KR101460576B1 - Curable composition, color filter and process for production thereof - Google Patents

Abstract

The present invention provides a curable composition having good pattern formability even when containing a high concentration of a colorant and excellent in adhesion to a hard surface as a base material, a color filter formed by forming a coloring pattern of resolution, and a method of producing the same.

(A) a curable composition comprising a radically polymerizable compound having an ethylenically unsaturated double bond and an adhesive group on a hard material in a molecule, and (B) a photopolymerization initiator. The adhesion group of the polymerizable compound to the hard material may be an acid group, an ester group, an acid salt of an acid, an acid metal salt, a substituent which generates a silanol group by hydrolysis, an onium group, a phenolic hydroxyl group, It is preferable to be one type selected from the group consisting of anionic group, acid group and chelating group. This curable composition is useful for forming a coloring pattern of a color filter.

Description

FIELD OF THE INVENTION The present invention relates to a curable composition, a color filter,

TECHNICAL FIELD The present invention relates to a curable composition, a color filter, and a method for manufacturing the same, which are suitable for manufacturing a color filter used for a liquid crystal display device (LCD) or a solid-state image pickup device (CCD, CMOS, etc.).

Color filters are indispensable components for liquid crystal displays and solid-state image pickup devices.

Since a liquid crystal display is compact as compared with a CRT as a display device and is equal in performance or more, it is replaced with a CRT as a television screen, a PC screen, and other display devices. In recent years, trends in the development of liquid crystal displays are shifting from the conventional monitor use, in which the screen is relatively small, to the TV use, in which the screen is large and a high image quality is required.

In the use of a color filter for a liquid crystal display (LCD), the substrate size is enlarged for production of a large-sized TV, and curing at a low energy is desired in order to improve the productivity when using a large substrate. Further, in a liquid crystal display for TV use, a higher image quality is required as compared with a conventional monitor. That is, the contrast and color purity are improved. With respect to the curable composition used for the production of the color filter for the purpose of improving the contrast, a smaller particle size of the colorant (organic pigment or the like) to be used is required. (See, for example, Japanese Unexamined Patent Publication (Kokai) No. 2006-30541). Accordingly, the amount of the dispersant added for pigment dispersion tends to increase. In order to improve the color purity, the content of the colorant (organic pigment) in the solid content of the curable composition is required to be higher. Therefore, the content of the photopolymerization initiator and the photopolymerizable monomer in the solid content in the curable composition tends to decrease.

On the other hand, also in the use of a color filter for a solid state imaging device, curing at low energy is desired. In addition, patterning of the pattern is progressing, thereby improving the pigment concentration in the composition. Further, in pigment-based color filters, the ratio of the pigment dispersant in the composition tends to increase as the pigment becomes finer. Further, in order to cope with problems such as color variation caused by relatively rough and loose particles of pigment, a technique of using a dye soluble in an organic solvent instead of a pigment has been proposed (for example, JP-A-2-127602 ). However, in the dye-based color filter, the problem of the polymerization inhibition effect from the dye has become remarkable as the dye concentration is improved. These factors limit the content of the photopolymerization initiator and the photopolymerizable monomer, which are components necessary for curing the curable composition in any case for the liquid crystal display or the solid-state imaging element, and the concentration of the colorant is high. Sufficient curing can not be obtained, adhesiveness with the substrate is insufficient, and desired pattern formation is remarkably difficult. As a countermeasure against this problem, there has been proposed a technique of introducing a silane coupling agent (for example, Japanese Patent Application Laid-Open No. 11-38226 and Japanese Patent No. 2874091) in order to improve substrate adhesion.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems in the prior art, and it is an object of the present invention to provide a curable composition which is cured with high sensitivity even when a colorant is contained at a high concentration, has good pattern formability, To provide a composition.

Another object of the present invention is to provide a color filter having a coloring pattern excellent in resolution and adhesion to a support obtained by using the curable composition of the present invention and a production method capable of producing the color filter with high productivity It is on.

As a result of intensive studies, the present inventors have found out what can solve the above problems by using a specific polymerizable compound, and accomplished the present invention. Means for solving the above problems are as follows.

≪ 1 > A curable composition comprising (A) a radically polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group to a hard material, and (B) a photopolymerization initiator.

&Lt; 2 > The positive resist composition as described in any one of (1) to (3) above, wherein (A) the adhesive group to the hard material in the radically polymerizable compound having an ethylenically unsaturated double bond and a bonding group to a hard material in the molecule is an acid group, an ester group, The curable composition according to < 1 >, wherein the curable composition according to &lt; 1 &gt; is in the form of a sheet selected from the group consisting of a substituent which generates a silanol group by decomposition, an onium group, a phenolic hydroxyl group, a positive ionic group and a chelating group.

(3) The hard material is a glass substrate or a silicon substrate, and the adhesive group to the hard material in the radically polymerizable compound having (A) the ethylenically unsaturated double bond in the molecule and the adhesive group to the hard material is Lt; 1 &gt; is a substituent which generates a silanol group.

<4> The curable composition according to <1>, wherein the (A) radically polymerizable compound having an ethylenically unsaturated double bond and a bonding group to a hard material in the molecule has a plurality of ethylenically unsaturated double bonds in the molecule .

<5> The curable composition according to <2>, wherein the radically polymerizable compound having an ethylenically unsaturated double bond and a bonding group to a hard material in the molecule (A) has a plurality of ethylenically unsaturated double bonds in the molecule .

<6> The curable composition according to <3>, wherein the (A) radically polymerizable compound having an ethylenically unsaturated double bond and a bonding group to a hard material in the molecule has a plurality of ethylenically unsaturated double bonds in the molecule .

<7> The curable composition according to <4>, wherein the (A) radically polymerizable compound having an ethylenically unsaturated double bond and a bonding group to a hard material in the molecule has an acryloyl group in the molecule.

<8> The curable composition according to any one of <1> to <4>, further comprising (C) a colorant having a maximum absorption in a visible wavelength region of 400 nm to 700 nm.

<9> A color filter having a coloring pattern formed by using the curable composition according to <8> above on a support.

<10> A method of manufacturing a curable film, comprising the steps of: applying a curable composition described in <8> on a support to form a curable composition layer; exposing the curable composition layer through a mask; And a step of forming the color filter.

Here, with respect to the preferable form of the curable composition of the present invention described in <1>, the curable composition of the present invention is useful for producing a colored pattern in a color filter, and from this viewpoint, as a hard material used as a support, , Inorganic materials such as glass and silicon substrates, cellulose acetate triacetate, cellulose triacetate, cellulose propionate, cellulose acetate butyrate, cellulose nitrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal , And the adhesive group which can be adhered to the support formed of such a hard material is preferably selected from the group consisting of a covalent bond, an ionic bond, a hydrogen bond, a polar interaction, Selected from the group consisting of Walsh interactions It may include a functional group capable of forming an interaction.

As a support for a color filter, general-purpose glass or an adhesive group to the surface of a resin material includes acid groups such as a sulfonic acid group, a phosphonic acid group and a carboxyl group; Ester groups of these acids; Metal salts of these acids; An onium group such as an ammonium group and a pyridinium group; A substituent which generates a silanol group by hydrolysis of an alkoxysilyl group or the like; Amphoteric groups such as phenolic hydroxyl groups and N-oxide groups; Imino-2-acetic acid and the like.

Hereinafter, the curable composition of the present invention, the color filter using the curable composition, and the method for producing the same will be described in detail.

[Curable composition]

The curable composition of the present invention comprises (A) a radically polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group to a hard material (hereinafter appropriately referred to as (A) a specific polymerizable compound) and (B) And a photopolymerization initiator.

First, the components (A) and (B) which are essential components of the curable composition of the present invention will be described.

&Lt; (A) Radically polymerizable compound having an ethylenically unsaturated double bond in the molecule and a bonding group to a hard material &

The specific polymerizable compound (A) that can be used in the present invention is an addition polymerizable compound having at least one ethylenic unsaturated double bond, and also has a close adhesion group to a hard material in the molecule.

