounds; halomethylated triazine-based compounds; halomethylated oxadiazole-based compounds; biimidazole-based compounds; titanocene-based compounds; benzoic acid ester-based compounds; acridine-based compounds, etc.; phosphine oxide-based compounds; It will be done. Among these, aminoketone compounds are preferred.
These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator is not particularly limited and may be set as appropriate as long as the effect of the present invention is exhibited, but for example, the total solid content of the curable resin composition of the present invention is It is preferably 2 to 35% by mass, more preferably 5 to 30% by mass.

Furthermore, if necessary, one or more kinds of photosensitizers, photoradical polymerization accelerators, etc. may be used in combination. Sensitivity and curability can be further improved by using a photosensitizer and/or a photoradical polymerization accelerator together with a photopolymerization initiator. The photosensitizer and photoradical polymerization accelerator are not particularly limited, and may be appropriately selected from known ones commonly used in curable resin compositions.

<Other ingredients>
The curable resin composition of the present invention may further contain other components as necessary. Other components mentioned above include, for example, solvent; coloring material (also referred to as coloring agent); dispersant; heat resistance improver; leveling agent; development aid; inorganic fine particles such as silica fine particles; silane type, aluminum type, titanium type, etc. Coupling agents; fillers, thermosetting resins such as epoxy resins, phenolic resins, and polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants; matting agents antifoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinonediazide compounds; polyhydric phenol compounds; cationically polymerizable compounds; acid generators; and the like. These may be used alone or in combination of two or more.
These other components may be used by appropriately selecting known ones, and the amounts used can also be set appropriately.

For example, when the curable resin composition is used for a color filter, it is preferable that the curable resin composition contains a coloring material.

(solvent)
The above-mentioned solvent is not particularly limited as long as it uniformly dissolves the above-mentioned alkali-soluble resin and does not react with it; for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether alcohols such as; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide; and the like. These may be used alone or in combination of two or more. The content of the solvent may be appropriately set depending on the optimum viscosity when using the curable resin composition.

(color material)
Examples of the coloring material include pigments and dyes. As the coloring material, either a pigment or a dye may be used, or a combination of a pigment and a dye may be used. For example, when forming red, blue, and green pixels of a color filter, it is preferable to use a known method that achieves the desired color characteristics by appropriately combining coloring materials such as blue and violet, green and yellow, etc. Further, when forming a black matrix, it is preferable to use a black coloring material.

Among coloring materials, pigments are preferred from the viewpoint of durability, and dyes are preferred from the viewpoint of improving the brightness of panels and the like. These can be appropriately selected depending on the required characteristics. In the curable resin composition of the present invention, pigments are preferred because they can further improve the solvent resistance or heat coloring resistance of the cured product. As the pigment, the same pigment as described in JP-A-2015-157909 can be used.

As the dye, for example, organic dyes described in JP-A No. 2010-9033, JP-A 2010-211198, JP-A 2009-51896, and JP-A 2008-50599 can be used. can. Among these, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like are preferred.
These coloring materials may be used alone or in combination of two or more.

The content of the coloring material is not particularly limited and can be set as appropriate depending on the purpose and use, but is preferably 5 to 30% by mass based on 100% by mass of the total solid content of the curable resin composition. % by mass, more preferably 5 to 25% by mass.

(dispersant)
When the curable resin composition of the present invention contains the above-mentioned coloring material, it is preferable that it further contains a dispersant. By including a dispersant, the dispersion of the coloring material into the dispersion medium can be stabilized. The above-mentioned dispersant is not particularly limited and includes known ones, such as resin-type dispersants, surfactants, pigment derivatives, and the like. These may be used alone or in combination of two or more.

Examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane. , long-chain polyaminoamide phosphates, hydrogen group-containing polycarboxylic acid esters, amides and their salts formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups, (meth)acrylic acid-styrene Copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/polypropylene oxide adducts, etc. Can be mentioned. Commercially available resin-type dispersants include those similar to those described in JP-A No. 2015-157909.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkyl betaines such as alkyldimethylaminoacetic acid betaines, and alkylimidazolines; and the like.

The above-mentioned dye derivative is a compound having a structure in which a functional group is introduced into the dye, and examples of the functional group include a sulfonic acid group, a sulfonamide group and its quaternary salt, a dialkylamino group, a hydroxyl group, a carboxyl group, and an amide group. , phthalimide group, etc. Examples of the base pigment structure include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, and diketopyrrolopyrrole. Examples include systems.

The content of the above-mentioned dispersant may be set appropriately depending on the purpose and use, but from the viewpoint of balance between dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency, for example, curing The amount is preferably 0.01 to 60% by mass based on 100% by mass of the total solid content of the resin composition. More preferably 0.1 to 50% by weight, still more preferably 0.3 to 40% by weight.

(Preparation of curable resin composition)
The method for preparing the above-mentioned curable resin composition is not particularly limited, and any known method may be used. It will be done. The mixing/dispersing step is not particularly limited, and may be performed by a known method. Moreover, it may further include other steps that are normally performed. In addition, when the said curable resin composition contains a coloring material, it is preferable to prepare it through the dispersion|distribution process of a coloring material.

In the dispersion treatment process for the coloring material, for example, first, a predetermined amount of the coloring material (preferably an organic pigment), a dispersing agent, and a solvent are weighed, and a dispersion machine is used to disperse the coloring material into fine particles to form a liquid coloring material. A method for obtaining a dispersion liquid (also referred to as a mill base) can be mentioned. Examples of the dispersing machine include a paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender, and the like. The above-mentioned dispersion treatment step preferably includes a method of performing kneading and dispersion treatment using a roll mill, kneader, blender, etc., and then performing fine dispersion treatment using a media mill such as a bead mill filled with beads of 0.01 to 1 mm. . A composition (preferably a transparent liquid) containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and, if necessary, a solvent and a leveling agent, etc., which have been separately stirred and mixed, is added to the obtained mill base. A curable resin composition can be obtained by mixing to obtain a uniform dispersion solution.
Note that the obtained curable resin composition is preferably subjected to a filtration treatment using a filter or the like to remove fine dust.

3. Laminate As described above, the alkali-soluble resin and curable resin composition of the present invention can provide a cured product with excellent solvent resistance and adhesion to a substrate. Furthermore, the cured product has excellent basic properties such as heat resistance and transparency. A laminate having a cured product of the above-mentioned alkali-soluble resin or a cured product of the above-mentioned curable resin composition on a substrate (base material) is also one of the aspects of the present invention.

When the cured product is a cured film, the film thickness is preferably 0.1 to 20 μm. When the film thickness is within the above range, it can have excellent image forming properties and surface smoothness in addition to solvent resistance. The above film thickness is more preferably 0.5 to 15 μm, and even more preferably 1 to 10 μm.

The method for obtaining a cured product using the alkali-soluble resin or curable resin composition of the present invention is not particularly limited, and any known method may be used. Examples include a method of applying and curing the applied material by drying, heating, or irradiating energy rays such as ultraviolet rays to obtain a cured product.
The above-mentioned base material is not particularly limited, and may be appropriately selected depending on the purpose and use, and examples thereof include base materials made of various materials such as glass plates and plastic plates.

The method for obtaining the laminate of the present invention is not particularly limited and any known method may be used. However, when the alkali-soluble resin or curable resin composition of the present invention is used, solvent resistance and For example, the following method is preferred because it can provide a cured product with excellent adhesion to the base material.
That is, a step of applying the above-mentioned curable resin composition onto a base material to form a coating film, a step of irradiating the formed coating film with light, and a step of heating the irradiated coating film at 200° C. or less. This is a method for manufacturing a laminate, including a step of forming a cured film. The laminate obtained by this method has excellent solvent resistance and adhesion to the substrate.

