KR20150024304A - Curable composition, cured film and display element - Google Patents

Abstract

A composition having excellent curability against radiation irradiation or heating is provided. The curable composition of the present invention is characterized by containing the following components (A ¹ ) and (B): (A ¹ ) a hydroxyl group of a polymer of a monomer containing a (meth) acrylic monomer having a hydroxy group, (B) a compound having at least two functional groups capable of reacting with a sulfanyl group.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable composition, a cured film,

More particularly, the present invention relates to an image forming material such as a three-dimensional stereolithography, a holographic film, a color filter, a photoresist, a flat plate, a color proof, an insulating film material, A curing composition usable for a coating material, an adhesive, a sealing material, a coating material, a dental material, etc., a cured film formed using the curable composition, and a display device comprising the cured film.

BACKGROUND ART Conventionally, a curable composition that is cured upon irradiation or heating of radiation has been widely used as an image forming material such as a three-dimensional stereolithography, a holography, a color filter, a photoresist, a plate printing plate, a color proof, an insulating film material, , Adhesives, sealing materials (liquid crystal display elements, LED elements, organic EL elements, etc.), coating agents, dental materials, and the like.

For example, Patent Documents 1 and 2 disclose that a radiation-sensitive or thermosetting resin composition using a specific epoxy resin is suitable as a material for forming a protective film or a planarizing film used in an optical device. In Patent Document 3, it is disclosed that a photopolymerizable composition containing a specific ethylenically unsaturated compound is suitable as a color filter resist.

Japanese Patent Application Laid-Open No. 6-43643 Japanese Unexamined Patent Application Publication No. 6-157716 Japanese Patent Laid-Open No. 8-327813

In recent years, along with the demand for energy saving, reduction in load on environment, improvement of productivity of devices, etc., curing compositions are required to have lower curing temperature and higher sensitivity to radiation. Further, it is known that it is effective to use a dye as a coloring agent in order to realize high brightness or high definition of a color filter. However, in the curable composition containing a dye, further improvement of curability is required.

Accordingly, an object of the present invention is to provide a composition having excellent curability against irradiation with radiation and heating. It is still another object of the present invention to provide a color filter comprising a coloring layer formed from the curable composition, and a display element comprising the color filter.

In view of such circumstances, the present inventors have conducted intensive studies and found that the above problems can be solved by using a specific polymer having a sulfonyl group (-SH), and have completed the present invention.

That is, the present invention provides a curable composition characterized by containing the following components (A ¹ ) and (B):

(A ¹ ) a polymer obtained by at least a step of esterifying a carboxylic acid having a sulfanyl group to a hydroxy group of a polymer of a monomer containing a (meth) acrylic monomer having a hydroxy group (hereinafter referred to as "(A ¹ ) polymer"Quot;),

(B) a compound having two or more functional groups capable of reacting with a sulfanyl group (hereinafter also referred to as "(B) crosslinking agent")).

The present invention also provides a curable composition characterized by containing the following components (A ² ) and (B):

(A ² ) a polymer having a repeating unit represented by the following formula (1) (hereinafter also referred to as "(A ² ) polymer"),

(B) a compound having two or more functional groups capable of reacting with a sulfanyl group.

[In the formula (1)

R ¹ represents a hydrogen atom or a methyl group,

R ² , R ³ and R ⁴ independently of one another represent a substituted or unsubstituted divalent hydrocarbon group,

X represents -COO- (* ¹ ) or -CONH- (* ¹ )

Z represents a single bond, -CO- or -COO- (* ² )

m represents an integer of 1 to 30,

n represents an integer of 0 to 30,

However, "* ^1" represents a bonding hand in combination with R ^2, "* ^2" represents a bonding hand, combined with R ^3]

The present invention also provides a cured film formed using the curable composition, and a display element comprising the cured film.

The curable composition of the present invention has excellent curability against radiation irradiation or heating.

Therefore, the curable composition of the present invention can be used for various color filters constituting color liquid crystal display devices, solid-state image pickup devices, organic EL display devices and the like, as well as insulating film materials, protective film materials, inks, paints, adhesives, Sealing materials, coating materials, dental materials, etc. for devices, organic EL devices and the like.

Hereinafter, the present invention will be described in detail.

Curable composition

The curable composition of the present invention contains (A ¹ ) or (A ² ) component and (B) component. Hereinafter, each component will be described in detail. In the following description, components (A ¹ ) and (A ² ) will be collectively described as component (A).

- (A) polymer-

(A) The polymer is a polymer having a plurality of sulfanyl groups. The curable composition of the present invention exhibits excellent curability because the polymer (A) crosslinks with a compound having an ethylenically unsaturated group or an epoxy compound and acts as a chain transfer agent in a radical curing reaction of a compound having an ethylenically unsaturated group.

(A ¹ ) polymer has a hydroxyl group of a polymer of a monomer (hereinafter also referred to as " hydroxy group-containing polymer ") comprising a (meth) acrylic monomer having a hydroxy group (hereinafter also referred to as " Is subjected to an esterification reaction. The term "(meth) acrylic monomer" is a concept including not only (meth) acrylate monomers but also (meth) acrylamide monomers.

The monomer (a1) is not particularly limited as long as it is a compound having a hydroxy group and a (meth) acryloyloxy group or a (meth) acryloylamide group, and examples thereof include a compound represented by the following formula (3) . The monomers (a1) may be used alone or in combination of two or more.

[In the formula (3)

R ¹ represents a hydrogen atom or a methyl group,

R ² and R ³ independently represent a substituted or unsubstituted divalent hydrocarbon group,

X represents -COO- (* ¹ ) or -CONH- (* ¹ )

Z represents a single bond, -CO- or -COO- (* ² )

m represents an integer of 1 to 30,

n represents an integer of 0 to 30,

However, "* ^1" represents a bonding hand in combination with R ^2, "* ^2" represents a bonding hand, combined with R ^3]

Examples of the divalent hydrocarbon group for R ² and R ³ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be either straight chain or branched, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In the present specification, the terms "alicyclic hydrocarbon group" and "aromatic hydrocarbon group" as used herein include not only a group consisting of a ring structure but also an alicyclic hydrocarbon group substituted with the ring structure, A hydrocarbon or an aromatic hydrocarbon.

The divalent aliphatic hydrocarbon group includes, for example, an alkanediyl group and an alkenediyl group, and the number of carbon atoms thereof is preferably from 1 to 20, more preferably from 2 to 12. Specific examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, A butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,4-diyl group, a pentane-1,2-diyl group, , A 5-diyl group, a hexane-1,5-diyl group, a hexane-1,6-diyl group, a 2-methylpropane-1,2-diyl group, a 2,2- A propene-1,2-diyl group, a propene-2,3-diyl group, a 1- Butene-1,4-diyl group, 2-pentene-1,5-diyl group, 3-hexene-1,6-diyl group, And a diary machine.

The bivalent alicyclic hydrocarbon group includes, for example, a cycloalkylene group and a cycloalkenylene group, and the number of carbon atoms thereof is preferably from 3 to 20, more preferably from 3 to 12. Specific examples thereof include a group represented by the following formula (4) in addition to a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclobutenylene group, a cyclopentenylene group, a cyclohexenylene group and the like.

[In the formula (4)

Y represents a divalent group selected from the group of groups represented by the following formulas (i) to (iv)

a and b each independently represent an integer of 0 to 6;

The divalent aromatic hydrocarbon group includes, for example, an arylene group, and a monocyclic to tricyclic arylene group having 6 to 14 carbon atoms is preferable. Specific examples thereof include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group and an anthrylene group.

Among them, as the divalent hydrocarbon group relating to R ² and R ³ , a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and more preferably 1 to 12 carbon atoms is preferable, and an alkanediyl group is particularly preferable. R ² and R ³ may be the same or different, and when a plurality of R ² and R ³ are present, they may be the same or different.

Examples of the substituent of the divalent hydrocarbon group for R ² and R ³ include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specific examples of the alkoxy group having 1 to 6 carbon atoms include, for example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group and pentyloxy group.