Examples of the ethylenically unsaturated bond include esters and amides of a vinyl group, an unsaturated carboxylic acid (e.g., (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), unsaturated phosphonic acid, styrene, Among them, (meth) acrylic acid is preferable.

The specific polymerizable compound (A) of the present invention has at least one, preferably two or more, more preferably three or more, more preferably four or more, and most preferably five or more ethylenic unsaturated bonds And is a compound having at least one adhesive group to a hard material described in detail below.

That is, the specific polymerizable compound (A) is characterized by having, in addition to the ethylenically unsaturated double bond group, an adhesive group capable of improving the adhesion with the surface of the hard material to which the curable composition of the present invention is applied.

As the hard material, a material to be a support substrate to which the curable composition of the present invention can be applied is, for example, an inorganic material such as glass or a silicon substrate, or an inorganic material such as cellulose acetate dibasic acid, cellulose triacetate, cellulose propionate, Organic resin materials such as polyethylene terephthalate, cellulose nitrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate and polyvinyl acetal. When the curable composition of the present invention is used for forming a color pattern of a color filter , Among them, a material selected from a transparent hard material or a silicon substrate, among which glass or silicon substrate is preferable.

The specific polymerizable compound (A) appropriately selects which adhesion group is to be introduced depending on the characteristics of the hard material to which the curable composition is applied.

The adhesion group is a group capable of forming an interaction selected from the group consisting of a covalent bond, an ionic bond, a hydrogen bond, a polar interaction, and a van der Waals interaction with a hard material surface. Specifically, A group having at least one partial structure selected from the group consisting of an ester group, an acid salt, an acid metal salt, a substituent which generates a silanol group by hydrolysis, an onium group, a phenolic hydroxyl group, a positive ionic group and a chelating group have.

Examples of preferable adhesion groups include sulfonic acid groups, phosphonic acid groups and their ester groups or salts thereof, carboxyl groups and salts thereof, ammonium groups, pyridinium groups, acetylacetone groups, and substituent groups which generate silanol groups by hydrolysis And a functional group selected from the group consisting of Among them, an ammonium group, a substituent which generates a silanol group by hydrolysis, a phosphonic acid group and an ester group thereof are preferable.

Above all, substituents capable of forming ionic bonds, multipoint hydrogen bonds, and covalent bonds from the viewpoint of strength of interaction are preferable. Among them, in view of substrate adhesiveness derived from the strength of interaction with the substrate, it is preferable that the substrate has a functional group selected from the group consisting of ammonium group, phosphonic acid group and ester group and alkoxysilyl group, But is preferable from the viewpoint of the film strength of the part.

Specific polymerizable compounds (A) of the present invention include those represented by the following general formula (A) as the polymerizable compound having an ethylenically unsaturated double bond and a bonding group to a hard material.

In the above general formula (A), M represents a moiety having an ethylenically unsaturated double bond, L represents an organic linking group having a valence of n + 1, and X represents a bonding group to a hard material. n represents an integer of 1 to 5, and m represents an integer of 1 to 3.

Preferable examples of the structure represented by M include esters and amides of unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.). The addition reaction of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines or thiols, or addition of a halogen group or a tolyl group such as a tosyloxy group A structure formed by substitution reaction of an unsaturated carboxylic acid ester or amide having a sex substituent with monofunctional or multifunctional alcohols, amines and thiols. As another example, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. Among them, a (meth) acryloyl group, a styrene, and a vinyl ether structure are preferable. (Meth) acryloyl group is more preferable.

In the general formula (A), L represents an organic linking group of n + 1 valency determined by the number (n) of partial structures having an ethylenically unsaturated double bond, but an oxygen atom, a nitrogen atom, A hydrocarbon ring structure having 3 to 10 carbon atoms, a partial structure selected from the group consisting of aromatic rings, heterocyclic rings, urethane bonds, thiourethane bonds, ester bonds, amide bonds, urea bonds and thiourea bonds, Or an n + 1-valent linkage composed of a plurality of species.

Such a linking group may further have a substituent. Examples of the substituent which can be introduced into the linking group of L include an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxyl group, a thiol group, a cyano group, , An aromatic oxy group, a heterocyclic oxy group, an aliphatic thio group, an aromatic thio group, a heterocyclic thio group, an aliphatic sulfonamide group, an aromatic sulfonamide group, a heterocyclic sulfonamide group, an acyl group, an acyloxy group, A heterocyclic oxycarbonylamino group, an aromatic oxycarbonylamino group, an aliphatic thiocarbonylamino group, an aromatic thiocarbonylamino group, a heterocyclic thiocarbonylamino group, a heterocyclic thiocarbonylamino group, an aryloxycarbonylamino group, an aryloxycarbonylamino group, An aliphatic aminocarbonylamino group, an aromatic aminocarbonylamino group, a heterocyclic amino A carbamoyloxy group, a carbamoylamino group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic oxyamino group, an aromatic oxyamino group, a heterocyclic oxyamino group, a silyl group, an aliphatic oxysilyl An aryloxy group, an aliphatic azo group, an aromatic group, a heterocyclic oxy group, an aryloxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyloxy group, a sulfamoyloxy group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, A sulfonyl group, a sulfonyl group, a phosphonylamino group, a sulfonylamino group, a sulfonylamino group, a sulfonylamino group, a sulfonylamino group, a sulfonylamino group, a sulfamoylamino group, a sulfamoylamino group, .

[Specific examples of (A) specific polymerizable compound]

Among the structures represented by M, specific examples [(M-1) to (M-11)] in the case where the ethylenic double bond group is an acryloyl group are shown below, but the present invention is not limited thereto. The acryloyl group may be substituted with a substituent other than the acryloyl group. And may have two or more ethylenic double bond groups different from each other in the structure represented by M,

When m is 1, X in the general formula (A) is preferably selected from the group consisting of monovalent functional groups represented by the following formulas.

R ¹¹ to R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkynyl group or an alkenyl group, M ¹ and M ² each independently represent a hydrogen atom, a metal atom or an onium group, X ^- represents a counter anion.

When m is 2, X in the above formula (A) is preferably selected from the group consisting of divalent functional groups represented by the following formulas.

Wherein R ¹² to R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkynyl group or an alkenyl group, M ² represents a hydrogen atom, a metal atom or an ammonium group, and X ^- represents a counter anion .

When m is 3, X in the general formula (A) is preferably selected from the group consisting of trivalent functional groups represented by the following formulas.

In the formula, R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an alkynyl group or an alkenyl group, and X ^- represents a counter anion.

When X in the general formula (A) has a counter anion as a partial structure, examples of counter anion X ^- include halogen anion such as a fluorine anion, a chlorine anion, a bromine anion and an iodine anion; A perchlorate anion, a tetrafluoroborate anion, a hexafluorophosphate anion, a hexachloroantimonate anion, a hexachloroantimonate anion, a hexafluorophosphate anion, a hexafluorophosphate anion, a hexafluorophosphate anion, a hexafluorophosphate anion, a hexafluorophosphate anion, And a fluoroantimonate anion. Of these, halogen atom, trifluoromethanesulfonic acid anion, methanesulfonic acid anion, sulfuric acid anion, hydrogen sulfate anion, tetrafluoroborate anion, and hexafluorophosphate anion are preferable from the viewpoints of solubility and stability of the compound . The counter anion X ^- may be any one of m 1 to 3, for example.

[(A) Method for synthesizing a specific polymerizable compound]

Next, an example of the synthesis method of the specific polymerizable compound (A) represented by the general formula (A) is shown, but the synthesis method is not limited thereto.

As a method for synthesizing the specific polymerizable compound (A) represented by the general formula (A), an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional Addition reaction with alcohols, amines and thiols, unsaturated carboxylic acid esters or amides having a halogen group or a silyl substituent group such as a tosyloxy group, monofunctional or polyfunctional alcohols having an adhesive group, amines, And a substitution reaction with thiols. The addition reaction with a compound having an electrophilic substituent such as an isocyanate group or an epoxy group and having an adhesive group and a compound having a hydroxyl group, an amino group or a mercapto group and having at least one ethylenic double bond . The specific polymerizable compound (A) represented by the general formula (A) can also be synthesized by a Michael addition reaction to a compound having two or more ethylenic double bonds of amines and thiols having a bonding group.