The method of applying the above-mentioned curable resin composition to form a coating film is not particularly limited, and known methods such as spin coating, slit coating, roll coating, and cast coating can be used.
In the method for manufacturing the laminate, it is preferable to apply the curable resin composition onto the base material and then dry the coated material to form a coating film. The above-mentioned drying can be performed by a known method, and specifically, it can be performed by a method similar to the drying method described in "Placement step" of "Color filter manufacturing method" described later.

After forming the coating film, there is a step of irradiating the coating film with light.
The method of the above-mentioned light irradiation is not particularly limited and can be carried out by a known method. Specifically, the method similar to the method described in "Light irradiation step" of "4. Color filter manufacturing method" described later. It can be done in a way.

When the coating film is irradiated with light, the irradiation may be performed through a photomask. As the photomask, it is preferable to use a mask in which a light-shielding portion is formed according to the intended pattern. When light irradiation is performed through a photomask, it is preferable to perform a development step after that. By performing the development process, a desired pattern can be formed in the coating film. The developing method is not particularly limited and can be carried out by any known method. Specifically, it is carried out by the same method as described in "Developing step" in "4. Color filter manufacturing method" described later. be able to.

After performing the above-mentioned light irradiation, the light-irradiated coating film is heated at 200° C. or lower to form a cured film. In the method for manufacturing the laminate, since the curable resin composition described above is used, the heating step after light irradiation (post-curing step) can be performed at a relatively low temperature condition of 200° C. or lower.
The heating temperature is preferably 190°C or lower, more preferably 180°C or lower. The lower limit of the heating temperature is preferably 85° C. or higher, more preferably 90° C. or higher, in terms of maintaining curability.
The above-mentioned heating method other than temperature is not particularly limited and can be performed by a known method, for example, a method similar to the method described in "Heating step" of "4. Color filter manufacturing method" described below. It can be done with

The cured product of the alkali-soluble resin or curable resin composition of the present invention and the laminate containing the cured product can be used, for example, in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state image sensors, touch panel display devices, etc. For use in various optical components such as color filters, black matrices, photo spacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, etc., and electrical and electronic devices. Preferably used. Among these, it is preferable to use it for color filters.
A color filter having a cured product of the above-mentioned alkali-soluble resin or a cured product of the above-mentioned curable resin composition on a substrate is also part of the present invention. The color filter will be explained below.

4. Color Filter The color filter of the present invention has the above-mentioned cured product on a substrate.
In the above color filter, for example, the cured product formed from the above-mentioned curable resin composition is particularly suitable for use as a black matrix or segments that require coloring such as red, green, blue, yellow, etc. pixels. However, it is also suitable for segments that do not necessarily require coloring, such as photo spacers, protective layers, and alignment control ribs.

Substrates used in the above color filters include, for example, glass substrates such as white glass, blue glass, alkali-strengthened glass, and silica-coated blue glass; ring-opening polymers of polyester, polycarbonate, polyolefin, polysulfone, and cyclic olefin, and their hydrogen Sheets, films, or substrates made of thermoplastic resins such as additives; Sheets, films, or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates. Ceramic substrates; Semiconductor substrates having photoelectric conversion elements; Members made of various materials such as glass substrates with coloring material layers on their surfaces (for example, color filters for LCDs); and the like. Among these, from the viewpoint of heat resistance, glass substrates and sheets, films, or substrates made of heat-resistant resin are preferred. Further, it is preferable that the substrate is a transparent substrate.
Further, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a silane coupling agent, etc., as necessary.

<Production method of color filter>
In order to obtain the above color filter, for example, a step (also referred to as a placement step) of arranging the curable resin composition on a substrate for each pixel of one color (that is, for each pixel of one color), and a step of placing the curable resin composition on the substrate. A step of irradiating the curable resin composition with light (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step). It is preferable to adopt a manufacturing method in which the same method is repeated for each color. Note that the order in which pixels of each color are formed is not particularly limited.

