JP2006312704A - Compound containing ethylenic unsaturated group and carboxy group, curable composition, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound containing an ethylenic unsaturated group and carboxy group, having excellent mechanical properties such as recovery rate and elastic recovery as well as pattern accuracy, substrate adhesiveness and curability and good storage stability, and a curable composition produced by using the compound having an ethylenic unsaturated group and carboxy group. <P>SOLUTION: The compound having an ethylenic unsaturated group and carboxy group is produced by reacting a compound having a carbonyloxy group containing ethylenic unsaturated group and derived from a compound having epoxy group with a polybasic carboxylic acid and/or its anhydride free from ≥4-valent polybasic carboxylic acid and/or its anhydride. The invention further relates to a curable composition produced by using the compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ethylenically unsaturated group- and carboxyl group-containing compound used for image formation, overcoat, ribs and spacers in color filters such as liquid crystal displays, and is suitable for these applications. Using an ethylenically unsaturated group and carboxyl group-containing compound having excellent characteristics and storage stability, a curable composition containing the ethylenically unsaturated group and carboxyl group-containing compound, and the curable composition And a liquid crystal display device.

  Conventionally, when forming a black matrix, an overcoat, a rib, a spacer, and the like in a color filter such as a liquid crystal display, a resin composition containing a resin, a photopolymerizable monomer, a photopolymerization initiator, and the like has been used. For this resin composition, various compositions have been proposed from the viewpoints of developability, pattern accuracy, adhesion, etc. As one of them, the above resin composition is used for the purpose of improving the efficiency in the forming process and improving the yield. A technique using an unsaturated group-containing resin obtained by further reacting a reaction product of an epoxy resin and an unsaturated group-containing carboxylic acid with a polybasic carboxylic acid or its anhydride as a resin contained in the product is disclosed. (Patent Document 1).

On the other hand, the resin composition for color filters may be required to have high curability and excellent mechanical properties. For example, a spacer (in the present specification, “spacer” is formed of a curable composition and indicates a so-called columnar spacer, photospacer, etc.) is a substrate of two substrates in a liquid crystal panel. Although it is used for the purpose of keeping the interval of the liquid crystal constant, it is not deformed by the high-temperature and high-pressure conditions at the time of pressure bonding because it undergoes a process of pressure bonding the color filter and the substrate under high temperature and high pressure when manufacturing the liquid crystal panel. The physical property that the spacer function is maintained is required. That is, even if it is deformed by the external pressure, the mechanical properties such as the recovery rate and elastic recovery rate for returning to the original shape when the external pressure is removed are the mechanical properties of the resin composition for color filters. As needed. As a material that satisfies this mechanical property, a resin composition that defines the content of a polyfunctional acrylate monomer has been proposed (Patent Document 2).
JP 2001-174621 A JP 2002-174812 A

  However, the spacer of the type in which the columnar convex portions are formed on the color filter is required to have pattern accuracy and substrate adhesion while having the above mechanical characteristics. On the other hand, for the purpose of improving pattern accuracy and substrate adhesion, a resin composition having mechanical properties such as a recovery rate and an elastic recovery rate suitable for spacers simply by using the above-mentioned general unsaturated group-containing resin. Could not get. Further, as a result of detailed studies by the present inventors, it has been found that some of the resins described in Patent Document 1 have poor storage stability of the resin solution and cannot withstand practical use.

  Therefore, the object of the present invention is to solve the above-mentioned conventional problems, and is excellent in mechanical properties such as recovery rate and elastic recovery rate, and is excellent in pattern accuracy, substrate adhesion, curability, and storage stability. As an image forming, overcoat, rib, and spacer in a color filter such as a liquid crystal display using the ethylenically unsaturated group and carboxyl group-containing compound and the ethylenically unsaturated group and carboxyl group-containing compound It is in providing a useful curable composition. Another object of the present invention is to provide a color filter and a liquid crystal display device formed using such a curable composition.

  As a result of intensive studies on the above problems, the present inventors have found that an ethylenically unsaturated group and carboxyl group-containing compound obtained from a specific epoxy group-containing compound can achieve the above object, and the present invention has been completed. It came to do. That is, the gist of the present invention is as follows.

1. An ethylenically unsaturated group- and carboxyl group-containing compound represented by the following general formula (I):

2. (1) An ethylenically unsaturated group and a carboxyl obtained by reacting a compound having an ethylenically unsaturated group-containing carbonyloxy group obtained from an epoxy group-containing compound with (2) a polyvalent carboxylic acid and / or its anhydride (2) an ethylenically unsaturated group, wherein the polyvalent carboxylic acid and / or its anhydride is substantially free of tetravalent or higher carboxylic acid and / or its anhydride, Carboxyl group-containing compound.

3. (1) After reacting an isocyanate group-containing compound with a compound having an ethylenically unsaturated group-containing carbonyloxy group obtained from an epoxy group-containing compound, (2) a polyvalent carboxylic acid and / or anhydride thereof (2) a polyvalent carboxylic acid and / or its anhydride substantially comprising a tetravalent or higher carboxylic acid and / or its anhydride. An ethylenically unsaturated group and carboxyl group-containing compound characterized by not containing.

4). (2) The polyvalent carboxylic acid and / or its anhydride is a trivalent or lower carboxylic acid compound. Or 3. The ethylenically unsaturated group- and carboxyl group-containing compound described in 1.

5. 1. Viscosity change rate is 0.7 to 1.3. ~ 4. The ethylenically unsaturated group and carboxyl group-containing compound according to any one of the above.

6.1. ~ 5. A curable composition comprising the ethylenically unsaturated group- and carboxyl group-containing compound according to any one of the above.

7.6. A color filter formed using the curable composition described in 1.

8.6. A liquid crystal display device formed using the curable composition described in 1.

  In the present invention, “substantially free” of “(2) the polyvalent carboxylic acid and / or anhydride thereof substantially does not contain tetravalent or higher carboxylic acid and / or anhydride thereof” To the extent that the storage stability effect of the ethylenically unsaturated group and carboxyl group-containing compound of the invention is maintained, this is to the effect that a carboxylic acid having a valence of 4 or more and / or its anhydride may be contained. The above carboxylic acid and / or its anhydride is 0 to 5% by weight, preferably 0 to 3% by weight, based on the total amount of (2) carboxylic acid and / or its anhydride. At this time, the viscosity change rate of the ethylenically unsaturated group and carboxyl group-containing compound of the present invention is usually 0.7 to 1.3, preferably 0.8 to 1.2, more preferably 0.9 to 1.1. It is.

  In the present invention, the “viscosity change rate” means a solid content concentration of 40 to 40 in a solvent used when the compound is synthesized into the compound or a solvent used when the compound is used as a resist solution. The ratio of the viscosity after preparing a solution dissolved at a ratio of 60% by weight and storing the solution in a sealed container at 70 ° C. for 24 hours to the viscosity before storage is shown.