As an example of the polymerizable compound (A) of the present invention, an example in which the structure of M in the general formula (A) is the above exemplified structure (M-6) and the adhesion unit X to the hard material is introduced into the structure [Exemplary Compounds (1) to (20)] are shown below, but the structure of M in Formula (A) can be suitably changed to those of M-1 to M- Or can be synthesized by a conventional synthesis method. The present invention is not limited to these examples.

As an example of the polymerizable compound (A) of the present invention, the structure of M in the general formula (A) is the same as the structures (M-1) to (M-11) except for the example structure (M-6) (Exemplary Compounds (21) to (30)], but the present invention is not limited thereto.

Details of the specific polymerizable compound (A), such as its structure, single use, combination use, addition amount, and the like, can be arbitrarily set according to the final performance design and use of the curable composition. For example, from the following viewpoints.

In view of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. Further, in order to increase the strength of the cured film, it is preferable to use trifunctional or higher functionalities, and when a combination of other functional water and another polymerizable group (for example, acrylate ester, methacrylate ester, styrene series compound or vinyl ether series compound) It is also effective to adjust both strength and strength.

When a glass plate is used as the support for the hard material, for example, since a large number of silanol groups and hydroxyl groups are present on the glass surface, a dialkyl group capable of forming a covalent interaction with these groups It is preferable to introduce an ammonium group capable of forming an alkoxysilyl group, an alkyldialkoxysilyl group, a trialkoxysilyl group, an ion dipole interaction, or a phosphonic acid or an ester group capable of forming a multi-point hydrogen bond.

In order to use cellulose-based materials such as cellulose acetate 2, cellulose acetate 3, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate butyrate, and the like, it is preferable to use an adhesive group such as polyethylene terephthalate, polyethylene, When a synthetic resin such as polystyrene, polypropylene, polycarbonate or polyvinyl acetal is used as a hard material, it is preferable to select an adhesive group such as phosphonic acid or its ester group.

The selection and use of the addition polymerization compound is also an important factor for compatibility with other components (for example, initiator, colorant (pigment, dye), binder polymer, etc.) contained in the curable composition and dispersibility. For example, the use of a low-purity compound or the combination of two or more kinds of compounds can improve the compatibility. In addition, for the purpose of improving the adhesion with a substrate or the like, a specific structure other than the introduction of the above-mentioned adhesive group may be selected.

In the present invention, in addition to the specific polymerizable compound (A), a general radical polymerizable compound (E) having no adhesive group as described above may be used in the molecule, as long as the effect of the present invention is not impaired . Examples of the general radically polymerizable compound having no adhesive group include those having no adhesive group in the molecule in the specific polymerizable compound (A). Two or more of them may be used in combination. Next, a general radically polymerizable compound (E) having no adhesive group will be described.

<General Radical Polymerizable Compound (E) Having No Adhesion Group>

As a general radically polymerizable compound (E) having no adhesive group usable in the present invention, a compound widely known as a compound having an ethylenically unsaturated double bond in the relevant industrial field can be used without particular limitation. They have chemical forms such as, for example, monomers, prepolymers, i.e. dimers, trimer and oligomers, or mixtures and copolymers thereof. Examples of the monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent group such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxy group, and a monofunctional or polyfunctional carboxyl A dehydration condensation reaction product with an acid is also suitably used. Further, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of a monofunctional or polyfunctional alcohol, an amine or a thiol, or a halogen group, Also preferred are unsaturated carboxylic acid esters or amides having a sex substituent and substitution reaction products with monofunctional or polyfunctional alcohols, amines and thiols. As another example, it is also possible to use a compound group substituted by an unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1 , 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol Triacrylate, sor (Acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, and the like can be given as examples of the acrylate oligomer. Also, EO-modified products or PO-modified products of these compounds may be mentioned.

Examples of the methacrylic ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol Dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate , Dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- Methacryloxyethoxy) phenyl] dimethylmethane, and EO-modified products thereof and PO-modified products thereof.

Examples of itaconic acid esters include ethylene glycol diacetonate, propylene glycol diacetonate, 1,3-butanediol diacetonate, 1,4-butanediol diacetonate, tetramethylene glycol diacetonate, pentaerythritol diacetonate, sorbitol tetra And taconate. Examples of the crotonic acid ester include ethylene glycol dichlonate, tetramethylene glycol dichlonate, pentaerythritol dichlonate, and sorbitol tetradecrhotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramale.

Examples of other esters include aliphatic alcohol esters described in JP-A-51-47334 and JP-A-57-196231, JP-A 59-5240, JP-A 59-5241, JP- Those having an aromatic skeleton described in JP-A No. 2-226149, those containing an amino group described in JP-A No. 1-165613, and the like are also preferably used. The above-mentioned ester monomer can also be used as a mixture.

Examples of the monomer of the amide of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebisacrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis -Methacrylamide, diethylenetriamintrisacrylamide, xylylenebisacrylamide, xylylene bismethacrylamide, and the like. Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726.

Also, urethane-based addition polymerizable compounds prepared by the addition reaction of isocyanate and hydroxyl group are also preferable. As specific examples thereof, there may be mentioned compounds having two or more isocyanate groups in one molecule described in Japanese Patent Publication No. 48-41708 Vinyl urethane compounds containing two or more polymerizable vinyl groups per molecule in which a vinyl monomer containing a hydroxyl group represented by the following general formula (E) is added to the polyisocyanate compound.

CH ₂ = C (R ¹ ) COOCH ₂ CH (R ² ) OH (E)

(Provided that R ¹ and R ² represent H or CH ₃ )

Urethane acrylates as described in JP-A-51-37193, JP-A-2-32293, JP-A-2-16765, JP-A-58-49860, JP- JP-B-56-17654, JP-A-62-39417, and JP-A-62-39418 are also preferable. In addition, the use of addition polymerizable compounds having an amino structure or sulfide structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 1-102383 , A curable composition having a very high photosensitive speed can be obtained.

Other examples include polyester acrylates as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-30490, epoxy resins, ) Acrylic acid, and epoxy acrylates, etc. These polyfunctional acrylates and methacrylates may be mentioned. Specific unsaturated compounds described in Japanese Patent Publication Nos. 46-43946, 1-40337 and 1-40336 and vinylphosphonic acid compounds described in Japanese Patent Application Laid-Open No. 25493 . Further, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Also, those which have been introduced as photocurable monomers and oligomers in Japan Adhesion Society vol.20, No. 7, pp. 300-308 (1984) can be used.

In the present invention, when a general radically polymerizable compound (E) having no adhesive group is added, it is preferable to contain two or more ethylenically unsaturated bonds from the viewpoint of curing sensitivity, more preferably three or more . Among them, it is preferable to contain two or more (meth) acrylic acid ester structures, more preferably three or more, and most preferably four or more. In addition, from the viewpoints of curing sensitivity and developability of the unexposed portion, it is preferable to contain an EO-modified product. Further, it is preferable to contain a urethane bond from the viewpoints of curing sensitivity and exposure part strength.

From the above viewpoints, it is preferable that bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, tetra But are not limited to, ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, (Acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO-modified product, dipentaerythritol hexaacrylate EO-modified product and the like are preferable UH-140 (made by Sanyo Kogaku Pulp), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T, UA-306I, AH -600, T-600, AI-600 (Kyocera Corporation).

Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate , DPA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T, UA-306I and AH-600 (manufactured by Nippon Kayaku Co., Ltd.) , T-600 and AI-600 (Kyocera Corporation) are more preferable.