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

(2) Light irradiation step In the light irradiation step, examples of active light sources used include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, Lamp light sources such as carbon arc and fluorescent lamps, laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers are used. Further, as the method of the exposure machine, there are a proximity method, a mirror projection method, and a stepper method, and the proximity method is preferably used.
Note that in the active energy ray irradiation step, the active energy ray may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed area is cured, and the cured area is made insoluble or poorly soluble in the developer.

(3) Development process The development process is a process in which, after the light irradiation process described above, development is performed using a developer to remove unexposed areas and form a pattern. Thereby, a patterned cured film can be obtained. The development treatment can be carried out usually at a development temperature of 10 to 50° C. by methods such as immersion development, spray development, brush development, and ultrasonic development.

The developer used in the above development step is not particularly limited as long as it dissolves the curable resin composition of the present invention, but organic solvents and alkaline aqueous solutions are usually used, and mixtures thereof may also be used. . In addition, when using an alkaline aqueous solution as a developer, it is preferable to wash|clean with water after image development.
Examples of the organic solvent and alkaline aqueous solution include those similar to those described in JP-A No. 2015-157909.

(4) Heating process The heating process is a process (also referred to as a post-curing process) of further curing the exposed area (cured area) by baking after the above-described development process. For example, a process of post-exposure using a light source such as a high-pressure mercury lamp with a light intensity of, for example, 0.5 to 5 J/cm ² or a process of post-heating at a temperature of, for example, 60 to 200°C for 10 seconds to 120 minutes, etc. Can be mentioned. By performing such a post-curing step, it is possible to further increase the hardness and adhesion of the patterned cured film.

The above heating step is generally performed at a temperature of about 200 to 260°C, but if the curable resin composition of the present invention is used, sufficient curing can be achieved at a relatively low temperature of 200°C or less. It can be carried out. Therefore, a product with excellent solvent resistance and adhesion can be obtained without impairing the properties held by the substrate or the cured product.

In the heating step, the heating temperature is preferably 200°C or less. Moreover, the heating temperature is preferably 130°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher.

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

The thickness of the cured film obtained by the heating step (ie, the cured coating film obtained by thermosetting the curable resin composition) is preferably 0.1 to 20 μm. The film thickness is more preferably 0.5 to 15 μm, and even more preferably 1 to 10 μm.

5. Display device The present invention is also a display device characterized by being equipped with the above-mentioned color filter.
Note that display device members and display devices having a cured product formed from the alkali-soluble resin or the curable resin composition are also included in the preferred embodiments of the present invention. The cured product (cured film) formed from the above-mentioned curable resin composition is stable, has excellent adhesion to the base material (substrate), has high hardness, and exhibits high smoothness and high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or an insulating film in various display devices.

As the display device, for example, a liquid crystal display device, a solid-state image sensor, a touch panel type display device, etc. are suitable.
In addition, when the above-mentioned cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multi-layer member composed of the above-mentioned cured film, or the above-mentioned single-layer or multi-layer member. It may be a member in which another layer is combined with the above member, or it may be a member that includes the above-mentioned cured film in its structure.

As described above, the alkali-soluble resin and curable resin composition of the present invention have excellent solvent resistance and adhesion to the substrate even when the post-curing step is performed at a relatively low temperature of 200°C or lower. It can give excellent cured products.
The alkali-soluble resin and curable resin composition of the present invention can be used in electrical appliances as various optical members and structural members used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state image sensors, touch panel display devices, etc. - Can be suitably used in various applications such as electronic equipment.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "parts" shall mean "parts by mass" and "%" shall mean "% by mass."

In this example, various physical properties were measured by the following methods.
(1) Weight average molecular weight (Mw)
The weight average molecular weight was measured by GPC (gel permeation chromatography) using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.