  According to the ethylenically unsaturated group and carboxyl group-containing compound of the present invention, it has excellent storage stability, high curability, pattern accuracy, substrate adhesion, and mechanical properties such as recovery rate and elastic recovery rate. In addition, an excellent curable composition is provided. This curable composition is useful as a curable composition for image formation, for overcoat, for ribs, and for spacers used in color filters such as liquid crystal displays.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content of is not specified.

[1] Ethylenically unsaturated group and carboxyl group-containing compound The ethylenically unsaturated group and carboxyl group-containing compound of the present invention is represented by the following general formula (I).

In the general formula (I), R ¹ and R ⁴ are each independently an alkylene group or an arylene group, which may have a substituent, preferably a carbon number which may have a substituent. An alkylene group having 1 to 5 carbon atoms, or an arylene group having 6 to 10 carbon atoms such as a phenylene group. Of these, R ¹ and R ⁴ are preferably alkylene groups.

Examples of the substituent that the alkylene group or arylene group of R ¹ and R ⁴ may have include a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and phenyl. Group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, a nitro group and the like, and a hydrogen atom (that is, unsubstituted) and an alkyl group having 1 to 10 carbon atoms are preferable.

R ² and R ⁶ are each independently an optionally substituted ethylenically unsaturated group-containing carbonyloxy group, preferably an optionally substituted substituent having 3 to 50 carbon atoms. An ethylenically unsaturated group-containing carbonyloxy group, particularly preferably an ethylenically unsaturated group-containing carbonyloxy group having 3 to 30 carbon atoms, a (meth) acryloyloxy group or a group represented by the following general formula (Ia) More preferably.

（式（Ｉａ）中、Ｒ，Ｒ’，Ｒ”は各々独立して水素原子又はメチル基を表し、Ｙは任意の２価基を表し、※は式（Ｉ）で表される化合物の−ＣＨ_２−とＲ^２，Ｒ^６との結合を表す。）

(In the formula (Ia), R, R ′, and R ″ each independently represent a hydrogen atom or a methyl group, Y represents an arbitrary divalent group, and * represents − of the compound represented by the formula (I) Represents a bond between CH ₂ — and R ² , R ^6. )

  In the general formula (Ia), Y is preferably a divalent group including an alkylene group which may have a substituent and / or an arylene group which may have a substituent, and a carbonyloxy group, More preferably, it is a divalent group containing an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms and a carbonyloxy group.

Examples of the substituent that the ethylenically unsaturated group-containing carbonyl group of R ² and R ⁶ may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. Group, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, a nitro group, and the like. Preferred are a hydrogen atom (that is, unsubstituted) and an alkyl group having 1 to 10 carbon atoms.

が挙げられる（上記例示構造式において、※は式（Ｉ）で表される化合物の−Ｃ（Ｏ）−とＲ^３，Ｒ^５との結合を表す）。 R ^{3, R 5} are each independently, -C (O) OR ⁷ (provided that, ^{R 7} is an optional substituent.) Is any substituent which does not contain three or more, as ^{R 7} is , Preferably they are a hydrogen atom and the C1-C10 alkyl group which may have a substituent, More preferably, R < ³ >, R < ⁵ > is a substituent containing one or more carboxyl groups. As R ³ and R ⁵ , specifically,

(In the above structural examples, * represents a bond between —C (O) — and R ³ , R ⁵ of the compound represented by formula (I)).

X is a divalent linking group not containing —C (O) R ⁸ (wherein R ⁸ is a substituent containing three or more —C (O) OR ⁹ (R ⁹ is an optional substituent)). Examples thereof include linear and cyclic organic groups. As a linear thing, for example, alkane, alkene, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. And divalent groups derived from homopolymers or copolymers, acid-modified epoxy acrylates, polyolefins, polyamides, polyesters, polyethers, polyurethanes, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, and the like.

In addition, the cyclic ring is a divalent ring derived from an alicyclic ring, an aromatic ring, an alicyclic heterocyclic ring, a heterocyclic ring, or the like, or a ring condensed or bonded via a linking group. Groups.
Here, as an alicyclic ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a tricyclodecane ring, etc., an aromatic ring as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, Biphenylene ring, indene ring, etc., alicyclic heterocycle, heterocycle includes furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole Ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and the like.

  Examples of the linking group via the bond of the cyclic organic group include a direct bond or a divalent or higher valent linking group. As the divalent or higher linking group, known ones can be used. For example, alkylene, polyoxyalkylene, amine, O atom, S atom, ketone group, thioketone group, —C (═O) O—, amide , Se, Te, P, As, Sb, Bi, Si, B, and other metals, heterocycles, aromatic rings, heteroaromatic rings, and any combination thereof.

  Examples of the organic group of X include, for example, an alkylene group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, and 2 to 50 carbon atoms, preferably 2 to 30 carbon atoms. Examples include polyethers, bisphenols such as bisphenol A and bisphenol F shown below, and residues obtained by removing hydroxyl groups from polyol compounds such as trisphenol and novolak.

  In the above exemplary formula, z represents an integer of 0 or more. In the examples (X-18), (X-19), and (X-20), * represents a bond. In these exemplary structures, when z is 1 or more and there are 3 or more bonds *, the bonds as the divalent linking group X can take any two of them. In this case, examples of the substituent linked to the remaining one or more bonds include an arbitrary substituent, and a group represented by the following general formula (Ib) is preferable.

In the above general formula (Ib), preferable as R ¹¹ and further preferable as an optionally substituted substituent are the same as those exemplified in the description of R ¹ and R ⁴ in general formula (I).
Further, preferred as R ¹² and further preferred as a substituent that may be present are the same as those exemplified in the description of R ² and R ⁶ in formula (I).
Preferred as R ¹³ and R ^{14 are the same} as those exemplified in the description of R ³ , R ⁵ and R ⁷ in formula (I).

The ethylenically unsaturated group and carboxyl group-containing compound of the present invention is not limited as long as it has the structure, but (1) an ethylenically unsaturated group obtained from the epoxy group-containing compound. (2) A method in which a compound having a carbonyloxy group is reacted with (3) an isocyanate group-containing compound, and then (2) a polyvalent carboxylic acid and / or an anhydride thereof (however, (2) a polyvalent carboxylic acid. Acid and / or anhydride thereof is substantially free of tetravalent or higher carboxylic acid and / or anhydride thereof).
Below, each raw material used for manufacture of the ethylenically unsaturated group and carboxyl group containing compound of this invention, and a manufacturing method are demonstrated.