In view of the curing composition of the present invention, the curing sensitivity, the developability of the unexposed portion, and the strength of the exposed portion, it is preferable that (A) the general radically polymerizable compound (E) having no adhesive group in addition to the specific polymerizable compound . (A) / (A) + (E)] of the (A) specific polymerizable compound to the total mass of the (E) ethylenic double bond-containing polymerizable compound and the (A) More preferably 0.01 or more and 1 or less, still more preferably 0.01 or more and 0.5 or less, still more preferably 0.01 or more and 0.3 or less, most preferably 0.01 or more and 0.15 or less. When [(A) / (A) + (E)] is less than 0.1, sufficient substrate adhesion can not be obtained.

The total mass of (E) the other polymerizable compound having an ethylenic double bond and (A) the specific polymerizable compound in the solid content in the composition of the present invention is preferably 1 to 90%, more preferably 1 to 80% , More preferably from 1 to 70%.

In particular, when the curable composition of the present invention is used for forming a coloring pattern of a color filter, the content is preferably 5 to 50%, more preferably 7 to 40%, and even more preferably 10 to 35% desirable.

(B) the photopolymerization initiator mass ratio [(B) / (A) + (E)] to the total mass of the (E) ethylenic double bond-containing polymerizable compound and (A) More preferably not less than 0.8, more preferably not less than 0.2 and not more than 0.7, and most preferably not less than 0.3 and not more than 0.6.

These components (A) and other radically polymerizable compounds can be arbitrarily selected from the viewpoints of polymerization inhibition against oxygen, resolution, fogging, refractive index change, surface tackiness, etc. have.

<(B) Photopolymerization initiator>

The curable composition of the present invention contains (B) a photopolymerization initiator.

The photopolymerization initiator in the present invention is a compound which is decomposed by light and initiates and promotes polymerization of the specific radically polymerizable compound (A), and preferably has absorption in a wavelength region of 300 to 500 nm. The photopolymerization initiator may be used singly or in combination of two or more.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds , Hexaarylbimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds and acylphosphine (oxide) compounds.

Specific examples of the organic halogenated compound include compounds described in Wakabayashi et al., &Quot; Bull Chem. Soc Japan "42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Application Laid-Open No. 48-36281, Japanese Patent Application Laid-open No. 55-32070, Japanese Patent Laid- Japanese Patent Application Laid-Open Nos. 239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, Japanese Patent Compounds described in M.P. Hutt "Jurnal of Heterocyclic Chemistry" 1 (No. 3), (1970), in particular, oxazol compounds substituted with a trihalomethyl group, s- Triazine compounds.

As s-triazine compounds, more preferably, s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to a s-triazine ring, specifically, 2,4,6-tris (Trichloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (?,?,? - trichloroethyl 4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6- (Trichloromethyl) -s-triazine, 2- (p-chlorophenyl) - 4,6-bis (Trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis -Triazine, 2-styryl-4,6-bis (tri 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4, (Trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio- -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) 6-bis (tribromomethyl) -s-triazine, and 2-methoxy-4,6-bis (tribromomethyl) -s-triazine.

Examples of the oxadiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole , 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) -Oxodiazole, and the like.

Examples of the carbonyl compound include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Benzophenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone,? -Hydroxy-2-methylphenylpropanone, (P-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone and 2-methyl- (4 ' Acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone and 2-benzyl-2-dimethylamino-4-morpholinobutylphenone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone derivatives such as thioxanthone, ethyl p-dimethylaminobenzoate, p-diethylamino And benzoic acid ester derivatives such as ethyl benzoate.

Examples of the ketal compound include benzyl methyl ketal, benzyl-beta-methoxyethyl ethyl acetal and the like.

Examples of the benzoin compound include m benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoyl benzoate.

Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5- Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy ) Hexane, 2,5-oxanooyl peroxide, peroxy succinic acid, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di- Ethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydi Butyl peroxyacetate, tert-butyl peroxyacetate, tert-butyl peroxy pivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxy octanoate, tert-butyl peroxylaurate, (T-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3' (T-butylperoxy dihydrogen 2 phthalate), carbonyldi (t-hexylperoxy dihydrogen 2 phthalate), 4,4'-tetra- (p-isopropylcumperoxycarbonyl) benzophenone, And the like.

Examples of the azo compound include an azo compound described in JP-A-8-108621.

Examples of the coumarin compound include 3-methyl-5-amino- ((s-triazin-2-yl) amino) 2-yl) amino) -3-phenylcoumarin and 3-butyl-5-dimethylamino- ((s-triazin-2-yl) amino) -3-phenyl coumarin.

Examples of the azide compound include organic azide compounds described in U.S. Patent No. 2848328, U.S. Patent Nos. 2852379 and 2940853, 2,6-bis (4-azidobenzylidene) -4-ethylcyclo Hexanone (BAC-E), and the like.

Examples of the metallocene compound include compounds disclosed in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, 2-4705 and JP-A 5-83588, for example, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti- Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis , 4,6-trifluorophenyi-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoropheny-1-yl, di-cyclopentadienyl-Ti Bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl- Cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tet Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, JP-A-1-304453, Iron-arene complexes described in JP-A-1-152109, and the like.

Examples of the hexaaryl biimidazole compound include various compounds described in each specification such as Japanese Patent Publication Nos. 6-29285, 3,479,185, 4,311,783 and 4,622,286, Bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) , 5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4' Bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and the like .

Examples of the organic borate compound include compounds described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, 188710, Japanese Patent Application Laid-Open No. 2000-131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808 and Kunz, Martin "Red Tech'98. Proceeding April 19- 22, 1998, Chicago ", JP-A-6-157623, JP-A-6-175564 and JP-A-6-175561, organic boron sulfonium complexes or organic Boron oxysulfonium complexes, organic boron iodonium complexes described in JP-A-6-175554 and JP-A-6-175553, organoboron phosphonium complexes described in JP-A-9-188710, Japanese Patent Laid-Open Publication No. Hei 6-348011, Japanese Patent Laid-Open No. 7-12878 Organic boron transition metal coordination complexes such as those disclosed in Japanese Patent Application Laid-Open No. Hei 5-191589, Hei 7-140589, Hei 7-306527, and Hei 7-292014.

Examples of the disulfonic acid compound include compounds described in JP-A-61-166544, JP-A-2002-328465, and the like.

As the oxime ester compound, Perkin II (1979) 1653-1660), J.C.S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP 2000-66385 A, JP 2000-80068 A, JP 2004-534797 A Based compounds and the like.

Examples of the onium salt compounds include those described in SI Schlesinger, Photogr, Sci. Ammonium salts described in US Pat. No. 4,069,055, Japanese Patent Application Laid-Open No. 4-365049, and the like disclosed in T. Bale et al., Polymer, 21, 423 (1980) 4,069,055, 4,069,056, EP 104,143, US 339,049, EP 410,201, JP-A 2-150848, JP-A 2- And the iodonium salts described in the respective publications of JP-A-296514.

The iodonium salt which can be suitably used in the present invention is a diaryliodonium salt. From the viewpoint of stability, it is preferable that two or more thereof are substituted with an electron-donating group such as an alkyl group, an alkoxy group or an aryloxy group. As other preferable forms of the sulfonium salt, an iodonium salt having one substituent group of a triarylsulfonium salt having a coumarin or anthraquinone structure and having absorption at 300 nm or more is preferable.

Examples of sulfonium salts that can be preferably used in the present invention include those described in European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent Nos. 4,933,377, 161,811, 410,201, Sulfonium salts described in the specification of each of U.S. Patent Nos. 4,760,013, 4,734,444, 2,833,827, 2,904,626, 3,604,580, and 3,604,581 can be mentioned. From the sensitivity point of stability, Group. As the electron-withdrawing group, it is preferable that the hitting value is larger than zero. Preferred examples of the electron-withdrawing group include a halogen atom and a carboxylic acid.

Examples of other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorption at 300 nm or more. As the preferable preferable sulfonium salt, a triarylsulfonium salt may include a sulfonium salt having an absorption at 300 nm or more having an aryloxy group or an arylthio group as a substituent.