X is -COO -, -COO of the (* ¹⁾ - - (* ¹⁾ and the -CONH ⁽¹⁾ is preferred.

m is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.

n is preferably an integer of 0 to 6, more preferably an integer of 1 to 3, further preferably 0 or 1.

More preferred examples of the compound represented by the formula (3) include compounds represented by the following formulas (5) to (8).

[In the formulas (5) to (8)

R ¹ , X, Y, a, b and m are as defined above,

R ⁷ and R ⁸ independently represent a substituted or unsubstituted divalent aliphatic hydrocarbon group,

and r represents an integer of 1 to 30;

As the divalent aliphatic hydrocarbon group related to R ⁷ and R ⁸ , an alkanediyl group having 1 to 20 carbon atoms and more preferably 1 to 12 carbon atoms is preferable. In addition, R ⁷ and R ⁸ each may be the same or may be different, and the substituents of the second aliphatic hydrocarbon group with a valence of the R ⁷ and R ⁸ is the substituent similar to those in R ² and R ^3, preferably Beach Whanin .

r is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.

Specific examples of the compound represented by the formula (5) include, for example, 2-hydroxyethyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl Hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 11-hydroxydecyl (meth) acrylate, HydroxyC _{1 - 12} alkyl (meth) acrylates such as 12-hydroxydecyl (meth) acrylate and 12-hydroxydodecyl (meth) acrylate; In addition to the polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) polyalkylene glycol acrylate mono (meth) acrylate, a hydroxy-C _{1 - 12} alkyl (meth) acrylate, (meth) corresponding to a polyalkylene glycol mono (meth) acrylate may be mentioned acrylamide.

Specific examples of the compound represented by the formula (6) wherein m = 1 and r = 1 include 2- (6-hydroxyhexanoyloxy) ethyl (meth) acrylate, 3- (Meth) acrylate, 5- (6-hydroxyhexanoyloxy) propyl (meth) acrylate, 4- (6-hydroxyhexanoyloxy) 6- (6-hydroxy-hexanoyl-oxy) hexyl (meth) acrylate such as a (hydroxy hexanoyl oxy) C _{1 - 12} in addition to the alkyl (meth) acrylate, and the like, of the (meth) acrylamides corresponding to these . Further, (6-hydroxy-hexanoyl-oxy), C _{1 -} to a commercially available _12-alkyl (meth) acrylate, flat raksel (PLACCEL) FM1D, flat raksel FM2D (trade name, manufactured by Daicel Kagaku Kogyo (Co., Ltd.)), etc. Can be used.

Specific examples of the compound represented by the above formula (7) wherein m = 1 and r = 1 include 2- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) ethyl ) Acrylate, 3- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) propyl (meth) acrylate, 4- (Meth) acrylate, 6- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) pentyl (meth) ) hexyl (meth) acrylate such as a (3-hydroxy-2,2-dimethyl-propoxycarbonyl-oxy) C _{1 - 12} in addition to the alkyl (meth) acrylate, and the like, of the (meth) acrylamides corresponding to these . Also, (3-hydroxy-2,2-dimethyl-propoxycarbonyl-oxy) C _{1 - 12} alkyl (meth) acrylate as the commercial products of, hemak (HEMAC) 1 (trade name, manufactured by Daicel Kagaku Kogyo (Co., Ltd.) ) Can be used.

Specific examples of the compound represented by the above formula (8) include, for example, 4-hydroxycyclohexyl (meth) acrylate, 3-hydroxybicyclo [2.2.1] hept- (Meth) acrylate, 2-hydroxyoctahydro-4,7-methanoinden-5-yl (meth) acrylate, 8-hydroxybicyclo [2.2.1] hept- (Meth) acrylate, 2- [4- (2-hydroxyethyl) cyclohexylmethyl (meth) acrylate, 3-hydroxyadamantan- (Meth) acrylate, 2- [3- (2-hydroxyethyl) ethyl (meth) acrylate, (Meth) acrylate, (2-hydroxymethyloctahydro-4,7-methanoinden-5-yl) methyl (meth) Acrylate, 2- (2- (2-hydroxyethyl) octahydro-4,7-methanoinden-5-yl] ethyl (meth) acrylate, Ethyl (meth) acrylate, and the like, as well as 2- (3- (2-hydroxyethyl) adamantan-1-yl] (Meth) acrylamide.

In the hydroxy group-containing polymer, monomers other than the monomer (a1) may be copolymerized. As the monomers other than the monomer (a1), for example,

N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, p-hydroxystyrene, p-hydroxy-? -Methylstyrene and acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (Meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, (Meth) acrylate such as ethylene oxide modified (meth) acrylate of p-cumylphenol;

And a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

These monomers may be used alone or in combination of two or more.

Among them, it is preferable that a monomer other than the monomer (a1) contains a (meth) acrylic acid ester.

In the hydroxy group-containing polymer, the use ratio of the monomer (a1) is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass. The upper limit of the use ratio of the monomer (a1) is preferably 80% by mass. The use ratio of the monomers other than the monomer (a1) is the balance of the use ratio of the monomer (a1).

The hydroxy group-containing polymer can be produced, for example, by radical polymerization of the monomer (a1) or the like. The Mw / Mn and the residual amount of the unreacted monomer are controlled by a living radical polymerization method, a living anion polymerization method, a living cation polymerization method, You may. Further, radical polymerization may be carried out in the presence of a trifunctional or more low-molecular polyfunctional thiol to give a star-shaped polymer.

On the other hand, the carboxylic acid having a sulfanyl group is not particularly limited, but a compound represented by the following formula (9) is preferable.

[In the formula (9), R ⁴ represents a substituted or unsubstituted divalent hydrocarbon group]

R ⁴ is the same as the divalent hydrocarbon group for R ² and R ³ . Among them, an alkanediyl group having 1 to 10 carbon atoms and more preferably 3 to 10 carbon atoms is preferred. The substituent may be the same as the substituent in R ² and R ³ , but is preferably unsubstituted.

Specific examples of the carboxylic acid having sulfanyl group include 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobutanoic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, 2- Mercaptoisopentanoic acid, 3-mercaptoisopentanoic acid, 3-mercaptoisohexanoic acid, and the like.

In the esterification reaction between the hydroxy group-containing polymer and the carboxylic acid having a sulfanyl group, a known esterification reaction may be employed. At this time, although the hydroxyl group of the hydroxy group-containing polymer may be all esterified, it is preferable to retain the hydroxyl group so that the hydroxyl value is 3 to 100 mg KOH / g, preferably 5 to 80 mg KOH / g. The hydroxyl value is measured according to the method described in the following Examples.

On the other hand, the (A ² ) polymer is a polymer having a repeating unit represented by the following formula (1), wherein the hydroxyl group of the polymer of the monomer containing the compound represented by the formula (3) It is preferably a polymer obtained by at least a step of subjecting the compound to an esterification reaction.

R ¹ , R ² , R ³ , R ⁴ , X, Z, m and n are as defined above]

(A ² ) polymer preferably further has a repeating unit represented by the following formula (2), and more preferably a repeating unit other than the repeating unit represented by the formula (1) and the repeating unit represented by the following formula (2) .

[In the formula (2)

R ¹ , R ² , R ³ , X, Z, m and n are as defined above,

R ⁵ represents a hydrogen atom or -CO-R ⁶ -COOH,

And R < ⁶ > represents a divalent hydrocarbon group.

In the polymer (A ² ), the content of the repeating unit represented by the above formula (1) is generally 5% by mass or more, preferably 10 to 80% by mass, and particularly preferably 15 to 70% by mass. In the polymer (A ² ), the content of the repeating unit represented by the formula (2) is preferably 1 to 50% by mass, particularly preferably 2 to 30% by mass.

As the polymer (A), the (A ¹ ) polymer or the (A ² ) polymer may be used as it is, but the polymer (A) having a carboxyl group introduced may also be obtained by reacting at least a part of the remaining hydroxyl groups with a polybasic acid anhydride. The polymer (A) obtained by the reaction of at least a part of the hydroxyl group with the polybasic acid anhydride is preferable in view of having alkali solubility.

As the polybasic acid anhydride, various compounds can be used, and any of saturated polybasic acid anhydrides and unsaturated polybasic acid anhydrides can be used. Among them, an anhydride of a dibasic acid represented by the following formula (10) is preferable.