[1-1] Epoxy group-containing compound (a)
In the present invention, the epoxy group-containing compound (a) used for the production of the compound (1) having an ethylenically unsaturated group-containing carbonyloxy group preferably has an epoxy equivalent of 400 or less. When the epoxy equivalent exceeds the above upper limit, for example, when a curable composition containing a compound produced using the epoxy equivalent is used for a color filter, the mechanical properties are inferior.

  As the epoxy group-containing compound (a), for example, the epoxy compound described in Patent Document 1 (Japanese Patent Laid-Open No. 2001-174621) [compound having two or more epoxy groups in one molecule in the publication] (A)], specifically, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, biphenyl type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, Triglycidyl isocyanurate, epoxy compound having trisphenolmethane structure, fluorene type epoxy compound, alicyclic epoxy resin, polyadduct structure of cyclic hydrocarbon compound having two or more unsaturated groups per molecule and phenols An epoxy compound having Polymerizable epoxy compounds, and the like. Among these, a biphenyl type epoxy compound, a bisphenol A type epoxy compound, and a fluorene type epoxy compound are preferable, and a bisphenol A type epoxy compound and a fluorene type epoxy compound are particularly preferable.

  Other epoxy group-containing compounds (a) include 2 to 20 carbon atoms such as diglycidyl ethers of alkylene glycols having 1 to 20 carbon atoms such as ethylene glycol, propylene glycol, butanediol and hexanediol, polyethylene glycol and polypropylene glycol. -50 diglycidyl ethers of polyalkylene glycols, polyglycidyl ethers of polyols such as glycerol and pentaerythritol, diglycidyl ethers of aromatic diols, polyglycidyl ethers of aromatic polyols and the like. Among these, diglycidyl ether of alkylene glycol, diglycidyl ether of polyalkylene glycol, and polyglycidyl ether of polyol are preferable, and diglycidyl ether of alkylene glycol and diglycidyl ether of polyalkylene glycol are particularly preferable.

  In producing the compound (1) having an ethylenically unsaturated group-containing carbonyloxy group, such an epoxy group-containing compound (a) may be used alone or in combination of two or more. Also good.

[1-2] Compound (1) having an ethylenically unsaturated group-containing carbonyloxy group
The compound (1) having an ethylenically unsaturated group-containing carboxyl group obtained from the epoxy group-containing compound (a) as described above is obtained as a result of a reaction using the above-mentioned epoxy group-containing compound (a) as a raw material. As long as the unsaturated group-containing carbonyloxy group is formed, the production method is not limited. Specifically, the above-mentioned epoxy group-containing compound (a) is added to ethylenically unsaturated group-containing carboxylic acids. The method of reacting (b) or the above-mentioned epoxy group-containing compound is first reacted with a carboxylic acid (c) that does not contain an ethylenically unsaturated group, and then the ethylenically unsaturated group-containing carbonyloxy group is converted by the subsequent reaction. A method of forming, for example, a method of reacting a compound (d) having a functional group that reacts with the generated hydroxyl group to form an ethylenically unsaturated group-containing carbonyloxy group, Etc. can be mentioned.

  Examples of the ethylenically unsaturated group-containing carboxylic acids (b) include unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples include (meth) acrylic acid (in this specification, “(Meth) acrylic”, “(meth) acrylate” and the like mean “acrylic or methacrylic” and “acrylate or methacrylate”, for example, “(meth) acrylic acid” means “acrylic acid or Monocarboxylic acids such as crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituents Reaction products of (meth) acrylic acid with lactone or polylactone, succinic anhydride, adipic anhydride, maleic anhydride, fumaric anhydride, anhydrous Saturated or unsaturated dicarboxylic anhydrides such as itaconic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, and hydroxy Ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) One or more hydro hydrates in one molecule such as acrylate, pentaerythritol tri (meth) acrylate, (meth) acrylate such as dipentaerythritol penta (meth) acrylate Half-esters obtained by reacting a (meth) acrylate derivative having a sil group; saturated or unsaturated dicarboxylic acid anhydrides as described above, phenylglycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (Meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] And half-esters obtained by reacting with an unsaturated group-containing glycidyl compound such as oxymethyl (meth) acrylate. Among these, in the present invention, (meth) acrylic acid, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride and the like, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy Half-esters obtained by reacting butyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are particularly preferred. These may be used individually by 1 type, or may use 2 or more types together.

  In addition, as the carboxylic acids (c) containing no ethylenically unsaturated group, hydroxyl group-containing carboxylic acids such as lactic acid and dihydroxypropionic acid and anhydrides thereof, dicarboxylic acids such as oxalic acid, phthalic acid and tartaric acid and anhydrides thereof Is mentioned. These may be used individually by 1 type, or may use 2 or more types together.

  Further, after reacting such an epoxy group-containing compound with a carboxylic acid (c) that does not contain such an ethylenically unsaturated group, the compound (d) having a functional group that reacts with the generated hydroxyl group or carboxyl group is reacted. As the compound (d) having a functional group that reacts with a hydroxyl group or a carboxyl group used when forming an ethylenically unsaturated group-containing carbonyloxy group, a compound having an epoxy group, a carboxyl group, or an isocyanate group is used. Preferably, specific examples include ethylenically unsaturated group-containing carboxylic acids, ethylenically unsaturated group-containing compounds such as unsaturated group-containing glycidyl compounds, and the like. Absent. These may be used individually by 1 type, or may use 2 or more types together.

[1-3] Isocyanate group-containing compound (3)
In the present invention, in order to adjust the developability of the resulting curable composition, the compound (1) having an ethylenically unsaturated group-containing carbonyloxy group obtained from the epoxy group-containing compound may optionally be an isocyanate group. The containing compound (3) may be reacted.

  As the isocyanate group-containing compound (3), organic monoisocyanates such as butane isocyanate, 3-chlorobenzene isocyanate, cyclohexane isocyanate, 3-isopropenoyl-α, α-dimethylbenzyl isocyanate; paraphenylene diisocyanate, 2,4-tolylene diisocyanate Aromatic diisocyanates such as 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate; hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid Aliphatic diisocyanates such as diisocyanates; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) ), Alicyclic diisocyanates such as ω, ω′-diisocyanate dimethylcyclohexane; aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate; Ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenylmethane), tris And triisocyanates such as (isocyanate phenyl) thiophosphate; and trimers thereof, water adducts, and polyol adducts thereof. Of these, preferred are dimers and trimers of organic diisocyanates, and most preferred are trimethylolpropane adduct of tolylene diisocyanate, trimer of tolylene diisocyanate, and trimer of isophorone diisocyanate. These may be used individually by 1 type, or may use 2 or more types together.