As onium salt compounds, there can be mentioned, for example, those described in J. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. V. Crivello et al., J. Polymer Sci., Polymer Chem. 1979), and onium salts such as arsonium salt described in C.S. Wen et al, Teh, Proc. Conf. Rec. Curing ASIA, p478 Tokyo, Oct (1988).

Examples of the acylphosphine (oxide) compound include Ilgacure 819, Darocite 4265, and DARACURE TPO available from Ciba Specialty Chemicals.

As the photopolymerization initiator (B) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Aminoketone compound, an acylphosphine compound, Based compound, a benzophenone-based compound, an acetophenone-based compound and a derivative thereof, a cyclopentadiene-benzene-iron complex And a salt thereof, a halomethyloxadiazole compound, and a 3-aryl substituted coumarin compound.

More preferably, the trihalomethyl triazine compound, the? -Aminoketone compound, the acylphosphine compound, the phosphine oxide compound, the oxime compound, the triallyl imidazole dimer, the onium compound, the benzophenone compound At least one compound selected from the group consisting of a trihalomethyl triazine compound, an? -Amino ketone compound, an oxime compound, a triallyl imidazole dimer, and a benzophenone compound is an acetophenone compound desirable.

The content of the photopolymerization initiator (B) contained in the curable composition of the present invention is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and particularly preferably 1 to 20 mass%, based on the total solid content of the curable composition. 20% by mass. Within this range, good sensitivity and pattern formability are obtained.

&Lt; (C) Colorant >

By using a coloring agent in the curable composition of the present invention, a colored cured body made of a curable composition can be formed, and it can be applied to formation of an image forming material and a coloring pattern of a color filter.

The colorant to be added to the curable composition of the present invention by any desired means is not particularly limited, and various conventionally known dyes and pigments may be used singly or in combination of two or more. The colorant is preferably a pigment from the viewpoint of durability such as heat resistance and light resistance.

As pigments usable in the curable composition of the present invention, various conventionally known inorganic pigments or organic pigments can be used. Considering that an inorganic pigment or an organic pigment is preferable to have a high transmittance, it is preferable to use as fine as possible, and considering the handling property, the average particle diameter of the pigment is preferably 0.01 탆 to 0.1 탆, Is more preferable. Specific examples of the inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, And composite oxides of the above metals.

As the organic pigment, for example,

C.I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C.I. Pigment Orange 36, 38, 43, 71;

C.I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment Violet 19, 23, 32, 39;

C.I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Green 7, 36, 37;

C.I. Pigment Brown 25, 28;

C.I. Pigment Black 1, 7;

Carbon black, and the like.

In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These basic N-atom pigments exhibit good dispersibility in the composition of the present invention. Although the cause thereof is not sufficiently clarified, it is presumed that the affinity between the photosensitive polymer component and the pigment affects the effect.

Examples of the pigments that can be preferably used in the present invention include the following pigments. However, the present invention is not limited to these.

C.I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C.I. Pigment Orange 36, 71,

C.I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C.I. Pigment Violet 19, 23, 32,

C.I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C.I. Pigment Black 1

These organic pigments may be used singly or in various combinations in order to increase the color purity. Specific examples of the combination are shown below. As the red pigment, for example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or And a mixture with a perylene-based red pigment can be used. Examples of the anthraquinone-based pigment include C.I. Pigment Red 177, and as the perylene pigment, C.I. Pigment Red 155, C.I. Pigment Red 224, and the diketopyrrolopyrrole pigments include C.I. Pigment Red 254, and from the viewpoint of color reproducibility, C.I. Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and the color purity may not be increased. In the case of 100: 51 or more, the dominant wavelength is near the short wavelength, and deviation from the NTSC target color may be large. Particularly, the mass ratio is most preferably in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used singly or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment. For example, in this example, C.I. Pigment Green 7, 36, 37 and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably from 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine-based pigment may be used alone, or a mixture of the phthalocyanine-based pigment and a dioxadine-based purple pigment may be used. For example, C.I. Pigment Blue 15: 6 and C.I. Pigment Violet 23 is preferred. The mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

As the pigment for black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60.

When the composition of the present invention is used for a color filter, the primary particle diameter of the pigment is preferably 10 to 100 nm, more preferably 10 to 70 nm, and more preferably 10 to 50 nm, from the viewpoint of color deviation and contrast. More preferably 10 to 40 nm.

When the composition of the present invention is used for a color filter, it is preferable to use a dye that is uniformly dissolved in the composition from the viewpoint of color deviation and contrast.

The dye that can be used as the colorant contained in the curable composition of the present invention is not particularly limited and a known dye for a conventional color filter can be used. For example, Japanese Patent Application Laid-Open Nos. 64-90403, 64-91102, 1-94301, 6-11614, 2592207, Patent Document 4,808,501, US Patent No. 5,667,920, US Patent No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, Japanese Patent Application Laid-Open Nos. 6-194828, 8-211599, 4-249549, 10-123316, 11-302283, Japanese Patent Application Laid-Open Nos. 7-286107, 2001-4823, 8-15522, 8-29771, 8-146215, Japanese Patent Application Laid-Open No. 11-343437, Japanese Patent Application Laid-Open No. 8-62416, 2002-14220, 2002-14221, 2002-14222, 2002-14223, JP-A-8-302224, JP-A-8-73758 Coloring agents disclosed in JP-A-8-179120 and JP-A-8-151531 can be used.

Examples of the chemical structure include a pyrazolone group, anilino group, triphenylmethane group, anthraquinone group, anthrapyridone group, benzilidene group, oxolin group, pyrazolotriazole group, pyridazo group, cyanine group, phenothiazine group, Dyes such as benzopyran, indigo, and the like can be used.

Further, in the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be preferably used from the viewpoint of completely removing the binder and / or dye of the uniramed portion by development.

Other dyes, such as direct dyes, alkaline dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes, and / or derivatives thereof may also be usefully used.

The acidic dye is not particularly limited as long as it has an acidic group such as a sulfonic acid or a carboxylic acid, but the acidic dye can be dissolved in an organic solvent or a developing solution, salt-forming property with a basic compound, absorbance, interaction with other components in the composition, , Heat resistance, and the like.

Specific examples of the acidic dyes are given below, but the present invention is not limited thereto. For example,

acid alizarin violet N;

acid black 1, 2, 24, 48;

acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 1, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 335, 340;

acid chrome violet K;

acid Fuchsin;

acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109;

acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95107, 108, 169, 173;

acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, 382, 383, 394, 401, 412, 417, 418, 422, 426;

acid violet 6B, 7, 9, 17, 19;

acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141;

Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 173, 181, 172, 173, 188, 189, 190, 192, 193, 163, 164, 166, 167, 170, 171, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;

Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

Mordant Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Mordant Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 48, 49, 53, 61, 74, 77, 83, 84;

Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;

Food Yellow 3;

And derivatives of these dyes.

Of the above acid dyes, acid black 24;

acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;

acid orange 8, 51, 56, 74, 63;

acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217, 249;

acid violet 7;

acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;

Acid Green 25 and derivatives of these dyes are preferable.

Acid dyes, azo dyes, phthalocyanine dyes and phthalocyanine dyes other than those described above are also preferable, and C.I. Solvent Blue 44, 38; C.I. Solvent orange 45; Rhodamine B, and Rhodamine 110, and derivatives of these dyes are also preferably used.

Among them, the colorant (C) is preferably at least one selected from the group consisting of triallyl methane, anthraquinone, azomethine, benzylidene, oxolin, cyanine, phenothiazine, pyrrolopyrazolamomethine, xanthene, phthalocyanine, It is preferably a colorant selected from the group consisting of benzopyran, indigo, pyrazole, anilinoazo, pyrazolotriazole, pyridonazo and anthrapyridone.

When the colorant is used in the curable composition of the present invention, the content is preferably 5 to 80 mass%, more preferably 10 to 70 mass%, and still more preferably 20 to 70 mass%, of the total solid content of the curable composition.

In particular, when the curable composition of the present invention is used for forming a coloring pattern of a color filter, the content of the colorant is preferably 20% by mass or more, and more preferably 30% by mass or more, in the above content range.