(2) Solid content About 1 g of the resin solution was weighed into an aluminum cup, and about 3 g of acetone was added to dissolve it, followed by air drying at room temperature. Then, it was dried under vacuum at 140° C. for 1.5 hours using a hot air dryer (trade name: PHH-101, manufactured by ESPEC), and then allowed to cool in a desiccator, and its mass was measured. The solid content (mass %) of the resin solution was calculated from the amount of mass loss.

(3) Solution Acid value 3 g of the resin solution was accurately weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1N KOH aqueous solution as a titrant. Titration was performed using an automatic titration device (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of solid content (mgKOH/g) was determined from the acid value of the solution and the solid content of the solution.

(4) Theoretical polymer acid value The theoretical polymer acid value was determined using the following formula.
Theoretical polymer acid value (mgKOH/g) = [number of moles of acid groups derived from structural units (C) and (E) (mmol)] x 56.11/[monomer charge amount (g)]

(5) Solvent resistance (preparation of coloring material composition)
12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparon DA-7301 as a dispersant, C.I. I. 2.25 parts of Pigment Green 58 and C.I. I. Pigment Yellow 138 was mixed with 1.5 parts and dispersed in a paint shaker for 3 hours to obtain a coloring material composition (solid content: 22% by mass).

(Preparation of curable resin composition)
In each case, in terms of solid content, 30 parts of the resin solution, 30 parts of dipentaerythritol hexaacrylate as the radically polymerizable compound, and 10 parts of Irgacure 907 (manufactured by BASF Japan) as the radically polymerizable photoinitiator were obtained as above. The curable resin composition was prepared by adding 30 parts of the resulting coloring material composition and further adding a diluent solvent (propylene glycol monomethyl ether acetate) so that the solid content concentration of the curable resin composition was 20% by mass, and stirring. Obtained.

(Evaluation of solvent resistance)
The curable resin composition was spin-coated onto a 5 cm square glass substrate, dried at 100°C for 5 minutes, exposed to light at 100 mJ using a high-pressure mercury lamp, and heat-treated at 150°C for 40 minutes to cure the film to a thickness of 5 μm. A membrane was obtained. Then, the cured film was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 40°C for 10 minutes and then taken out. The absorbance was measured using The larger the absorbance value, the more the coloring material eluted into the immersion liquid, and the lower the solvent resistance of the curable resin composition was evaluated.

(6) Adhesion In the above solvent resistance evaluation, peeling of the cured film after being immersed in NMP and taken out was visually observed and evaluated using the following evaluation criteria.
(Evaluation criteria)
○: All of the cured film remains.
Δ: Part of the cured film has peeled off.
×: The cured film is completely peeled off.

(Synthesis example 1)
Preparation of Resin Solution 1 70 parts of propylene glycol monomethyl ether acetate was charged into a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, and after purging with nitrogen, the mixture was heated to 90°C. It was warm. On the other hand, as the dropping tank (A), 10 parts of maleic anhydride (MA), 80 parts of propylene glycol monomethyl ether acetate (PGMEA) and t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation) were used. ), and add 12 parts of vinyltoluene (VT) and OXE-10 (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd., acrylic acid (3-ethyl-3) to a dropping tank (B). A mixture of 32 parts of (oxetanyl)methyl, 46 parts of 1-[2-(methacryloyloxy)ethyl] succinate (HOMS), and 2.5 parts of n-dodecylmercaptan was prepared by stirring.The temperature of the reaction tank was 90°C. After the temperature reached ℃, dropwise addition was started from the dropping tank over 3 hours while maintaining the same temperature, and polymerization was carried out.After the dropwise addition was completed, the temperature was maintained at 90℃ for 30 minutes, and then the temperature was raised to 115℃. Aging was performed for a minute. Thereafter, it was cooled to room temperature to obtain resin solution 1. Various physical properties are shown in Table 1.