[1-4] Polycarboxylic acid and / or its anhydride (2)
The ethylenically unsaturated group- and carboxyl group-containing compound of the present invention is optionally added to the above-mentioned isocyanate group in the compound (1) having an ethylenically unsaturated group-containing carbonyloxy group obtained from the epoxy group-containing compound (a). Obtained by reacting polyvalent carboxylic acid and / or anhydride (2) substantially free of tetravalent or higher carboxylic acid and / or anhydride thereof after reacting containing compound (3) I can do it.

In the present invention, the polyvalent carboxylic acid and its anhydride (2) include, for example, succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methyl Saturated or unsaturated dicarboxylic acids such as endomethylenetetrahydrophthalic acid and phthalic acid and their anhydrides; trimellitic acid and its anhydride, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetra Examples thereof include tetracarboxylic acids such as carboxylic acid and butanetetracarboxylic acid, and acid anhydrides thereof. Among these, dicarboxylic acids such as oxalic acid, tetrahydrophthalic acid, and phthalic acid, and acid anhydrides thereof, trimellitic acid And its anhydride, etc. An acid compound. In a tetravalent or higher carboxylic acid compound, the storage stability of the obtained ethylenically unsaturated group and carboxyl group-containing compound tends to deteriorate. Among the trivalent or lower carboxylic acid compounds, from the viewpoint of dissolution and removal of the non-image area during alkali development, an acid anhydride of a polyvalent carboxylic acid having an acid dissociation constant (first dissociation constant) of 3.5 or more. Is more preferable. The acid dissociation constant is further preferably 3.8 or more, and particularly preferably 4.0 or more. As such an acid anhydride, succinic acid and an acid anhydride of tetrahydrophthalic acid are particularly preferable.
The acid dissociation constant can be referred to Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955 (Brown, HC et al.).
In this invention, polyvalent carboxylic acid and its acid anhydride (2) may be used individually by 1 type, or may use 2 or more types together.

  In addition, the ethylenically unsaturated group- and carboxyl group-containing compound of the present invention may be used as a part of the carboxyl group in the compound obtained by reacting the polyvalent carboxylic acid and / or its anhydride (2). Furthermore, the compound which added the said epoxy-group containing compound (a) may be sufficient.

[1-5] Method for Producing Ethylenically Unsaturated Group and Carboxyl Group-Containing Compound A specific method for producing the ethylenically unsaturated group and carboxyl group-containing compound of the present invention is described in, for example, JP-A-4-355450. Specifically, the epoxy group-containing compound (a) is dissolved in an organic solvent such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, and the like, and triethylamine, benzyldimethylamine, tribenzylamine, etc. Or tertiary amines such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride, In the presence of a phosphorus compound such as phenylphosphine, or a catalyst such as stibine such as triphenylstibine, in the presence of a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or methylhydroquinone, the ethylenically unsaturated group-containing carboxyl The acid (b) is added in an amount that is usually 0.8 to 1.5 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to one chemical equivalent of the epoxy group of the epoxy group-containing compound (a). In general, the compound (1) having an ethylenically unsaturated group-containing carbonyloxy group is obtained by addition reaction at a temperature of 60 to 150 ° C., preferably 80 to 120 ° C., and then the polyvalent carboxylic acid and / or its anhydride is obtained. The product (2) is usually added in an amount of 0.05 to 1.0 chemical equivalent, preferably 0.5 chemical equivalent, relative to 1 chemical equivalent of the hydroxyl group generated in the above reaction. Can be prepared by methods such as the reaction is continued under conditions similar. Moreover, when using an isocyanate group containing compound (3), before reacting polyhydric carboxylic acid and / or its anhydride (2), for example, the method of making these react on the same conditions is used preferably.

[1-6] Preferred physical properties of ethylenically unsaturated group and carboxyl group-containing compound The ethylenically unsaturated group and carboxyl group-containing compound of the present invention thus produced has a viscosity change rate of 0.7. It is preferable that it is -1.3. If the rate of change in viscosity is less than 0.7 or more than 1.3, the storage stability is inferior, which is not preferable. The viscosity change rate is 0.8 or more, particularly 0.9 or more, and preferably 1.2 or less, particularly 1.1 or less.

  The ethylenically unsaturated group and carboxyl group-containing compound of the present invention has an acid value of 30 mg · KOH / g or more, particularly 40 mg · KOH / g or more, and 150 mg · KOH / g or less, particularly 100 mg · It is preferable that it is below KOH / g. When the acid value is less than or exceeds the above range, for example, when a curable composition containing the acid value is used for a color filter, there are problems such as poor developability and adhesion, which is not preferable.

  Further, the ethylenically unsaturated group- and carboxyl group-containing compound of the present invention has a polystyrene-reduced weight average molecular weight of 1,000 or more, particularly 1,500 or more, and 100,000 or less, particularly 10 by gel permeation chromatography. 1,000 or less. When the weight average molecular weight is smaller than the above range, there is a problem such as poor film-forming property of the curable composition containing the weight average, and when the weight average molecular weight is larger, the solubility in a solvent may be impaired.

  Such an ethylenically unsaturated group and carboxyl group-containing compound of the present invention is used, for example, as a curable composition containing the compound, for example, for a color filter or a liquid crystal display device.

[2] Curable composition The curable composition of the present invention contains the above-mentioned ethylenically unsaturated group and carboxyl group-containing compound of the present invention as essential components, and other resins and polymers as necessary. Containing a reactive monomer, heat and / or photopolymerization initiator.
The curable composition of the present invention is usually used in a state dissolved or dispersed in a solvent in order to form a resin composition layer on a substrate by means of coating-drying or the like.
The curable composition in the present invention is any of a state in which the curable composition is dissolved or dispersed in a solvent, a state in which the solvent component is volatilized and removed, and a state in which the curable composition is subsequently cured by heat and / or light. Is also shown.

[2-1] Ethylenically unsaturated group and carboxyl group-containing compound The content of the ethylenically unsaturated group and carboxyl group-containing compound of the present invention in the curable composition of the present invention is that of the curable composition of the present invention. It is usually 10% by weight or more, preferably 15% by weight or more, more preferably 20% by weight or more based on the total solid content. If the content of the ethylenically unsaturated group and carboxyl group-containing compound is too small, sufficient mechanical properties may not be obtained, which is not preferable. The upper limit of the content of the ethylenically unsaturated group and carboxyl group-containing compound in the curable composition is not particularly limited, but the necessary amount of other components required for use as a curable composition is blended Therefore, it is usually 90% by weight, preferably 85% by weight or less.
In the present invention, “total solid content” means all components other than the solvent.

  One type of the ethylenically unsaturated group and carboxyl group-containing compound of the present invention may be contained alone or two or more types may be contained in the curable composition of the present invention.