When the amount of the colorant is too small, there is a tendency that an appropriate chromaticity can not be obtained when the color filter is produced by the curable composition of the present invention. On the other hand, when the amount is too large, the photocuring does not sufficiently proceed and the strength as a film is lowered, and the developing latitude at the time of alkali development tends to become narrow.

The curable composition of the present invention may further contain optional components as described below in detail, if necessary, together with the components (A) and (B) described above and the component (C) added by desirability. Hereinafter, optional components that the curable composition of the present invention may contain will be described.

<(D) Dispersant>

When the curable composition of the present invention contains (C) a pigment as a colorant, (D) a dispersant is preferably added from the viewpoint of improving the dispersibility of the pigment.

Examples of the dispersant (pigment dispersant) that can be used in the present invention include polymer dispersants such as polyamide amines and salts thereof, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, (Meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

The polymer dispersant can be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer from the structure.

The polymeric dispersant is adsorbed on the surface of the pigment to prevent re-aggregation. Therefore, a terminal modified polymer, a graft polymer, and a block polymer having an anchor site on the surface of the pigment are preferable structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Specific examples of the pigment dispersant that can be used in the present invention include Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) , "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA 4047, 4050, 4010, 4165 (manufactured by EFKA) Polybutadiene), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 Phthalocyanine derivative), 6750 (azo pigment derivative), Azine Super PB821 and PB822 manufactured by Ajinomoto Pan Techno Co., Ltd., Floren TG-710 (urethane oligomer) manufactured by Kyowa Shokagaku Co., (Aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703 (polyacrylic ester), &quot; DERPARON KS-860, 873SN, 874, (Aromatic sulfonic acid formalin polycondensate), &quot; Homogenol L-18, DA-705, DA-725 &quot;, Kao Corp., &quot; Demol RN, N (naphthalenesulfonic acid formalin polycondensate) (Polyoxyethylene nonylphenyl ether), &quot; acetamin 86 (stearylamine acetate) &quot;, Lubrizol &quot; Solspers 5000 (polyvinylpolycarboxylic acid) &quot;, &quot; Emalgene 920, 930, 935, 28000, 32000, 38500 (graft type polymer) "," Nikko Chemical Co., Ltd. "), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 NIKOL T106 (polyoxyethylene sorbitan monooleate), and MYS-IEX (polyoxyethylene monostearate).

These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymeric dispersant.

The content of the dispersant in the present invention is preferably from 1 to 100 mass%, more preferably from 3 to 100 mass%, and still more preferably from 5 to 80 mass% with respect to the pigment.

Specifically, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 to 100 mass%, more preferably in the range of 10 to 80 mass% with respect to the pigment. When the pigment derivative is used, the amount of the pigment derivative is preferably in the range of 1 to 30 mass%, more preferably in the range of 3 to 20 mass%, more preferably in the range of 5 to 15 mass% Is particularly preferable.

In the present invention, when the pigment and the dispersant are used as the colorant, the total sum of the content of the colorant and the dispersant is preferably 30% by mass or more and 90% by mass or less with respect to the total solid content constituting the curable composition More preferably 40% by mass or more and 85% by mass or less, and still more preferably 50% by mass or more and 80% by mass or less.

<(F) sensitizer>

The curable composition of the present invention may contain (F) a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the wavelength of the photosensitive wavelength. As the sensitizer that can be used in the present invention, it is preferable to increase or decrease the photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer usable in the present invention include those having the absorption wavelength in the wavelength range of 300 nm to 450 nm belonging to the compounds listed below.

Examples of preferred sensitizers include those having the absorption wavelength in the region from 330 nm to 450 nm, belonging to the following compounds.

For example, polynuclear aromatic compounds (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (such as fluorene, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (such as thiacarbocyanine, oxacarbocyanine), melocyanin For example, melocyanine, carbomeroxy), phthalocyanines, thiazines (e.g., thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, (Such as anthraquinone), squalidium (e.g., squarium), acridine orange, coumarins such as 7-diethylamino-4-methylcoumarin, Tocumarine, phenothiazine, phenazine, styrylbenzenes, azo compounds, diphenylmethane, triphenyl There can be mentioned compounds represented by the following formulas: methane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigos, styryls, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, Aromatic ketone compounds such as benzophenone, thioxanthone and Michler's ketone, heterocyclic compounds such as N-aryloxazolidinone, and the like. Compounds described in European Patent No. 568,993, U.S. Patent No. 4,508,811, U.S. Patent No. 5,227,227, JP-A-2001-125255, JP-A-11-271969, and the like.

Examples of the more preferable sensitizer include compounds represented by the following general formulas (I) to (V).

(In the formula (I), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, L ² represents a nonmetal atomic group capable of forming a basic nucleus of a coloring matter in association with adjacent A ² and adjacent carbon atoms , R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetal atomic group, and R ⁵¹ and R ⁵² may combine with each other to form an acidic nucleus of the dye, and W represents an oxygen atom or a sulfur atom. )

(In the formula (II), Ar ¹ and Ar ² each independently represent an aryl group, and they are linked via -L ³ -, wherein L ³ represents -O- or -S-, and W Is the same as that represented by the general formula (XIV).)

(In the formula (III), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetal atomic group which forms a basic nucleus of a coloring matter in association with adjacent A ² and a carbon atom, and R ⁵³ , R ⁵⁴ and R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent group of a non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

(In the formula (IV), A ³ and A ⁴ each independently represent -S- or -NR ⁶² - or -NR ⁶³ -, and R ⁶³ and R ⁶⁴ each independently represent a substituted or unsubstituted alkyl group, And L &lt; ⁵ &gt; and L &lt; ⁶ &gt; each independently represent a nonmetal atomic group which forms a basic nucleus of the coloring matter in association with adjacent A ³ and A ⁴ and adjacent carbon atoms; and R ⁶⁰ and R ⁶¹ each independently represent an aryl group of 1 Lt; / RTI &gt; atoms, or they may be bonded to each other to form an aliphatic or aromatic ring.

(In the formula (V), R ⁶⁶ represents an aromatic ring or a heterocycle which may have a substituent, A ⁵ represents an oxygen atom, a sulfur atom or -NR ⁶⁷ -, R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently And R ⁶⁷ and R ⁶⁴ and R ⁶⁵ and R ⁶⁷ may bond to each other to form an aliphatic or aromatic ring.

Specific preferred examples of the compounds represented by the general formulas (I) to (V) include those shown below.

The sensitizers may be used singly or in combination of two or more.

The content of the sensitizer in the curable composition of the present invention is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 15% by mass, in terms of solid content, from the viewpoints of the light absorption efficiency to the core portion and the decomposition efficiency .

&Lt; (G) Binder polymer &

In the curable composition of the present invention, a binder polymer may be further used if necessary for the purpose of improving the film properties. As the binder, it is preferable to use a linear organic polymer. As such &quot; linear organic polymer &quot;, known ones can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline development. The linear organic polymer is used not only as a film-forming agent, but also as a water, a weak alkaline water or an organic solvent developer. For example, the use of water-soluble organic polymers makes water development possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as those disclosed in Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Those described in JP-A-54-25957, JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048, that is, resins obtained by singly or copolymerizing monomers having a carboxyl group, A resin in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated, or an epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid or an acid anhydride, alone or in combination with monomers having an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Monomers having an acid anhydride include maleic anhydride.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, it is useful that a cyclic acid anhydride is added to a polymer having a hydroxyl group.

When an alkali-soluble resin is used as the copolymer, monomers other than the monomers may be used as the copolymerizing compound. Examples of other monomers include the following compounds (1) to (12).

(1) a polyfunctional monomer selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, Acrylate esters having an aliphatic hydroxyl group such as acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate, and methacrylic acid esters.

(2) acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, Acrylate such as vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-aryloxyethyl acrylate, propargyl acrylate and the like such as 3,4-epoxycyclohexylmethyl acrylate, Late.