[In the formula (10), R ⁶ represents a divalent hydrocarbon group]

Examples of R ⁶ include the same divalent hydrocarbon groups as R ² and R ³ . Among them, an alkanediyl group having 1 to 10 carbon atoms, an alkenediyl group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkenylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 14 carbon atoms are preferable .

Specific examples of the dibasic acid anhydride include maleic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride, anhydroglutaric acid, anhydroglutaconic acid, itaconic anhydride, diglycolic anhydride, phthalic anhydride, Hexane-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, and anhydrous diphenic acid.

The polymer (A) may be used alone or in combination of two or more.

The thiol equivalent (g / eq) of the polymer (A) is preferably 150 to 2,000 g / eq, more preferably 200 to 1,500 g / eq in order to enhance the desired effect. The thiol equivalent is determined according to the method described in the following examples.

The molecular weight of the (A) polymer can be measured as the weight average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as the mobile phase. The weight average molecular weight (Mw) of the polymer (A) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000. Within this range, the desired effect can be further enhanced.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured under the same conditions as the weight average molecular weight (Mw), that is, the dispersion degree (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, More preferably 1.0 to 2.5. Within this range, the desired effect can be further enhanced.

The content of the polymer (A) in the present invention is preferably 0.1 to 70% by mass, more preferably 0.5 to 50% by mass, and particularly preferably 1 to 30% by mass in the solid content of the curable composition. Here, in the present specification, the term " solid content " is a component other than the solvent described later.

- (B) a compound having two or more functional groups capable of reacting with a sulfanyl group -

The compound (B) having two or more functional groups capable of reacting with the sulfanyl group is not particularly limited as long as it has two or more functional groups capable of reacting with the sulfanyl group, and may be a low molecular compound or a high molecular compound. Hereinafter, the compound (B) having two or more functional groups capable of reacting with the sulfanyl group is also referred to as (B) a crosslinking agent.

In the present invention, the crosslinking agent (B) is preferably a compound having at least one of an ethylenic unsaturated group and a group having a cyclic ether structure. The ethylenically unsaturated group is preferably a (meth) acryloyl group, and the group having a cyclic ether structure is preferably an oxiranyl group or an oxetanyl group.

Examples of the crosslinking agent (B) include a monomer having two or more ethylenically unsaturated groups, a polymer having two or more ethylenically unsaturated groups, a monomer having two or more cyclic ether structures, a polymer having two or more cyclic ether structures, A monomer having two or more ethylenic unsaturated groups and a cyclic ether structure, and a polymer having two or more ethylenic unsaturated groups and cyclic ether structures in total.

The molecular weight of the polymer (B) crosslinking agent is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, in terms of polystyrene as measured by GPC using tetrahydrofuran as a mobile phase, and the dispersion degree (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Within this range, the desired effect can be further enhanced.

Examples of the monomer having two or more ethylenic unsaturated groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, caprolactone modified polyfunctional (meth) acrylates, alkylene oxide modified (Meth) acrylate obtained by reacting a polyfunctional (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate and a polyfunctional (meth) acrylate having a hydroxyl group with an acid anhydride (Meth) acrylate having a carboxyl group to be obtained are preferable.

Specific examples of polyfunctional (meth) acrylates obtained by reacting the aliphatic polyhydroxy compound with (meth) acrylic acid include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tripentaerythritol octa (meth) acrylate. Further, specific examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Specific examples of the alkylene oxide-modified polyfunctional (meth) acrylate include compounds described in claim 1 of Japanese Patent Application Laid-Open No. 10-62986, Japanese Patent Application Laid-Open No. 2008-83508 1, and the like. Further, specific examples of the polyfunctional urethane (meth) acrylate obtained by reacting the (meth) acrylate having a hydroxyl group with the polyfunctional isocyanate are described in paragraphs [0014] to [0015] of JP 2003-315998 A And the like. Specific examples of the polyfunctional (meth) acrylate having a carboxyl group obtained by reacting the polyfunctional (meth) acrylate having a hydroxyl group with an acid anhydride include compounds obtained by reacting pentaerythritol triacrylate with succinic anhydride, di And compounds obtained by reacting pentaerythritol pentaacrylate with succinic anhydride.

These monomers having two or more ethylenic unsaturated groups may be used alone or in admixture of two or more.

The polymer having two or more ethylenically unsaturated groups is preferably a polymer having an ethylenic unsaturated group such as a (meth) acryloyl group and a carboxyl group. Specific examples of such a polymer include (meth) acrylic copolymers having an ethylenically unsaturated group introduced through a glycidyl group as disclosed in JP-A-5-19467 and the like; Vinyl-based copolymers having a vinyl group introduced through an isocyanate group described in JP-A-6-230212 and the like; (Meth) acrylic copolymers having an alicyclic (meth) acryloyl group described in International Patent Publication WO 96/23237 and the like; (Meth) acrylates described in Japanese Patent Application Laid-Open Nos. 7-207211, 9-325494, 11-140144, 2008-181095, An epoxy resin into which an acryloyl group and a carboxyl group are introduced; And a photosensitive resin having a fluorene skeleton described in International Publication No. 09/119622. Also, polysiloxanes having a (meth) acryloyl group in the side chain described in paragraphs [0111] to [0112] of JP 2008-242078 A may be suitably used, for example.

These polymers having two or more ethylenic unsaturated groups may be used singly or in combination of two or more.

Examples of the monomer having two or more cyclic ether structures include glycidyl ethers of aliphatic polyhydroxy compounds, oxetanyl alkyl ethers of aliphatic polyhydroxy compounds, glycidyl ethers of bisphenol, oxetanyl Alkyl ethers and the like are preferable. Specific examples of glycidyl ethers of aliphatic polyhydroxy compounds include 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, and the like. Specific examples of the oxetanyl alkyl ethers of the aliphatic polyhydroxy compound include (poly) ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis Ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis ) Ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, and the like.

Specific examples of glycidyl ethers of bisphenol include bisphenol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenated products thereof. Specific examples of the oxetanyl alkyl ethers of bisphenol include oxyethylene-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, oxypropylene-modified bisphenol A bis , Hydrogenated products thereof, and oxyethylene-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

These monomers having two or more cyclic ether structures may be used alone or in combination of two or more.

As the polymer having two or more cyclic ether structures, a copolymer of an ethylenically unsaturated monomer having an oxiranyl group or an oxetanyl group and an ethylenically unsaturated monomer having a carboxyl group is preferable. Specific examples of such copolymers are disclosed in JP-A-6-43643, JP-A-6-157716, JP-A-2001-302712, JP-A-2007-292840 And the like. In addition to the bisphenol type epoxy resin, fluorene type epoxy resin and phenol novolak type epoxy resin, there may be used, for example, a cyclic ether structure in the side chain described in paragraphs [0114] to [0115] of Japanese Patent Laid- Is also preferred.

These polymers having two or more cyclic ether structures may be used alone or in admixture of two or more.

As the monomer having two or more ethylenic unsaturated groups and cyclic ether structures, (meth) acrylate or vinyl ether having an oxiranyl group or oxetanyl group is preferable. Specific examples thereof include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, 3,4-epoxycyclohexylmethyl , 3 - [(meth) acryloyloxymethyl] oxetane, 3 - [(meth) acryloyloxymethyl ] -3-ethyloxetane.

These monomers having two or more of these ethylenic unsaturated groups and cyclic ether structures may be used singly or in combination of two or more.

The polymer having two or more ethylenic unsaturated groups and cyclic ether structures is preferably a polymer having an ethylenic unsaturated group such as a (meth) acryloyl group and an oxetanyl group. Specific examples of such polymers are disclosed in JP-A-2010-44365 and the like.

These polymers having two or more of these ethylenic unsaturated groups and cyclic ether structures may be used singly or in combination of two or more.