[2-2] Other resins Other resins used in the curable composition of the present invention include compounds other than the ethylenically unsaturated group and carboxyl group-containing compounds of the present invention, and are known color filter resins. Resins used in the composition can be used. Examples of such resins include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Examples of the polymer include acid-modified epoxy acrylates, polyamides, polyesters, polyethers, polyurethanes, polyvinyl butyrals, polyvinyl alcohols, polyvinyl pyrrolidones, and acetyl celluloses. A resin containing resin, a copolymer containing a carboxyl group and an epoxy group, and acid-modified epoxy acrylates are preferable.

  Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other unsaturated carboxylic acids, and styrene. , Α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycy Zir (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, Examples thereof include copolymers with vinyl compounds such as N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, and vinyl acetate.

  Among these, a styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and 3-30 mol% of styrene, 10-70 mol% of (meth) acrylate, 10-60 mol% of (meth) acrylic acid. A copolymer consisting of 5 to 25 mol% of styrene, 20 to 60 mol% of (meth) acrylate, and 15 to 55 mol% of (meth) acrylic acid is particularly preferable. These carboxyl group-containing vinyl resins preferably have an acid value of 30 to 250 mg · KOH / g and a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000.

  Further, as the carboxyl group-containing vinyl-based resin, those having an ethylenically unsaturated bond in the side chain are suitable. Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate is added to the carboxyl group-containing polymer. , Α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Group epoxy group-containing unsaturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1. ] Dec-2-yl] An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate, 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer Reaction products obtained by reacting, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, Compounds having two or more unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1- Propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) a The ratio of the compound having two or more kinds of unsaturated groups such as chloramide and the unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the unsaturated group. The reaction product etc. which were copolymerized so that it may become 10-90 mol%, preferably about 30-80 mol% are mentioned. In addition, a reaction product of an epoxy group-containing polymer and an ethylenically unsaturated compound having a functional group capable of reacting with an epoxy group such as a carboxyl group or a hydroxyl group, and a compound obtained by further reacting an acid anhydride with this product. I can do it.

  Examples of the copolymer containing a carboxyl group and an epoxy group include unsaturated carboxylic acids, unsaturated compounds having an epoxy group, and copolymers with other compounds as required. Examples include alkali-soluble resins used in the composition described in No. 133600.

  One of these other resins may be included alone in the curable composition, or two or more thereof may be included.

  The content of these other resins is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content of the curable composition of the present invention. When there is too much content of other resin, since it exists in the tendency to reduce a mechanical characteristic, it is unpreferable.

[2-3] Polymerizable monomer The curable composition of the present invention preferably contains a polymerizable monomer. Examples of the polymerizable monomer include compounds having at least one ethylenically unsaturated group. Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acid having an ethylenically unsaturated bond and many (single) And monoesters of monohydric alcohols.

  In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, methacrylic acid esters in which the acrylates of these exemplary compounds are replaced with methacrylates, and itaconic acid esters in which itaconate is similarly replaced, Crotonic acid ester instead of clonate or maleate ester instead of maleate And the like. Further, among these, there may be mentioned a reaction product of a compound having a hydroxyl group such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with the above polyvalent carboxylic acid and / or its anhydride.

  Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. Etc.

  The ester obtained by the esterification reaction of a polyvalent hydroxy compound with a polybasic carboxylic acid and an unsaturated carboxylic acid is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, And a condensate of ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin.

  In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.

  One kind of these polymerizable monomers may be contained alone in the curable composition, or two or more kinds thereof may be contained.

  The content of the polymerizable monomer in the curable composition of the present invention is usually less than 80% by weight, preferably less than 70% by weight, preferably 10% by weight or more, based on the total solid content of the curable composition. It is. When the content of the polymerizable monomer is out of the above range, it is difficult to obtain an image with a good pattern.

[2-4] Heat and / or photopolymerization initiator The curable composition of the present invention may contain heat and / or a photopolymerization initiator depending on the method of curing the curable composition. good. The polymerization initiator is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group with heat and / or actinic rays, and a known heat and / or photopolymerization initiator can be used.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, Halomethylated oxadiazole derivatives such as 2-trichloromer-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxadiazole; 2- (2′-chlorophenyl) -4,5- Diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole Dimer etc. Dazole derivatives; benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone A benzophenone derivative such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone; 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1- Droxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- Acetophenone derivatives such as 1-one, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2- Thioxanthone derivatives such as ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; ethyl p-dimethylaminobenzoate, p-diethylaminobenzoate Benzoate derivatives such as ethyl acetate; 9-phenyl acetate Acridine derivatives such as gin and 9- (p-methoxyphenyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; anthrone derivatives such as benzanthrone; dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl -Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5 , 6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-di-fluoro-3- (pyr-1-yl) -phen-1-yl and the like. Furthermore, oxime initiators described in JP-A No. 2000-80068 can be particularly preferably used.

  In addition, photopolymerization initiators that can be used in the present invention are described in Fine Chemical, March 1, 1991, Vol. 20, no. 4, P. 16-P26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, JP-A-10-39503 Has been.

  One of these photopolymerization initiators may be included alone in the curable composition, or two or more thereof may be included.

  Specific examples of the thermal polymerization initiator used in the present invention include azo compounds, organic peroxides and hydrogen peroxide. Of these, azo compounds are preferably used.

  As the azo compound, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis [2-Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2 , 2'-azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropionamide], 2,2'-azobis (N-cyclohexyl- 2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionate), 2,2'-azobis (2,4 , 4-Trimethylpen Emissions), or the like can be cited, among these, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like are preferable.

  Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butylperoxypivalate, di (3,5,5-trimethylhexanoyl) peroxy , Di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2, 5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2- Ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy)- 3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- ( t-Butylperoxy) cyclohexyl) Bread, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl -2,5-di- (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5- Di-methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl4, 4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (T-Butylpas Oxy) hexane, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1 , 3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, di (3-methylbenzoyl) And a mixture of peroxide, benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide.

  One of these thermal polymerization initiators may be contained alone in the curable composition, or two or more thereof may be contained. Moreover, you may use together a photoinitiator and a thermal-polymerization initiator.

  The content of these heat and / or photopolymerization initiators is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably based on the total solid content of the curable composition of the present invention. The amount is 0.5% or more, usually 30% by weight or less, preferably 20% by weight or less. If the content is too low, the sensitivity may be lowered. On the other hand, if the content is too high, the solubility of the unexposed portion in the developer is lowered, and development defects are likely to be induced.

[2-5] Other components In addition to the above components, the curable composition of the present invention includes a solvent, a colorant, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, and a polymerization inhibitor. An antioxidant, a silane coupling agent, an epoxy compound, an amino compound, a polymerization accelerator and the like can be appropriately blended.

[2-5-1] Solvent Although there is no restriction | limiting in particular as a solvent used for the curable composition of this invention, For example, water, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n- Hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl Nonyl ketone, propyl ether, dodecane, Social solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, acetic acid (n, sec, t) butyl, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene Recall monobutyl ether acetate, diethylene glycol monobutyl ether, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol , Cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether Ter, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether , 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxy It can be mentioned solvents such as butyl acetate specifically.