(Synthesis example 2)
Preparation of resin solution 2 Regarding the amount of monomers charged in the dropping tank (A), maleic anhydride was 15 parts, vinyltoluene was 20 parts, OXE-10 was 23.5 parts, and HOMS was 41.5 parts. Resin solution 2 was obtained in the same manner as in Synthesis Example 1 except for the following steps. Various physical properties are shown in Table 1.

(Synthesis example 3)
Preparation of Resin Solution 3 Regarding the amount of monomers charged in the dropping tank (A), 10 parts of maleic anhydride, 12 parts of vinyltoluene, OXE-30 (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd., methacrylic acid ( Resin solution 3 was obtained in the same manner as in Synthesis Example 1, except that 34 parts of 3-ethyl-3-oxetanyl (methyl) and 44 parts of HOMS were used. Various physical properties are shown in Table 1.

(Synthesis example 4)
Preparation of resin solution 4 Regarding the amount of monomers charged in the dropping tank (A), 10 parts of maleic anhydride, 12 parts of vinyltoluene, 44 parts of OXE-10, 10 parts of acrylic acid (AA), and Resin solution 4 was obtained in the same manner as in Synthesis Example 1 except that HOMS was changed to 24 parts. Various physical properties are shown in Table 1.

(Synthesis example 5)
Preparation of resin solution 5 Regarding the amount of monomers charged in the dropping tank (A), 10 parts of maleic anhydride, 12 parts of vinyltoluene, 42 parts of OXE-10, 12 parts of methacrylic acid (MAA), and Resin solution 5 was obtained in the same manner as in Synthesis Example 1 except that HOMS was changed to 24 parts. Various physical properties are shown in Table 1.

(Synthesis example 6)
Preparation of resin solution 6 Synthesis example 1 except that the amount of monomers charged in the dropping tank (A) was 5 parts of maleic anhydride, 6 parts of vinyltoluene, 69 parts of OXE-10, and 20 parts of HOMS. Resin solution 6 was obtained in the same manner as above. Various physical properties are shown in Table 1.

(Synthesis example 7)
Preparation of resin solution 7 Regarding the amount of monomers charged in the dropping tank (A), maleic anhydride was 10 parts, vinyltoluene was 12 parts, methyl methacrylate (MMA) was 32 parts, and HOMS was 46 parts. Resin solution 7 was obtained in the same manner as in Synthesis Example 1 except for this. Various physical properties are shown in Table 1.

(Synthesis example 8)
Preparation of resin solution 8 Regarding the amount of monomers charged in the dropping tank (A), 15 parts of phenylmaleimide (PMI), 50.5 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate (HEMA), A resin solution 8 was obtained in the same manner as in Synthesis Example 1 except that 14.5 parts of acrylic acid was used. Various physical properties are shown in Table 1.

(Synthesis example 9)
Preparation of resin solution 9 In the same manner as in Synthesis Example 1, except that the amount of monomers charged in the dropping tank (A) was 15 parts of phenylmaleimide, 58 parts of vinyltoluene, and 27 parts of acrylic acid. , a polymer solution was obtained. After once cooling the internal temperature to room temperature, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (v/v) was started. Next, 10 parts of glycidyl methacrylate (GMA), 0.15 parts of 6-t-butyl-2,4-xylenol, and 0.3 parts of TEA were placed in a reaction tank, and the mixture was allowed to react at 115° C. for 7 hours. Thereafter, it was cooled to room temperature to obtain a resin solution 9. Various physical properties are shown in Table 1.

(Synthesis example 10)
Preparation of resin solution 10 Synthesis except that the amount of monomers charged in the dropping tank (A) was 10 parts of maleic anhydride, 12 parts of vinyltoluene, 32 parts of glycidyl methacrylate, and 46 parts of HOMS. Resin solution 10 was prepared in the same manner as in Example 1, but the resin gelled and no resin solution was obtained.