(3) a polyfunctional monomer selected from the group consisting of methylmethacrylate, ethylmethacrylate, propylmethacrylate, butylmethacrylate, isobutylmethacrylate, amylmethacrylate, hexylmethacrylate, 2-ethylhexylmethacrylate, methacrylic acid Cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1 - alkyl methacrylates such as propenyl methacrylate, allyl methacrylate, 2-aryloxyethyl methacrylate and propargyl methacrylate.

(4) A method for producing an acrylic resin composition, which comprises the steps of: (1) mixing acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexylmethacrylamide, N-cyclohexyl acrylamide, N- , N-nitrophenylacrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, Acrylamide or methacrylamide such as allyl methacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(7) styrenes such as styrene,? -Methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like.

(11) Unsaturated imides such as maleimide, N-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide and N- (p-chlorobenzoyl) methacrylamide.

(12) A methacrylic acid-based monomer having a hetero atom bonded to the? -Position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like.

Among them, a (meth) acrylic resin having an allyl group, a vinyl ester group and a carboxyl group in its side chain, an alkali-soluble resin having a double bond in the side chain described in Japanese Patent Application Laid-Open Nos. 2000-187322 and 2002-62698 , And alkali-soluble resins having an amide group in the side chain described in JP-A-2001-242612 are excellent in balance of film strength, sensitivity, and developability.

Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Laid- 63-287947, and JP-A-1-271741, and urethane-based binder polymers having an acid group and a double bond in the side chain described in Japanese Patent Application Laid-Open No. 2002-107918, It is advantageous from the standpoint of light resistance and low exposure suitability.

The acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 is preferable because it has excellent balance of film strength and developability.

As other water soluble linear organic polymers, polyvinyl pyrrolidone, polyethylene oxide and the like are useful. Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured coating.

The weight average molecular weight of the binder polymer usable in the present invention is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000, the number average molecular weight is preferably 1,000 or more, more preferably 2,000 &Lt; / RTI &gt; The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.

These binder polymers may be random polymers, block polymers, graft polymers, or the like.

The binder polymer usable in the present invention can be synthesized by a conventionally known method. Examples of the solvent used for the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, lactic acid Methyl, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents may be used alone or in combination of two or more.

Examples of the radical polymerization initiator used for synthesizing the binder polymer usable in the present invention include known compounds such as an azo-based initiator and a peroxide initiator.

<(H) Notarization>

It is also preferable that the curable composition of the present invention contains a notarization accelerator. In the present invention, the notarization agent has an action of further increasing the sensitivity to the active radiation of the sensitizing dye or initiator, or inhibiting polymerization inhibition of the polymerizable compound by oxygen.

Examples of such notarization agents include amines such as M.I. R. Sander et al., Journal of Polymer Society Vol. 10, p. 3173 (1972), Japanese Patent Publication Nos. 44-20189, 51-82102, 52-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, and Research Disclosure 33825 Specific examples thereof include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodymethyl aniline.

Other examples of the notarization agent include thiols and sulfides such as thiol compounds disclosed in Japanese Patent Application Laid-Open Nos. 53-702, 55-500806 and 5-142772, And disulfide compounds disclosed in JP 56-75643 A, and specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, 2-mercapto -4 (3H) -quinazoline,? -Mercaponaphthalene, and the like.

Examples of the notarization agent include amino acid compounds (e.g., N-phenylglycine), organometallic compounds disclosed in Japanese Patent Publication No. 48-42965 (e.g., tributyltin acetate), Japanese Patent Publication 55- A hydrogen donor disclosed in JP-A-34414, and a sulfur compound disclosed in JP-A-6-308727 (e.g., trithian and the like).

The content of these notarization agents is preferably in the range of 0.1 to 30 mass%, more preferably in the range of 1 to 25 mass% with respect to the mass of the total solid content of the curable composition from the viewpoint of improvement of the curing rate by balance of polymerization growth rate and chain transfer, , And more preferably in the range of 0.5 to 20 mass%.

&Lt; (I) Polymerization inhibitor >

In the present invention, it is preferable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated double bond-containing compound during or during the production of the curable composition.

Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cetylsulfate .

The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be localized on the surface of the photosensitive layer in the course of drying after coating. The amount of the higher fatty acid derivative to be added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Other additives>

In the present invention, known additives such as an inorganic filler, a plasticizer, and a sensitizer (sensitizer) capable of improving ink deposition of the surface of the photosensitive layer may be added in order to improve the physical properties of the cured coating .

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. , 10 mass% or less can be added to the total mass of the compound having an ethylenically unsaturated double bond and the binder.

The curable composition of the present invention cures at a high sensitivity, and storage stability is also good. And exhibits high adhesion to the surface of a hard material such as a substrate to which the curable composition is applied. Therefore, the curable composition of the present invention can be suitably used in fields such as image forming materials such as three-dimensional stereolithography, holography, and color filters, inks, paints, adhesives, and coatings.

[Color filter and manufacturing method thereof]

Next, a color filter and a manufacturing method thereof according to the present invention will be described.

The color filter of the present invention is characterized by having a coloring pattern formed by using the curable composition of the present invention on a support.

Hereinafter, the color filter of the present invention will be described in detail through a manufacturing method thereof (a manufacturing method of a color filter of the present invention).

(Hereinafter, referred to as &quot; curable composition layer forming process &quot; as appropriate) on a support by applying the curable composition of the present invention and a step of exposing the curable composition layer through a mask (Hereinafter, abbreviated as &quot; exposure step &quot; as appropriate), and a step of developing the curable composition layer after exposure to form a colored pattern do.

Hereinafter, each step in the manufacturing method of the present invention will be described.

&Lt; Curable composition layer forming step &

In the step of forming the curable composition layer, the curable composition of the present invention is applied on a support to form a curable composition layer.

Examples of the support which can be used in the present step include soda glass, Pyrex (registered trademark) glass, quartz glass and a transparent conductive film adhered thereto, photoelectric conversion element substrates used for image pickup devices, For example, a silicon substrate or the like, or a complementary metal oxide semiconductor (CMOS). In these substrates, a black stripe for isolating each pixel may be formed.

On the support, if necessary, a lower layer may be formed for improving adhesion with the upper layer, preventing diffusion of the material, or planarizing the surface of the substrate.

As a coating method of the curable composition of the present invention on a support, various coating methods such as slit coating, inkjet coating, spin coating, flex coating, roll coating, screen printing and the like can be applied.

The coating film thickness of the curable composition is preferably 0.1 to 10 mu m, more preferably 0.2 to 5 mu m, and further preferably 0.2 to 3 mu m.

Drying (prebaking) of the layer of the photocurable composition applied on the substrate can be performed in a hot plate, an oven or the like at a temperature of 50 to 140 DEG C for 10 to 300 seconds.

<Exposure Step>

In the exposure step, the curable composition layer formed in the step of forming the curable composition layer is exposed through a mask having a predetermined mask pattern.

In the exposure in this step, the pattern exposure of the coating film is exposed through a predetermined mask pattern, only the portion of the coated film that is irradiated with light is cured and developed with a developer, and a pattern composed of pixels of each color (three colors or four colors) And forming an overcoat. As the radiation that can be used at the time of exposure, ultraviolet rays such as g line and i line are preferably used. The irradiation dose is preferably 5 to 1500 mJ / cm 2, more preferably 10 to 1000 mJ / cm 2, and most preferably 10 to 500 mJ / cm 2.

In the case where the color filter of the present invention is used for a liquid crystal display element, it is preferably 5 to 200 mJ / cm 2, more preferably 10 to 150 mJ / cm 2, and most preferably 10 to 100 mJ / cm 2 in the above range. In the case where the color filter of the present invention is for a solid-state image sensor, it is preferably 30 to 1500 mJ / cm 2, more preferably 50 to 1000 mJ / cm 2, and most preferably 80 to 500 mJ / cm 2 in the above range.