  The solvent can dissolve or disperse each component and is selected according to the method of using the curable composition of the present invention, but it is preferable to select a solvent having a boiling point in the range of 60 to 280 ° C. More preferably, it has a boiling point of 70 to 260 ° C. These solvents can be used alone or in combination of two or more.

  These solvents are used in such an amount that the ratio of the total solid content in the curable composition of the present invention is usually 10% by weight or more and 90% by weight or less.

[2-5-2] Colorant As the colorant used in the curable composition of the present invention, known colorants such as pigments and dyes can be used. For example, when a pigment is used, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the curable composition without agglomeration. Although there is no restriction | limiting in particular in content of a coloring agent, Usually, it is 70 weight% or less with respect to the total solid of a curable composition.

[2-5-3] Coating property improver, development improver Examples of the coating property improver or development improver used in the curable composition of the present invention include, for example, known cationic, anionic, nonionic, and fluorine. And silicon surfactants can be used. As the development improver, known ones such as organic carboxylic acids and / or anhydrides thereof can be used. Moreover, the content is 20 weight% or less normally with respect to the total solid of a curable composition, Preferably it is 10 weight% or less.

[2-5-4] Polymerization inhibitor, antioxidant Further, the curable composition of the present invention has a polymerization inhibitor such as hydroquinone and methoxyphenol, and 2,6-di- It is preferable to contain a hindered phenol antioxidant such as tert-butyl-4-cresol (BHT). The content thereof is usually 5 ppm or more, preferably 10 ppm or more, and usually 1000 ppm or less, preferably 600 ppm or less, based on the total solid content of the curable composition. If this content is small, the stability tends to deteriorate, and if it is too large, for example, curing by heat and / or light may cause insufficient curing, which is not preferable. In particular, when used in a normal photolithography method, it is necessary to set the optimum amount in view of both storage stability and sensitivity of the curable composition.

[2-5-5] Silane coupling agent The curable composition of the present invention preferably contains a silane coupling agent in order to improve adhesion to the substrate. As for the type of silane coupling agent, various types such as epoxy, (meth) acrylic, amino and the like can be used singly or as a mixture of two or more, and in particular, epoxy silane coupling agents Is preferred. The content is usually 20% by weight or less, preferably 15% by weight or less, based on the total solid content in the curable composition.

[2-5-6] Epoxy Compound Further, the curable composition of the present invention is one kind of an epoxy compound such as the aforementioned epoxy group-containing compound (a) in order to improve curability and adhesion to a substrate. It is also preferable to add two or more kinds. The content thereof is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content in the curable composition. When this content is too large, the storage stability of the resin composition may deteriorate.

[2-5-7] Amino compound Further, the curable composition of the present invention improves its curability (curing speed of the curable composition, mechanical properties of the cured product) and adhesion to the substrate. It is also preferable to add one or more amino compounds. The content thereof is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content in the curable composition. Moreover, it is 0.5 weight% or more normally, Preferably it is 1 weight% or more. When there is too much this content, the storage stability of a curable composition may deteriorate. Moreover, when there is too little content, the improvement effect of the said sclerosis | hardenability and adhesiveness with a board | substrate will become low.
In particular, when the curing rate is expected, the content is usually 10% by weight or less, preferably 5% by weight or less. Moreover, it is 0.5 weight% or more normally, Preferably it is 1 weight% or more. If this content is too large, the pattern formability may deteriorate.

  Examples of the amino compound include a methylol group as a functional group and an amino compound having at least two alkoxymethyl groups obtained by condensing and modifying the alcohol with 1 to 8 carbon atoms. For example, melamine obtained by polycondensation of melamine and formaldehyde. Resin, benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde, glycoluril resin obtained by polycondensation of glycoluril and formaldehyde, urea resin obtained by polycondensation of urea and formaldehyde, melamine, benzoguanamine, glycoluril, or urea And a resin obtained by copolycondensation of two or more of the above and formaldehyde, and a modified resin obtained by alcohol condensation modification of the methylol group of these resins. Among them, in the present invention, a melamine resin and a modified resin thereof are preferable, a modified resin having a methylol group modification ratio of 70% or more is more preferable, and a modified resin having a methylol group modification ratio of 80% or more is particularly preferable.

  Specific examples of these amino compounds include “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, Mitsui Cytec Co., Ltd. 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nicarac” (registered trademark) MW-390, MW-100LM, MX- from Sanwa Chemical Co., Ltd. 750LM, MW-30M, MX-45, and MX-302 are also benzoguanamine resins and modified resins thereof, “Cymel” (registered trademark) 1123, 1125, and 1128, and glycoluril resins and modified resins thereof as “ Cymel "(registered trademark) 1170, 1171, 1174, 1172, “Nikarak” (registered trademark) MX-270, BX-4000, and urea resin and modified resins thereof, “UFR” (registered trademark) 65, 300, and “Nikarak” (registered trademark) manufactured by Mitsui Cytec Co., Ltd. ) MX-290, etc.

[2-5-8] Polymerization accelerator It is also preferable to add one or more polymerization accelerators to the curable composition of the present invention in order to promote polymerization and curing.

  Examples of the polymerization accelerator include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, Mercapto group-containing compounds such as β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakis Derivatives such as polyfunctional thiol compounds such as thiopropionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine or its ammonium salt, sodium salt, etc. Niruaranin, or salts such as its ammonium and sodium salts, derivatives, and the like, such as amino acid or a zwitterionic compound having an aromatic ring such as derivatives of esters.

  The content of these polymerization accelerators is usually 10% by weight or less, preferably 5% by weight or less, based on the total solid content in the curable composition. When this content is too large, there are problems such as poor developability and adhesion, which is not preferable.

[3] Method of using curable composition The curable composition of the present invention is used in the same manner as a known curable composition for a color filter. A description will be given of the case.

  Usually, a curable composition dissolved or dispersed in a solvent is supplied in a film or pattern by a method such as coating on a substrate on which a spacer is to be provided, and the solvent is dried and then supplied in a film. If necessary, pattern formation is performed by a method such as photolithography in which exposure and development are performed as necessary. Thereafter, if necessary, additional exposure or thermosetting treatment is performed to form spacers on the substrate.

[3-1] Supplying Method to Substrate The curable composition of the present invention is usually supplied onto the substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred. The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually 0.5 μm or more, preferably 1 μm or more, and usually 10 μm or less, preferably 9 μm or less, particularly preferably 7 μm or less. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation in the spacer height is large, a nonuniformity defect occurs in the liquid crystal panel. Further, the curable composition may be supplied in a pattern by an ink jet method or a printing method.