As the crosslinking agent (B) in the present invention, a monomer having two or more ethylenic unsaturated groups, a polymer having two or more ethylenic unsaturated groups, a polymer having two or more cyclic ether structures, a polymer having an ethylenic unsaturated group and a cyclic ether structure (Meth) acrylate, which is obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and a polyfunctional (meth) acrylate having a hydroxyl group (Meth) acrylate having a carboxyl group obtained by reacting (meth) acrylate with an acid anhydride, and more preferably at least one member selected from the group consisting of dipentaerythritol penta (meth) acrylate, dipentaerythritol Lithol hexa (meth) acrylate and dipentaerythritol pentaacrylate and anhydride And at least one compound selected from the compounds obtained by reacting an acid. The polyfunctional (meth) acrylate preferably has three or more (meth) acryloyloxy groups, and more preferably five or more (meth) acryloyloxy groups.

In the present invention, the crosslinking agent (B) may be used alone or in combination of two or more.

The content of the crosslinking agent (B) in the present invention is preferably 10 to 100,000 parts by mass, particularly preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the (A) polymer. In this range, excellent curability can be obtained by using the combination of the (A) polymer and the (B) crosslinking agent.

- (C) Colorant -

The curable composition of the present invention may contain (C) a colorant. Thus, for example, a colored curable composition for forming a colored layer can be used. Here, the "colored layer" means each color pixel used in a color filter, a black matrix used in a liquid crystal display element, a black spacer, and the like. The colorant is not particularly limited as long as it has colorability, and the color and the material can be appropriately selected depending on the use of the curable composition. When the curable composition of the present invention is used for forming a coloring layer of a color filter, at least one coloring agent selected from pigments and dyes is preferable in that color filters are required to have high color purity, brightness, contrast and the like.

Examples of the pigment include organic pigments and inorganic pigments. Preferred examples of the organic pigments include CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242 , CI Pigment Red 254, CI Pigment Red 264, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15: 6, CI Pigment Blue 80, CI Pigment Yellow 83 , CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Orange 38, Pigment Violet 23 and the like. Specific examples of preferable inorganic pigments include carbon black, titanium black and the like.

As the pigment, a lake pigment is also preferable, and specifically, a lake obtained by laking with a triarylmethane dye or a xanthene dye with an isopoly acid or a heteropoly acid. The triarylmethane lake pigment is disclosed in, for example, Japanese Patent Laid-Open Publication No. 186043/1986. The xanthan gum lake pigment is disclosed in, for example, Japanese Patent Application Laid-Open No. 2010-191304.

As the dyes, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes and azo dyes are preferable. More specifically, Japanese Patent Application Laid-Open Nos. 2010-32999, 2010-254964, 2011-138094, 10/123071, 2011- Organic dyes described in Japanese Patent Application Laid-Open No. 116803, Japanese Patent Application Laid-Open No. 2011-117995, Japanese Patent Application Laid-Open No. 2011-133844, Japanese Patent Laid-Open No. 2011-174987, and the like.

In the present invention, the pigment and the dye may be used alone or in combination of two or more.

In the present invention, the pigment may be purified and used by recrystallization, reprecipitation, solvent cleaning, sublimation, vacuum heating, or a combination thereof. Further, the pigment may be used by modifying its particle surface with a resin, if necessary. Further, the organic pigment can be used by refining the primary particles by so-called salt milling. As a method of the salt milling, for example, a method disclosed in Japanese Unexamined Patent Application Publication No. 08-179111 can be adopted.

The content ratio of the (C) coloring agent is usually from 5 to 70% by mass, preferably from 5 to 60% by mass, more preferably from 5 to 60% by mass, in the solid content of the curable composition, from the viewpoint of forming a pixel having a high luminance and excellent color purity, to be.

In the present invention, when a pigment is used as a colorant, it may be used together with a dispersant and a dispersion auxiliary agent as required. As the dispersing agent, for example, a suitable dispersing agent such as cationic, anionic, nonionic, or the like can be used, but a polymer dispersant is preferable. Specific examples thereof include acrylic copolymers, polyurethanes, polyesters, polyethyleneimines, polyallylamines, and the like.

Such dispersants are commercially available and include, for example, acrylic copolymers such as Disperbyk-2000, Disperby-2001, BYK-LPN6919, BYK-LPN21116 and BYK-LPN21324 (manufactured by BYK- Disperbyk-162, Disperbyk-162, Disperbyk-167, Disperbyk-167, Disperbyk-170, Disperbyk-182 and Disperbyk-2164 (manufactured by BYK Corporation) as polyurethanes, (Manufactured by Lubrizol Corporation) as a polyethyleneimine and Ajisper PB821, Ajisper PB822 and Ajisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as polyesters, Respectively. As the acrylic copolymer, copolymers disclosed in JP-A Nos. 2011-232735, 2011-237769 and 2012-32767 can be suitably used. Further, the content of the dispersant can be suitably determined within a range not hindering the object of the present invention.

Examples of the dispersion aid include pigment derivatives, and specific examples thereof include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. Further, the content of the dispersion auxiliary agent can be suitably determined within a range not hindering the object of the present invention.

- (D) photo-radical generator -

The curable composition of the present invention may contain (D) a photo-radical generator. Thus, when a compound having two or more ethylenic unsaturated groups is used as the crosslinking agent, the curable composition of the present invention exhibits a high sensitivity to radiation.

Such a photo-radical generator is not particularly limited, but a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound and the like are preferable.

Specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Specific examples of the acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- -Morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, when a non-imidazole-based compound is used as the photo radical generator, it is preferable to use a hydrogen donor in view of improving the sensitivity. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, 4,4'- Amino) benzophenone, and the like. In the present invention, the hydrogen donors may be used singly or in combination of two or more. However, the combination of at least one mercaptan-based hydrogen donor and at least one amine-based hydrogen donor makes it possible to further improve the sensitivity .

Specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan- Bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] 2- (4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4 , 6-bis (trichloromethyl) -s-triazine, and the like.

Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), ethanone, 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- -9H-carbazol-3-yl] -, 1- (O-acetyloxime), ethanone, 1- [ -Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- (O-acetyloxime), as disclosed in WO 08/078678, Oxime ester compounds described in JP-A-2011-132215. As commercially available products of O-acyloxime compounds, NCI-831 and NCI-930 (manufactured by ADEKA) can be used.

In the present invention, the photo-radical generating agents may be used alone or in admixture of two or more.

When the photo-radical generator is used in the present invention, its content is preferably from 1 to 10,000 parts by mass, particularly preferably from 10 to 5,000 parts by mass, per 100 parts by mass of the polymer (A).

In the present invention, when a photopolymerization initiator is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, Dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- 3- Coumarin, 4- (diethylamino) chalcone, anthracene, 2-tert-butyl anthracene, perylene and the like.

- (E) Binder Resin -

The curable composition of the present invention may contain (E) a binder resin (excluding the above (A) polymer and (B) crosslinking agent). This makes it possible to improve the alkali solubility, binding properties, storage stability, and the like of the curable composition. As the binder resin, a resin having an acidic functional group such as a carboxyl group and a phenolic hydroxyl group is preferable, as long as it does not correspond to the above (A) polymer and (B) the crosslinking agent. Among them, a polymer having a carboxyl group is preferable, and for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as " unsaturated monomer (e1) ") and a copolymerizable ethylenically unsaturated monomer Quot; monomer (e2) ").

Examples of the unsaturated monomer (e1) include unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone mono (meth) p-vinylbenzoic acid and the like.

These unsaturated monomers (e1) may be used alone or in combination of two or more.

Examples of the unsaturated monomer (e2) include monomers other than the monomer (a1) and the monomer (a1).

These unsaturated monomers (e2) may be used singly or in combination of two or more.

As specific examples of the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2), for example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Laid-Open Nos. 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118 And Japanese Patent Application Laid-Open No. 2004-101728.

In the present invention, the (E) binder resin may be used alone or in combination of two or more.

In the present invention, the content of the binder resin (E) is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass based on 100 parts by mass of the crosslinking agent (B).

-additive-

The curable composition of the present invention may contain various additives as required.

Examples of additives include fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like; (Meth) acryloyloxyethyl] phthalate mono [2- (meth) acryloyloxyethyl], and omega -carboxypolycaprolactone mono (meth) .

-menstruum-

The curable composition of the present invention contains the above components (A) to (B), and optionally other components, which are usually prepared as a liquid composition by blending a solvent.