Examples 1 to 6, Comparative Examples 1 to 3
Using the obtained resin solutions 1 to 9, the adhesion to the substrate and solvent resistance were evaluated by the evaluation method described above. The results are shown in Table 2.

Note that the descriptions in Table 1 are as follows.
MA: Maleic anhydride PMI: Phenylmaleimide VT: Vinyltoluene OXE-10: (3-ethyl-3-oxetanyl)methyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. OXE-30: (3-ethyl-3-methacrylate) Oxetanyl) methyl, manufactured by Osaka Organic Chemical Industry Co., Ltd. GMA: Glycidyl methacrylate MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate AA: Acrylic acid MAA: Methacrylic acid HOMS: Mono(2-methacryloyloxyethyl succinate)
Further, the structural formulas of OXE-10, OXE-30, and HOMS are shown below.

From Tables 1 and 2, a curable resin containing a polymer having an oxetanyl group-containing monomer unit, an acid anhydride monomer unit, and an acid group-containing compound adduct unit of a hydroxyl group-containing monomer as structural units. The compositions (Examples 1 to 6) are more stable at a low temperature of 200°C or less compared to curable resin compositions (Comparative Examples 1 to 3) containing polymers that do not have these monomer units. Even when cured, it was confirmed that the adhesiveness to the glass substrate was high and the solvent resistance remained at a high level. Furthermore, when comparing Examples 1 to 5 and Example 6, it is found that the total amount of unsaturated dicarboxylic anhydride monomer units and acid group-containing compound adduct units of the hydroxyl group-containing monomer is It was also confirmed that adhesion and solvent resistance were even more excellent when the content was 30% by mass or more relative to 100% by mass. In this way, it is not possible to maximize the desired physical properties with a resin containing a large amount of only a portion of each structural unit, such as in Example 6, so it is necessary to appropriately adjust the content ratio of the structural units. .
As described above, the curable resin composition of the present invention can provide a cured product with excellent solvent resistance and adhesion to a substrate even under low-temperature curing conditions, and is suitable for use in applications such as color filters. It has the properties of an alkali-soluble resin that can be used as an alkali-soluble resin and a curable resin composition.

Claims (9)

A structural unit (A) derived from a monomer represented by the following general formula (2) , a structural unit (B) derived from an unsaturated dicarboxylic anhydride monomer, and an acid group-containing hydroxyalkyl (meth)acrylate An alkali-soluble resin characterized by having a structural unit (C) derived from a compound adduct.

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a single bond or an alkylene group having 1 to 6 carbon atoms. R ⁷ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.) The alkali-soluble resin according to claim 1, wherein the structural unit (C) is a structural unit represented by the following general formula (3).

(In the formula, R ⁸ represents a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are the same or different and are a divalent chain or cyclic group having 1 to 12 carbon atoms which may have a substituent. represents a saturated hydrocarbon group or an unsaturated hydrocarbon group) The alkali-soluble resin according to claim 1 or 2, further comprising a structural unit (D) derived from an aromatic vinyl monomer. Any one of claims 1 to 3, wherein the total content of the structural unit (B) and the structural unit (C) is 30% by mass or more based on 100% by mass of all structural units of the alkali-soluble resin. Alkali-soluble resin described in Crab. The alkali-soluble resin according to any one of claims 1 to 4, wherein the alkali-soluble resin has a theoretical polymer acid value of 40 to 300 mgKOH/g. A curable resin composition comprising the alkali-soluble resin according to any one of claims 1 to 5 and a polymerizable compound. A laminate comprising a cured product of the alkali-soluble resin according to any one of claims 1 to 5 or a cured product of the curable resin composition according to claim 6 on a base material. A color filter comprising a cured product of the alkali-soluble resin according to any one of claims 1 to 5 or a cured product of the curable resin composition according to claim 6 on a substrate. A display device comprising the color filter according to claim 8.