[3-2] Drying method Drying after supplying the curable composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 130 ° C., preferably 30 to 50 to 110 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of seconds to 3 minutes.

[3-3] Exposure Method Exposure is performed by superimposing a negative mask pattern on the coating film of the curable composition and irradiating an ultraviolet light source or a visible light source through this mask pattern. Further, a scanning exposure method using a laser beam without using a mask pattern may be used. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, it is carried out in a deoxygenated atmosphere or oxygen such as a polyvinyl alcohol layer on the photopolymerizable layer made of the curable composition of the present invention. Exposure may be performed after the blocking layer is formed.

  The light source used for said exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[3-4] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids. These may be used individually by 1 type, or may use 2 or more types together.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. An organic solvent may be used individually by 1 type, may be 2 or more types of mixed solvents, and may be used as aqueous solution.

[3-5] Additional Exposure and Thermosetting Treatment If necessary, the substrate after development may be subjected to additional exposure by the same method as the above exposure method, or may be subjected to thermosetting treatment. The thermosetting treatment conditions in this case are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. It is particularly preferable to perform such a thermosetting treatment.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

<Example 1>
In a 1000 ml four-necked flask, 231 g of diglycidyl etherified product (epoxy equivalent 231) of 9,9-bis (4′-hydroxyphenyl) fluorene, 72 g of acrylic acid, 6.06 g of triethylbenzylammonium chloride, and p-methoxyphenol 0.15 g and propylene glycol monomethyl ether acetate 170 g were charged and dissolved by heating at 70 to 80 ° C., and further, the solution was gradually heated to 85 ° C. in a cloudy state and completely dissolved, and subsequently became transparent and viscous. The solution was stirred and heated for 8 hours until the acid value reached 3.0 mg · KOH / g, and a colorless and transparent reaction product was obtained. Propylene glycol monomethyl ether acetate was added to the obtained reaction product to adjust the solid content to 50% by weight.

Subsequently, 8.7 g of 1,2,3,6-tetrahydrophthalic anhydride is added to 100 g of the obtained 50% by weight solid solution, and the temperature is gradually raised and reacted at 80 to 85 ° C. for 3 hours. The solution of the ethylenically unsaturated group and carboxyl group-containing compound (I-1) of the present invention was obtained.
The obtained compound (I-1) had an acid value of 55 mg · KOH / g and a weight average molecular weight of 1,100.

<Example 2>
By reacting 118 parts by weight of succinic anhydride with 596 parts by weight of commercially available pentaerythritol triacrylate at 85 ° C. for 5 hours in the presence of 2.5 parts by weight of triethylamine and 0.25 parts by weight of hydroquinone, A polyfunctional acrylate mixture having an acid value of 92.7 comprising 66% by weight of a polyfunctional acrylate having one carboxyl group and two or more acryloyl groups and 34% by weight of pentaerythritol tetraacrylate (ethylenically unsaturated group-containing carboxylic acid) A mixture (b-1)) was obtained.

A solution of compound (I-2) was obtained in the same manner as in Synthesis Example 1 except that 605 g of this ethylenically unsaturated group-containing carboxylic acid mixture (b-1) was used instead of 72 g of acrylic acid.
The obtained compound (I-2) had an acid value of 55 mg · KOH / g and a weight average molecular weight of 2,500.

<Example 3>
100 parts by weight of 9,9-bis (4′-hydroxyphenyl) fluorene diglycidyl etherification product (epoxy equivalent 231), ethylenically unsaturated group-containing carboxylic acid mixture (b-1) (acid value 90.5) 248 .8 parts by weight, 0.17 parts by weight of p-methoxyphenol, 7.0 parts by weight of triphenylphosphine, and 349 parts by weight of propylene glycol monomethyl ether acetate were charged into a reaction vessel, and the acid value at 90 ° C. was 5 mg · KOH / g. Stir until: It took 10 hours for the acid value to reach the target (acid value 1.0 mg · KOH / g). Next, 6 parts by weight of propylene glycol monomethyl ether acetate is added to 80 parts by weight of the reaction solution obtained by the above reaction, 1.6 parts by weight of hexamethylene diisocyanate and 0.01 parts by weight of dibutyltin dilaurate are added, and the mixture is heated at 85 ° C. for 3 hours. Then, 3.6 parts by weight of trimellitic anhydride was added and reacted at 85 ° C. for 3 hours to obtain a solution of the ethylenically unsaturated group- and carboxyl group-containing compound (I-3) of the present invention.
The obtained compound (I-3) had an acid value of 51 mg · KOH / g and a weight average molecular weight of 3,100.

<Example 4>
280 parts by weight of the following epoxy compound (epoxy equivalent 260), 442.7 parts by weight of the ethylenically unsaturated group-containing carboxylic acid mixture (b-1), 0.36 parts by weight of p-methoxyphenol, 14.4 parts by weight of triphenylphosphine Part, and 722.7 parts by weight of propylene glycol monomethyl ether acetate were charged in a reaction vessel and stirred at 85 ° C. until the acid value was 5 mg · KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 4.0 mg · KOH / g). 80 parts by weight of propylene glycol monomethyl ether acetate is added to the reaction solution obtained by the above reaction, 97.9 parts by weight of tetrahydrophthalic anhydride is added, and the mixture is reacted at 85 ° C. for 3 hours to obtain the ethylenically unsaturated group of the present invention. And the solution of the carboxyl group-containing compound (I-4) was obtained.
The obtained compound (I-4) had an acid value of 58 mg · KOH / g and a weight average molecular weight of 2,700.

<Comparative example 1>
Instead of 8.7 g of 1,2,3,6-tetrahydrophthalic anhydride in Example 1, 6.0 g of 1,2,3,6-tetrahydrophthalic anhydride and 11.0 g of biphenyltetracarboxylic anhydride were used. A solution of the ethylenically unsaturated group and carboxyl group-containing compound (II-1) having an acid value of 95.1 mg · KOH / g and a weight average molecular weight of 4,000 was obtained in the same manner except that it was used.

<Comparative example 2>
Instead of 8.7 g of 1,2,3,6-tetrahydrophthalic anhydride in Example 2, 2.6 g of 1,2,3,6-tetrahydrophthalic anhydride and 5.2 g of biphenyltetracarboxylic anhydride were used. A solution of the ethylenically unsaturated group and carboxyl group-containing compound (II-2) having an acid value of 53 mg · KOH / g and a weight average molecular weight of 5200 was obtained in the same manner except that it was used.