As the solvent, any of the components (A) to (B) and other components constituting the curable composition may be appropriately selected and used as long as they are dispersible or dissolving, do not react with these components, and have appropriate volatility.

As such a solvent, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl (meth) acrylate such as propylene glycol monoethyl ether Termini and the like;

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as ethoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Methylhexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy- Ketones;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Propyl acetate, n-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylacetate , N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide

And the like.

Of these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate are preferable from the viewpoints of solubility, pigment dispersibility, Butylene glycol diacetate, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, Diethyl acetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, Amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate are preferable.

In the present invention, the solvents may be used alone or in admixture of two or more.

The content of the solvent is not particularly limited, but from the viewpoints of coatability, stability, and the like of the curable composition to be obtained, an amount such that the total concentration of each component except for the solvent of the curable composition is 5 to 50 mass% By mass to 40% by mass.

Curing membrane  And a method for forming the same

The cured film of the present invention is formed from the curable composition of the present invention. The cured film formed from the curable composition of the present invention is not particularly limited, and for example, each color pixel, a black matrix, a protective film, and a spacer constituting a color filter can be mentioned. Hereinafter, these will be described in detail.

As a method of forming the colored layer constituting the color filter, firstly, the following method can be mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion for forming a pixel if necessary. Subsequently, the liquid composition of the radiation sensitive curable composition of the present invention containing, for example, a blue coloring agent is applied on the substrate, and then the pre-baking is performed to evaporate the solvent to form a coating film. Subsequently, the coating film is exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which blue pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, the respective radiation-sensitive curable compositions were coated, pre-baked, exposed, developed, and post-baked in the same manner as above using each of the green or red sensitive radiation curable compositions to form a green pixel array and a red And pixel arrays are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of three primary colors of blue, green, and red are arranged on a substrate is obtained. However, the order of forming the pixels of each color in the present invention is not limited to the above.

The black matrix can be formed by forming a metal thin film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by photolithography. By using a radiation-sensitive composition containing a black coloring agent, May be formed in the same manner as in the case of forming. The curable composition of the present invention can be suitably used for forming such a black matrix.

Examples of the substrate used for forming the colored layer include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

If necessary, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, and the like.

When the radiation sensitive composition is applied to a substrate, a suitable coating method such as a spraying method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method or a bar coating method can be employed, , Slit die coating method is preferably employed.

Prebaking is usually carried out in combination with reduced pressure drying and heat drying. The reduced-pressure drying is usually carried out until 50 to 200 Pa is reached. The conditions for heating and drying are usually about 70 to 110 DEG C for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 占 퐉, preferably 1.2 to 5 占 퐉, as a film thickness after drying.

Examples of the light source of radiation used for forming the pixel and / or the black matrix include a lamp light source such as 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 laser light source such as an ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser. An ultraviolet LED may be used as an exposure light source. Radiation with a wavelength in the range of 190 to 450 nm is preferred.

The exposure dose of the radiation is generally preferably from 10 to 10,000 J / m ² . When the curable composition of the present invention is used, a color filter having excellent solvent resistance and electrical characteristics can be produced even when the exposure amount is not more than 500 J / m ² .

Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7- undecene, Azobicyclo- [4.3.0] -5-nonene and the like are preferable.

A water-soluble organic solvent such as methanol, ethanol or the like or a surfactant may be added to the alkali developer in an appropriate amount. After the alkali development, it is usually washed with water.

As the development processing method, a shower development method, a spray development method, a dipping (developing) developing method, a puddle (liquid immersion) developing method, and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

The post-baking condition is usually about 120 to 280 DEG C for about 10 to 60 minutes. The film thickness of the thus formed pixel is usually 0.5 to 5.0 mu m, preferably 1.0 to 3.0 mu m. By using the curable composition of the present invention, it is possible to produce a color filter having excellent solvent resistance and electrical characteristics even when the post-baking temperature is 200 占 폚 or less.

As a second method for forming a colored layer on a substrate, there is a method in which pixels of respective colors are obtained by an inkjet method disclosed in JP-A-7-318723 and JP-A-2000-310706 Method can be adopted. In this method, first, a partition wall serving also as a light shielding function is formed on the surface of the substrate. Subsequently, the thermosetting composition of the present invention containing, for example, a red coloring agent is ejected in the partition wall formed by the ink jet apparatus, followed by prebaking to evaporate the solvent. Subsequently, this coating film is exposed, if necessary, and then baked by post-baking to form a red pixel pattern.

Subsequently, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as above using each of the green and blue thermosetting compositions. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, the order of forming the pixels of each color in the present invention is not limited to the above.

In addition, the partition wall has a thicker film than the black matrix used in the first method, because it functions not only to shield the light-shielding function but also to prevent the curable composition of each color discharged in the partition from being mixed. Thus, the barrier ribs are usually formed using a black radia radiation composition.

Methods and conditions such as a substrate, a light source of radiation used for forming the colored layer, and prebaking are the same as the first method described above. By using the curable composition of the present invention, it is possible to obtain a colored layer having good solvent resistance even if the post-baking temperature is low as compared with the conventional one.

In addition, a transparent conductive film may be formed by sputtering after forming a protective film on the pixel pattern obtained through the above-described steps, if necessary, and a spacer may be further formed to form a color filter. In general, a thermosetting and / or radiation-sensitive resin composition is used for forming a protective film or a spacer. The curable composition of the present invention can be suitably used for forming the protective film or the spacer. The conditions for forming the protective film and the spacer are the same as those for the colored layer.

Display element

The display element of the present invention comprises the cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and an electronic paper.

The color liquid crystal display element having the cured film of the present invention may be of a transmissive type or of a reflective type, and a suitable structure may be employed. For example, the color filter may be formed on a substrate different from the substrate on which the thin film transistor (TFT) is disposed, and a structure in which the substrate on which the driving substrate and the color filter are formed faces each other via the liquid crystal layer A structure in which a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed and a substrate on which ITO (indium oxide doped with indium) electrode are formed face each other with a liquid crystal layer interposed therebetween It can also be adopted. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When adopting the latter structure, the black matrix or the spacer may be formed on either the substrate on which the color filter is formed or the substrate on which the ITO electrode is formed. The cured film of the present invention can also be applied as an interlayer insulating film constituting a driving substrate on which thin film transistors (TFTs) are arranged.

Further, the organic EL display device having the cured film of the present invention can adopt a suitable structure, and for example, there is a structure disclosed in Japanese Patent Laid-Open No. 11-307242.

Further, the electronic paper having the cured film of the present invention can adopt a suitable structure, for example, a structure disclosed in Japanese Patent Laid-Open No. 2007-41169.

<Examples>

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(A) Synthesis of polymer

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 16.8 parts by mass of 2-hydroxyethyl methacrylate, 11.2 parts by mass of 2-ethylhexyl methacrylate, 0.3 parts by mass of 2,2'-azobisisobutyronitrile, 0.8 part by mass of a sol-1-dithiocarboxylic acid cyano (dimethyl) methyl ester was dissolved in 56 parts by mass of toluene and subjected to nitrogen bubbling for 30 minutes. Thereafter, the mixture was gently stirred, the temperature of the reaction solution was raised to 80 DEG C, and the temperature was maintained for 6 hours to perform living radical polymerization.

Subsequently, 28.6 parts by mass of toluene, 14.4 parts by mass of 3-mercaptopropionic acid, 0.8 parts by mass of methanesulfonic acid and 0.1 part by mass of p-methoxyphenol were added to the obtained polymer solution, the temperature of the reaction solution was raised to 110 ° C, The internal pressure was lowered to 300 mmHg over 2 hours, and the esterification reaction was carried out by maintaining the temperature and the pressure for 6 hours.

Subsequently, the temperature of the polymer solution was lowered to 50 占 폚, and then 6.4 parts by mass of 20 mass% KOH aqueous solution was added. After stirring for 10 minutes, stirring was stopped and the mixture was allowed to stand for 60 minutes.