<Comparative Example 3>
100 parts by weight of the epoxy compound used in Example 4, 29 parts by weight of acrylic acid, 0.06 parts by weight of p-methoxyphenol, 2.6 parts by weight of triphenylphosphine, and 126 parts by weight of propylene glycol monomethyl ether acetate were added to the reaction vessel. The mixture was stirred and stirred at 95 ° C. until the acid value became 5 mg · KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 4.0 mg · KOH / g). 48 parts by weight of propylene glycol monomethyl ether acetate is added to 257 parts by weight of the resulting reaction solution, 30.84 parts by weight of biphenyltetracarboxylic dianhydride is added, and the mixture is reacted at 90 ° C. for 2 hours. Further, tetrahydrophthalic anhydride 16 Part by weight was added and reacted at 95 ° C. for 3 hours to obtain a solution of an ethylenically unsaturated group and carboxyl group-containing compound (II-3) having an acid value of 106 mg · KOH / g and a weight average molecular weight of 3700.

  The compounds synthesized in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated as follows, and the results are shown in Table 1.

[Evaluation of viscosity change rate (storage stability)]
After the synthesis of the solution of the ethylenically unsaturated group and carboxyl group-containing compound obtained in each example, a solvent was added to adjust the solid content concentration to 40% by weight, the viscosity immediately after the concentration adjustment (initial viscosity), and Viscosity after storage for 24 hours at 70 ° C. in each sealed container (viscosity after treatment) was measured under the condition of 23 ° C. and evaluated according to the following criteria.
○: Viscosity after treatment / initial viscosity is 0.8 or more and 1.2 or less Δ: Viscosity after treatment / initial viscosity is 0.7 or more and 1.3 or less (except in the range of 0.8 to 1.2)
X: Viscosity after treatment / initial viscosity is less than 0.7 or more than 1.3

[Evaluation of curable composition]
<1> Preparation of curable composition 100 parts by weight of the ethylenically unsaturated group and carboxyl group-containing compound obtained in each example, 80 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable monomer, and heat And / or 6 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator and 0.2 part by weight of FC430 (manufactured by Sumitomo 3M, fluorine-based surfactant) as a surfactant, After being dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 35% by weight, it was filtered through a Millipore filter (2 μm) to obtain a curable composition.

<2> Formation of Spacer Pattern After applying the curable composition obtained in the above <1> on the ITO film of the glass substrate having an ITO film formed on the surface using a spinner, hot at 80 ° C. for 3 minutes A film was formed by heating and drying on a plate. The obtained coating film was exposed to an exposure amount of 100 mJ / cm ² using ultraviolet rays having an intensity at 365 nm of 32 mW / cm ² using a predetermined pattern mask. The ultraviolet irradiation at this time was performed under air. Subsequently, spray development was carried out with a 0.1 wt% potassium hydroxide aqueous solution at 23 ° C. for twice the minimum development time, followed by rinsing with pure water for 1 minute. Here, the minimum development time means a time during which the unexposed area is completely dissolved under the same development conditions. By these operations, the substrate on which the unnecessary portion was removed and the spacer pattern was formed was cured by heating in an oven at 230 ° C. for 30 minutes to obtain a cylindrical spacer pattern having a height of 4 μm and a top surface diameter of 10 μm.

The diameter of the upper surface of the spacer pattern was measured as follows.
That is, with respect to the obtained cylindrical spacer pattern, a vertical section passing through the central axis of the spacer pattern was profiled as shown in FIG. 1 using an ultra-deep color 3D shape measuring microscope “VK-9500” manufactured by Keyence Corporation. The straight line AA ′ parallel to the substrate surface in the spacer pattern graphic at 90% of the height from the substrate surface of the profiled graphic (schematic diagram shown in FIG. 2) to the highest point Q Was the upper surface diameter.

<3> Evaluation of mechanical properties The strength of the spacer pattern obtained in the above <2> was evaluated by a load-unloading test using a Shimadzu dynamic ultra-micro hardness meter “DUH-W201S”. A load was applied to the spacer at a constant speed (0.22 gf / sec) with a flat indenter with a diameter of 50 μm at a measurement temperature of 23 ° C. and held for 5 seconds when the load reached 5 gf, and then unloaded at the same speed. Went. From the load-displacement curve obtained from this test (shown schematically in FIG. 3),
Maximum displacement (μm) = H [max]
Final displacement (μm) = H [last]
Recovery rate (%) = (Pattern height before test−H [last]) / (Pattern height before test) × 100
Elastic recovery rate (%) = (H [max] -H [last]) / H [max] × 100
Asked.

  From Table 1, according to the ethylenically unsaturated group and carboxyl group-containing compound of the present invention, the curable composition is excellent in mechanical properties such as recovery rate and elastic recovery rate of the cured product, and also excellent in storage stability. It can be seen that

It is a schematic diagram which shows the position to profile when a spacer pattern is seen from the top. It is a schematic diagram which shows the profile of the longitudinal cross-section of a spacer pattern. It is a figure which shows the load and displacement in a load-unloading test.

Explanation of symbols

1 Spacer pattern 2 Center axis of spacer pattern 3 Profile position 4 Profile of spacer pattern longitudinal section 5 Height from substrate surface to highest position 6 Height 90% of height from substrate surface to highest position 7 Circle of upper section Diameter AA '

Claims (8)

An ethylenically unsaturated group- and carboxyl group-containing compound represented by the following general formula (I):

(1) To a compound having an ethylenically unsaturated group-containing carbonyloxy group obtained from an epoxy group-containing compound,
(2) An ethylenically unsaturated group and carboxyl group-containing compound obtained by reacting a polyvalent carboxylic acid and / or an anhydride thereof,
(2) A compound containing an ethylenically unsaturated group and a carboxyl group, wherein the polyvalent carboxylic acid and / or its anhydride is substantially free of tetravalent or higher carboxylic acid and / or its anhydride. (1) To a compound having an ethylenically unsaturated group-containing carbonyloxy group obtained from an epoxy group-containing compound,
(3) After reacting the isocyanate group-containing compound,
(2) An ethylenically unsaturated group and carboxyl group-containing compound obtained by reacting a polyvalent carboxylic acid and / or an anhydride thereof,
(2) A compound containing an ethylenically unsaturated group and a carboxyl group, wherein the polyvalent carboxylic acid and / or its anhydride is substantially free of tetravalent or higher carboxylic acid and / or its anhydride.   (2) The ethylenically unsaturated group and carboxyl group-containing compound according to claim 2 or 3, wherein the polyvalent carboxylic acid and / or anhydride thereof is a trivalent or lower carboxylic acid compound.   Viscosity change rate is 0.7-1.3, The ethylenically unsaturated group and carboxyl group containing compound of any one of Claim 1 thru | or 4 characterized by the above-mentioned.   A curable composition comprising the ethylenically unsaturated group- and carboxyl group-containing compound according to any one of claims 1 to 5.   A color filter formed using the curable composition according to claim 6.   A liquid crystal display device formed using the curable composition according to claim 6.

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