Subsequently, 52 mass parts of a 20 mass% NaOH aqueous solution was added while maintaining the temperature of the polymer solution at 50 deg. C, and the mixture was stirred for 10 minutes. After stirring was stopped, the mixture was allowed to stand for 60 minutes and the aqueous layer was discharged. Subsequently, 52 mass parts of a 10 mass% NaCl aqueous solution was added, and the mixture was stirred for 10 minutes. After stirring was stopped, the mixture was allowed to stand for 60 minutes and the water layer was discharged. Thereafter, a propylene glycol monomethyl ether acetate solution having a solid concentration of 33 mass% was prepared by concentration under reduced pressure. The polymer obtained had a weight average molecular weight (Mw) of 6,500 as measured by GPC (dissolution solvent: tetrahydrofuran) in terms of polystyrene and a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight of 1.21. This polymer is referred to as Polymer (A-1).

Synthesis Examples 2, 3 and 5

(A-2), the polymer (A-3) and the polymer (A-2) were obtained in the same manner as in Synthesis Example 1, except that the types and amounts of the monomers, 5) was synthesized. The physical properties and the like of the polymer (A) thus obtained are shown in Table 1.

Synthesis Example 4

10 parts by mass of toluene was charged into a flask equipped with a stirrer, a cooling tube and a stirrer. The internal temperature was maintained at 80 DEG C and nitrogen bubbling was performed for 30 minutes. Then, 5.6 mass parts of 2-hydroxyethyl methacrylate dissolved in 26 parts by mass of toluene , 4.2 parts by mass of 2-ethylhexyl methacrylate, 4.2 parts by mass of benzyl methacrylate, 7.0 parts by mass of cyclohexyl methacrylate, methoxypolyethylene glycol monomethacrylate (trade name: PME- 200) and 1.1 parts by mass of 2,2'-azobisisobutyronitrile dissolved in 20 parts by mass of toluene was added dropwise over 2 hours. Thereafter, radical polymerization was carried out at 80 占 폚 for 2 hours.

Subsequently, 28.6 parts by mass of toluene, 4.8 parts by mass of 3-mercaptopropionic acid, 0.3 parts by mass of methanesulfonic acid and 0.1 part by mass of p-methoxyphenol were added to the obtained polymer solution, the temperature of the reaction solution was raised to 110 占 폚, The internal pressure was lowered to 300 mmHg over 2 hours, and the esterification reaction was carried out by maintaining the temperature and the pressure for 6 hours.

Subsequently, the temperature of the polymer solution was lowered to 50 占 폚, 2.1 mass parts of a 20 mass% KOH aqueous solution was added, and the mixture was stirred for 10 minutes. Stirring was stopped and the mixture was allowed to stand for 60 minutes.

Subsequently, while maintaining the temperature of the polymer solution at 50 占 폚, 48 mass parts of 20 mass% NaOH aqueous solution was added and stirred for 10 minutes, stirring was stopped, and the mixture was allowed to stand for 60 minutes. Subsequently, 52 mass parts of a 10 mass% NaCl aqueous solution was added and stirred for 10 minutes, stirring was stopped, and the mixture was allowed to stand for 60 minutes and the water layer was discharged. Thereafter, a propylene glycol monomethyl ether acetate solution having a solid concentration of 33 mass% was prepared by concentration under reduced pressure. The polymer obtained had a weight average molecular weight (Mw) of 10,500 as measured by GPC (elution solvent: tetrahydrofuran) in terms of polystyrene and a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight of 1.81. This polymer is referred to as polymer (A-4).

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 16.8 parts by mass of 2-hydroxyethyl methacrylate, 11.2 parts by mass of 2-ethylhexyl methacrylate, 0.3 parts by mass of 2,2'-azobisisobutyronitrile, 0.8 part by mass of a sol-1-dithiocarboxylic acid cyano (dimethyl) methyl ester was dissolved in 56 parts by mass of toluene and subjected to nitrogen bubbling for 30 minutes. Thereafter, the mixture was gently stirred, the temperature of the reaction solution was raised to 80 DEG C, and the temperature was maintained for 6 hours to perform living radical polymerization.

Subsequently, 28.6 parts by mass of toluene, 14.4 parts by mass of 3-mercaptopropionic acid, 0.8 parts by mass of methanesulfonic acid and 0.1 part by mass of p-methoxyphenol were added to the obtained polymer solution, the temperature of the reaction solution was raised to 110 ° C, The internal pressure was lowered to 300 mmHg over 2 hours, and the esterification reaction was carried out by maintaining the temperature and the pressure for 6 hours.

Subsequently, the temperature of the polymer solution was lowered to 50 占 폚, and then 6.4 parts by mass of 20 mass% KOH aqueous solution was added. After stirring for 10 minutes, stirring was stopped and the mixture was allowed to stand for 60 minutes.

Subsequently, 52 mass parts of a 20 mass% NaOH aqueous solution was added while maintaining the temperature of the polymer solution at 50 deg. C, and the mixture was stirred for 10 minutes. After stirring was stopped, the mixture was allowed to stand for 60 minutes and the aqueous layer was discharged. Subsequently, 52 mass parts of a 10 mass% NaCl aqueous solution was added, and the mixture was stirred for 10 minutes. After stirring was stopped, the mixture was allowed to stand for 60 minutes and the water layer was discharged. Thereafter, a propylene glycol monomethyl ether acetate solution having a solid concentration of 40% by mass was prepared by concentration under reduced pressure.

Subsequently, 2.6 parts by mass of succinic anhydride and 0.3 parts by mass of N, N-dimethyl-4-aminopyridine were added, the temperature of the reaction solution was raised to 90 ° C, the addition reaction was carried out by maintaining this temperature for 4 hours, And diluted with a PGMEA solution so as to be 33 mass%.

The polymer thus obtained had a weight average molecular weight (Mw) of 6,800 as measured by GPC (elution solvent: tetrahydrofuran) in terms of polystyrene, and a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight of 1.31. This polymer is referred to as polymer (A-6).

(A) Measurement of hydroxyl value of polymer

The hydroxyl value of the polymer (A) obtained in each of the above Synthesis Examples was measured in the following manner. Table 1 shows the measurement results.

2 g of the polymer solution (A) was precisely weighed to a unit of 1 mg, dissolved in 4.1 mL of pyridine and 0.9 mL of acetic anhydride, and heated in an oil bath heated to 100 캜 for 1 hour. After cooling for 15 minutes, 1 mL of water was added, and the mixture was further heated in an oil bath heated to 100 DEG C for 10 minutes. Thereafter, 20 mL of neutral ethanol and 0.1 g of phenolphthalein indicator were added, and titration was performed with a 0.5 mol / L ethanolic potassium hydroxide solution. A blank test was similarly conducted to calculate the hydroxyl value (unit: mgKOH / g) of the polymer (A).

(A) Thiol Equivalent of  Measure

The thiol equivalent of the polymer (A) obtained in each Synthesis Example was measured in the following manner. Table 1 shows the measurement results. The thiol equivalent is the molecular weight per sulfanyl group.

The thiol equivalent was determined by iodometric titration. Specifically, the polymer solution (A) was redeposited, and 0.2 g of the polymer (A) was precisely weighed to a unit of 1 mg, dissolved in 20 mL of chloroform, further added with 10 mL of isopropanol, 20 mL of water and 1 mL of starch indicator, / L iodine solution.

The "reprecipitation" is an operation of adding PGMEA to a polymer solution to dilute the solid content concentration to 10 mass% and slowly dropping the mixture in a normal hexane / toluene = 80/20 mixed solvent (mass ratio) to obtain a white precipitate.

In Table 1, the meanings of the abbreviations are as follows.

HEMA: 2-hydroxyethyl methacrylate (corresponding to monomer (a1))

EHMA: 2-ethylhexyl methacrylate

PME-200: methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by NIPPON BUSINESS CO., LTD.)

BzMA: Benzyl methacrylate

BMA: butyl methacrylate

CHMA: cyclohexyl methacrylate

PLACCEL FM1D: 2- (6-hydroxyhexanoyloxy) ethyl methacrylate (trade name: Fraxel FM1D, manufactured by Daicel Chemical Industries, Ltd., corresponding to monomer (a1)

AIBN: 2,2'-azobisisobutyronitrile

Molecular weight control agent: Pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester

Preparation of pigment dispersion

Production Example 1

9.2 parts by mass of CI Pigment Green 58 as colorant, 5.8 parts by mass of CI Pigment Yellow 150, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersant (nonvolatile component = 40% by mass) , 64.5 parts by mass of propylene glycol monomethyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether were treated with a bead mill to prepare a pigment dispersion (C-1).

Production Examples 2 to 9

(C-2) to (C-9) were produced in the same manner as in Production Example 1, except that the kind and the amount of the colorant were changed as shown in Table 2.

In Table 2, the meanings of the abbreviations are as follows.

G58: C.I. Pigment Green 58

Y150: C.I. Pigment Yellow 150

Y138: C.I. Pigment Yellow 138

R177: C.I. Pigment Red 177

R254: C.I. Pigment Red 254

B15: 6: C.I. Pigment Blue 15: 6

V23: C.I. Pigment Violet 23

Lake pigment: A triarylmethane lake pigment represented by the following formula (x = 1 to 2 in the formula)

Dye 1: A xanthene dye represented by the following formula

Dye 2: A xanthene dye represented by the following formula

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

LPN21116: BYK-LPN21116 (manufactured by BYK)

LPN6919: BYK-LPN6919 (manufactured by BYK)

(B) Of crosslinking agent (polymer type)  synthesis

Synthesis Example 7

In a flask equipped with a cooling tube and a stirrer, 44.0 parts by mass of p-vinylbenzyl glycidyl ether, 40.0 parts by mass of N-phenylmaleimide and 16.0 parts by mass of benzyl methacrylate were dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate , 8.0 parts by mass of 2,2'-azobisisobutyronitrile and 8.0 parts by mass of? -Methylstyrene dimer were further charged, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 DEG C with stirring and nitrogen bubbling and polymerized for 5 hours.

Subsequently, 17.0 parts by mass of methacrylic acid, 0.5 parts by mass of p-methoxyphenol and 4.4 parts by mass of tetrabutylammonium bromide were added to this polymer solution, and the reaction was carried out at 120 ° C for 9 hours. Thereafter, 18.5 parts by mass of succinic anhydride was further added, and the mixture was reacted at 100 ° C for 6 hours. The mixture was washed twice with maintaining the liquid temperature at 85 ° C and concentrated under reduced pressure to obtain 33% by mass of the crosslinking agent (B- Was obtained. The crosslinking agent (B-1) had a weight average molecular weight (Mw) of 7,800 as measured by GPC (dissolution solvent: tetrahydrofuran) in terms of polystyrene and a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight of 2.8.

Synthesis Example 8

In a flask equipped with a cooling tube and a stirrer, 25.0 mass parts of 3-methacryloyloxymethyl-3-ethyloxetane, 18.0 mass parts of methacrylic acid, 9.0 mass parts of mono 2-acryloxyethyl succinate, 10.0 parts by mass of benzyl methacrylate, 24.0 parts by mass of benzyl methacrylate and 14.0 parts by mass of 2-hydroxyethyl methacrylate were dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate, 6.0 parts by mass of 2,2'-azobisisobutyronitrile And 6.0 parts by mass of an? -Methylstyrene dimer were further charged, followed by nitrogen purging for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 DEG C while stirring and nitrogen bubbling and polymerized for 5 hours to obtain a precursor copolymer solution.

To 200 parts by mass of the obtained precursor copolymer solution, 13.4 parts by mass of 2-methacryloyloxyethyl isocyanate and 0.2 part by mass of 4-methoxyphenol as a polymerization inhibitor were added and reacted at 90 DEG C for 2 hours. The reaction solution was rinsed twice with 75 g of ion-exchanged water per one time and concentrated under reduced pressure to obtain a solution containing 33 mass% of the crosslinking agent (B-2). The crosslinking agent (B-2) had a weight average molecular weight (Mw) of 11,000 as measured by GPC (dissolution solvent: tetrahydrofuran) in terms of polystyrene and a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight of 1.9.

Synthesis Example 9

5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Subsequently, 30 parts by mass of glycidyl methacrylate, 10 parts by mass of styrene, 30 parts by mass of methacrylic acid, and 30 parts by mass of N-cyclohexylmaleimide were charged, and after nitrogen replacement, gentle stirring was started. The solution was heated until the solution temperature reached 70 캜, and this temperature was maintained for 5 hours to obtain a solution containing 33% by mass of the crosslinking agent (B-3). The crosslinking agent (B-3) had a weight average molecular weight (Mw) of 14,600 as measured by GPC (dissolution solvent: tetrahydrofuran) in terms of polystyrene and a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight of 2.0.

(E) Synthesis of binder resin

Synthesis Example 10

To a flask equipped with a cooling tube and a stirrer were added 30.0 parts by mass of benzyl methacrylate, 20.0 parts by mass of butyl methacrylate, 15.0 parts by mass of 2-hydroxyethyl methacrylate, 20.0 parts by mass of styrene and 15.0 parts by mass of methacrylic acid, Glycol monomethyl ether acetate, 3.0 parts by mass of 2,2'-azobisisobutyronitrile and 5.0 parts by mass of? -Methylstyrene dimer were further added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 캜 while stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (E-1). The binder resin (E-1) had a weight average molecular weight (Mw) of 10,000 as measured by GPC (dissolution solvent: tetrahydrofuran) in terms of polystyrene and a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight of 2.5 .

Example 1

Preparation of colored curable composition

100 parts by mass of the pigment dispersion (C-1), 8.9 parts by mass of the polymer (A-1) solution, 35.5 parts by mass of the crosslinking agent (B-1) 9.8 parts by mass of a mixture of erythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.), (D) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butan-1-one, 0.1 part by mass of Megaface F-554 (manufactured by DIC Corporation) as a fluorine surfactant, and ethyl 3-ethoxypropionate as a solvent were mixed to obtain a colorant having a solid content concentration of 20 mass% Curable composition (S-1) was prepared.

Contrast  evaluation

The colored curable composition (S-1) was applied on a glass substrate using a spin coater, and then pre-baked on a hot plate at 100 캜 for 2 minutes to form three coat films having different film thicknesses (chromaticity coordinate values y) Respectively. At this time, the film thickness was set so that the chromaticity coordinate value y was in the vicinity of y = 0.560, y = 0.570, y = 0.580. Subsequently, these substrates were cooled to room temperature, and then a high-pressure mercury lamp was used as a coating film on the substrate. Radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was irradiated onto each coating film at 1,000 J / m ² Lt; / RTI &gt; exposure dose. Thereafter, post baking was performed at 220 캜 for 20 minutes to form a cured film on the substrate. The contrast was measured using a contrast meter (contrast meter CT-1, manufactured by Tsubo Sakadake Co., Ltd.) for the three cured films obtained. From the measurement results, the contrast was obtained when the chromaticity coordinate value y = 0.570. The evaluation results are shown in Table 3. The larger the value of the contrast in the same chromaticity coordinate value, the better.

Evaluation of Sensitivity

The colored curable composition (S-1) was coated on a glass substrate using a spin coater and then pre-baked on a hot plate at 90 캜 for 2 minutes to form a coating film having a thickness of 2.5 탆 after the pre-baking. Subsequently, after cooling the substrate to room temperature, a high-pressure mercury lamp was used, and radiation containing wavelengths of 365 nm, 405 nm, and 436 nm was irradiated onto the coating film through a photomask having a slit having a width of 30 m at 500 J / m ² &lt; / RTI &gt; exposure dose. Then, by discharging the developing solution containing 0.04% by weight aqueous potassium hydroxide solution of 23 ℃ with respect to the substrate to a developing pressure 1kgf / cm ² (nozzle diameter of 1mm), and then subjected to a shower development, more in 220 ℃ 30 bungan post-baking To form a stripe pattern on the substrate. At this time, the line width of the formed stripe pattern was measured. The evaluation results are shown in Table 3. The larger the line width, the higher the sensitivity.

Solvent-resistant  evaluation

The colored curable composition (S-1) was coated on a glass substrate using a spin coater and then pre-baked on a hot plate at 90 캜 for 2 minutes to form a coating film having a thickness of 2.5 탆 after the pre-baking. Subsequently, after cooling the substrate to room temperature, a high-pressure mercury lamp was used and the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 500 J / m ² through a photomask. Then, by discharging the developing solution containing 0.04% by weight aqueous potassium hydroxide solution of 23 ℃ with respect to the substrate to a developing pressure 1kgf / cm ² (nozzle diameter of 1mm), and then subjected to a shower development, for 30 minutes post-baking at 180 ℃ And a dot pattern of 200 x 200 mu m was formed on the substrate.

The substrate on which the dot pattern was formed was immersed in N-methylpyrrolidone at 60 占 폚 for 30 minutes. As a result, a case where cracks occurred after immersion or a case where a pixel pattern to be peeled off from the substrate was not observed was evaluated as &quot; &quot;, and a case where a crack occurred or peeled from the substrate after peeling was observed was evaluated as &quot; . The evaluation results are shown in Table 3.

Evaluation of voltage holding ratio

The colored curable composition (S-1) was applied on a glass substrate having an ITO (indium-tin oxide alloy) electrode deposited in a predetermined shape using a spin coater, and then prebaked in a clean oven at 90 캜 for 10 minutes To form a coating film having a thickness of 1.8 mu m.

Subsequently, using a high-pressure mercury lamp, the coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 500 J / m ² without interposing a photomask. Thereafter, this substrate was immersed in a developing solution containing 0.04 wt% aqueous potassium hydroxide solution at 23 DEG C for 1 minute and developed, washed with ultrapure water and air-dried, post-baked at 180 DEG C for 30 minutes The coating film was cured to form green pixels on the substrate.

Subsequently, the liquid crystal cell was placed in a constant temperature layer at 60 占 폚, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention rate measuring system VHR-1A (trade name) manufactured by Toyo Technica. The applied voltage at this time was a square wave of 5.0 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is the value of the potential difference of the liquid crystal cell after 16.7 milliseconds / voltage immediately after voltage application). The evaluation results are shown in Table 3. The larger the value of the voltage holding ratio, the better.

Examples 2 to 10 and Comparative Examples 1 to 3

The preparation and evaluation of the colored curable composition were carried out in the same manner as in Example 1 except that the kind and amount of each component in Example 1 were changed as shown in Table 3. [ The evaluation results are shown in Table 3. With regard to the evaluation of the contrast, the contrasts at the chromaticity coordinate values y = 0.570 in Examples 2 to 3 and Comparative Example 1 which are the green curable compositions were compared with those at the chromaticity coordinate values x = 0.650 In Examples 5 to 8 and 10 and Comparative Examples 2 to 3 which are blue curable compositions were measured for contrast at the chromaticity coordinate value y = 0.090, respectively.

The components in Table 3 are as follows.

B-3: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name: M-402, manufactured by Toagosei Co., Ltd.)

B-4: Mixture of a monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name: TO-1382, manufactured by Toagosei Co., Ltd.)

D-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, BASF)

D-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime) (trade name Irgacure OX02, Priests)

D-3: 2,4-Diethyl thioxanthone

F-1: fluoric surfactant (trade name: Megaface F-554, manufactured by DIC)

F-2: Melamine crosslinking agent (trade name: MW-30, manufactured by Sanwa Chemical Co., Ltd.)

EEP: ethyl 3-ethoxypropionate

MBA: 3-methoxybutylacetate

Example 11

100 parts by mass of the polymer (A-1) solution, 300 parts by mass of the crosslinking agent (B-3) solution, 40 parts by mass of a phenol novolac epoxy resin (trade name: Epicoat 152, , 5 parts by mass of isopropyltrimethoxysilane, 0.2 part by mass of a surfactant FTX-218 (NEOS Corp.), and diethylene glycol methyl ethyl ether as a solvent were mixed to prepare a thermosetting resin composition having a solid content concentration of 20 mass%.

Subsequently, red, green and blue stripe coloring patterns were formed on the glass substrate using the green curable composition obtained in Example 1, the red curable composition obtained in Example 4, and the blue curable composition obtained in Example 7. The thermosetting resin composition was coated on the obtained stripe-shaped coloring pattern using a slit and spin coater. Baked on a hot plate at 80 DEG C for 2 minutes to form a coating film, and further baked in a 180 DEG C clean oven for 60 minutes to form a protective film having a thickness of 1.5 mu m.

Example 12

50 parts by mass of a polymer (A-1) solution, 300 parts by mass of a crosslinking agent (B-2) solution as a component (B), 40 parts by mass of a polyfunctional acrylate KAYARAD DPHA (dipentaerythritol hexaacrylate, 10 parts by mass of 1,9-nonanediacrylate as a photo radical generator, 5 parts by mass of NCI-831 (manufactured by Adeka Co., Ltd.) as a photo radical generator, , 5 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name Irgacure 907, BASF) and 2,2'- Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole as a sensitizer and 5 parts by mass of 4,4'-bis (diethylamino) benzophenone as a sensitizer 5 parts by mass of? -Glycidoxypropyltrimethoxysilane as an adhesion promoter, 0.5 parts by mass of FTX-218 (NEOS) as a surfactant, 0.5 parts by mass of 4-methoxyphenol as a storage stabilizer, And propylene glycol moiety as a solvent A mixture of methyl ether acetate to prepare a solid content of the radiation concentration for the spacer of 30% by mass-forming resin composition.

Subsequently, a transparent conductive film was formed by sputtering on the substrate on which the stripe colored pattern and the protective film obtained in Example 10 were formed, and the above radiation sensitive resin composition for forming a spacer was applied by using a slit and spin coater. And prebaked on a hot plate at 100 占 폚 for 3 minutes to form a film having a film thickness of 3.5 占 퐉. A high-pressure mercury lamp was used to expose the obtained coating film with an exposure amount of 500 J / m &lt; ² &gt; through a photomask of a pattern, leaving a 10 mu m corners. Thereafter, the resultant was developed with a 0.05 wt% aqueous solution of potassium hydroxide at 25 ° C, washed with pure water for 1 minute, and further baked in an oven at 180 ° C for 30 minutes to form a spacer. Thus, a color filter was produced.

Subsequently, a liquid crystal display element was produced using this color filter. The obtained color liquid crystal display element exhibited excellent display characteristics and reliability.

Claims (8)

A curable composition comprising the following components (A ¹ ) and (B):
(A ¹ ) a polymer obtained by at least a step of esterifying a carboxylic acid having a sulfanyl group to a hydroxy group of a polymer of a monomer containing a (meth) acrylic monomer having a hydroxy group,
(B) a compound having two or more functional groups capable of reacting with a sulfanyl group. A curable composition characterized by comprising the following components (A ² ) and (B):
(A ² ) a polymer having a repeating unit represented by the following formula (1)
(B) a compound having two or more functional groups capable of reacting with a sulfanyl group.

[In the formula (1)
R ¹ represents a hydrogen atom or a methyl group,
R ² , R ³ and R ⁴ independently represent a substituted or unsubstituted divalent hydrocarbon group,
X represents -COO- (* ¹ ) or -CONH- (* ¹ )
Z represents a single bond, -CO- or -COO- (* ² )
m represents an integer of 1 to 30,
n represents an integer of 0 to 30,
However, "* ^1" represents a bonding hand in combination with R ^2, "* ^2" represents a bonding hand, combined with R ^3] The curable composition according to claim 2, wherein the (A ² ) polymer further has a repeating unit represented by the following formula (2).

[In the formula (2)
R ¹ , R ² , R ³ , X, Z, m and n are as defined above,
R ⁵ represents a hydrogen atom or -CO-R ⁶ -COOH,
And R &lt; ⁶ &gt; represents a divalent hydrocarbon group. 4. The positive resist composition according to any one of claims 1 to 3, wherein the compound (B) having at least two functional groups capable of reacting with the sulfanyl group is at least one of an ethylenic unsaturated group and a group having a cyclic ether structure Wherein the curable composition is a compound having two or more groups. The curable composition according to any one of claims 1 to 4, which is used for a display element. 6. The curable composition according to any one of claims 1 to 5, further comprising (C) a colorant. A cured film formed using the curable composition of any one of claims 1 to 6. A display device comprising the cured film according to claim 7.