<Development Process>

Subsequently, by performing the alkali developing treatment, only the portion where the light-irradiated portion is eluted into the alkaline aqueous solution by the above-described exposure and is photo-cured remains. As the developing solution, an organic alkali developing solution which does not cause damages to the underlying circuit or the like is preferable. The developing temperature is usually 20 to 30 占 폚, and the developing time is 20 to 90 seconds.

Examples of the alkali agent to be used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, And organic alkaline compounds such as mercaptopropylcyclo- [5,4,0] -7-undecene. These alkaline agents are diluted with pure water to a concentration of 0.001 to 10 mass%, preferably 0.01 to 1 mass% An alkaline aqueous solution is preferably used as the developer. When a developer composed of such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with pure water after development.

Subsequently, the surplus developing solution is washed away, dried, and then subjected to heat treatment (post-baking). The curing coating can be produced by repeating the above steps sequentially for each color. Thus, a color filter is obtained.

The post-baking is a post-development heat treatment for making the curing to be complete, and is generally subjected to a heat curing treatment at 100 캜 to 240 캜. When the substrate is a glass substrate or a silicon substrate, the temperature is preferably 200 ° C to 240 ° C in the above temperature range.

This post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a Ken Vecction oven (hot air circulation type drier), or a high-frequency heater so that the coated film after development can be in the above conditions.

The manufacturing method of the present invention may include a curing step of curing the colored pattern formed as necessary after heating, and / or exposure after the above-described curable composition layer forming step, the exposure step, and the developing step do.

By repeating the above-described curable composition layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) as many as the desired number of colors, a color filter having a desired color is produced.

As the use of the curable composition of the present invention, mainly the use of the color filter in the pixel has been mainly described, but it goes without saying that it is also applicable to the black matrix formed between the pixels of the color filter. The black matrix is subjected to pattern exposure and alkali development in the same manner as in the above-described method for producing a pixel except that a black colorant such as carbon black or titanium black is added to the curable composition of the present invention as a colorant, Thereby promoting the curing of the film.

Since the color filter of the present invention uses the curable composition of the present invention as described above, the formed colored pattern exhibits high adhesiveness to the support substrate and the cured composition is excellent in developing resistance. Therefore, the color filter has excellent exposure sensitivity, It is possible to form a high-resolution pattern having good adhesion with the substrate and giving a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state image pickup device such as a liquid crystal display element and a CCD, and is particularly preferable for a high-resolution CCD element or CMOS exceeding one million pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing.

[Example]

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. Unless otherwise stated, &quot;% &quot; and &quot; part &quot; are based on mass.

Hereinafter, a specific synthesis method of the Exemplary Compound (1) will be described. Other (A) specific polymerizable compounds usable in the present invention can be synthesized by the same scheme. The synthesis method is not limited to the following method.

[Synthesis Example 1]: Synthesis of Exemplified Compound (1)

20 ml of acetonitrile was added to and dissolved in 12 g (0.023 mol) of dipentaerythritol pentaacrylate, followed by the addition of 0.16 g (0.25 mmol) of bismuth tris (2-ethylhexanoate) and triethoxy (3-isocyanatepropyl) silane (0.23 mol), and the mixture was stirred at 55 to 65 ° C for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and then 50 ml of n-hexane was added thereto, followed by washing three times, and the lower layer was collected. The solvent was distilled off to obtain 17 g (0.022 mol, Yield: 95%) of the compound (1).

(5H, dd), 6.10ppm (5H, dH) in the compound (1) obtained above was confirmed by NMR. , dd), 5.85 ppm (5H, dd), 5.10 ppm (1H, brt), 4.25 ppm (6H, s), 4.20 ppm (4H, s), 4.16 ppm (2H, s), 3.15 ppm (2H, m), 1.62 ppm (2H, m), 1.23 ppm (9H, t), 0.63 ppm .

The curable composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the scope thereof is exceeded.

(Example 1)

[Preparation of a curable composition]

Here, an example in which a curable composition containing a colorant (pigment) is prepared for forming a color filter for a liquid crystal display element will be described.

1-1. Pigment kneading dispersion treatment

First, each of the following components was kneaded and dispersed with two rolls.

C.I. Pigment Red 254 22 parts by mass

C.I. Pigment Yellow 139 8 parts by mass

· Resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl

  Methacrylate copolymer, molar ratio: 80/10/10,

  Mw: 10000, solvent: propylene glycol methyl ether acetate 60%,

  Resin solid content concentration: 40%) 40 parts by mass

Solvent: 20 parts by mass of propylene glycol methyl ether acetate

Dispersing agent: 2 parts by mass (trade name: BY-161, manufactured by BYK)

Further, the following components were added to the dispersion obtained above, and finely dispersed overnight with a sand mill.

Solvent: propylene glycol methyl ether acetate (PGMEA)

                                                 200 parts by mass

1-2 Preparation of curable composition (coating liquid)

The following components were further added to the dispersion-treated pigment and mixed with stirring to prepare a curable composition solution.

12 parts by mass of the above-mentioned Exemplified Compound (1) [(A) specific polymerizable compound]

· 4-Benzoxorane-2,6-di (trichloromethyl) -s-triazine

  [(B) Photopolymerization initiator] 0.5 parts by mass

- 0.2 parts by mass of a surfactant (trade name: Tetronic 150R1, BASF)

Solvent: PGMEA 100 parts by weight

[2. Production of color filter]

2-1. Formation of Curable Composition Layer

The slurry was applied to a glass substrate of 550 mm x 650 mm in the following conditions using the curable composition containing the pigment as a resist solution, followed by standing for 10 minutes under the same conditions, followed by vacuum drying and prebaking ) To form a curable composition coating film (curable composition layer).

(Slit application condition)

Clearance at the opening of the coating head tip: 50 탆

Coating speed: 100 mm / sec

Clearance between substrate and coating head: 150 m

Coating thickness (dry thickness): 2 탆

Application temperature: 23 ℃

2-2. Exposure and development

Thereafter, the photo-curable coating film was exposed in a pattern using a test photomask with a line width of 20 mu m using an ultra-high pressure mercury lamp of 2.5 kw, and the entire surface of the coated film after exposure was irradiated with an organic developer (trade name: CD, Fuji Film Arch ), And then stopped for 60 seconds.

2-3. Heat Treatment

After stopping, the pure water was sprayed into a shower, the developer was washed away, and the coated film subjected to the photo-curing treatment and the developing treatment was heated in an oven at 220 캜 for 1 hour (post-baking). As a result, a colored resin film (color filter) was formed on the glass substrate.

[3. Performance evaluation]

The storage stability of the coloring curable composition prepared above and the curability of the curable composition film (colored layer) formed on the glass substrate using the colored curable composition, the exposure sensitivity, the substrate adhesion, the developability, and the cross- And evaluated in the following manner. The results are shown in Table 1.

3-1. Storage stability of coating liquid

After the coating liquid was stored at room temperature for one month, the degree of precipitation of foreign matter was visually confirmed and evaluated according to the following criteria.

<Criteria>

○: Precipitation was not confirmed.

B: A little precipitation was confirmed.

X: precipitation was confirmed.

3-2. Exposure sensitivity of the coating film (colored layer)

The exposure amount was changed to various exposure amounts of 10 to 100 mJ / cm &lt; 2 &gt; to expose, and the exposure amount at which the post-baked pattern line width became 20 mu m was evaluated as the exposure sensitivity. The smaller the value of the exposure sensitivity, the higher the sensitivity.

3-3. Developability, pattern cross-sectional shape, substrate adhesion

The substrate surface and cross-sectional shape after post-baking were confirmed by an ordinary microscope by an optical microscope and an SEM photograph.

In the exposure process, the presence or absence of a residue of a region not exposed to light (unexposed portion) was observed, and the developability was evaluated.

<Developability>

○: No residues were observed in minerals.

?: A little residue was left on the unexposed portion, but there was no practical problem.

X: Remnant was remarkably confirmed in the unexposed area.

Sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a net taper, and the rectangle is next preferred. Reverse taper is not desirable.

As an evaluation of the substrate adhesion, it was observed whether a pattern defect occurred or not. These evaluation items were evaluated based on the following criteria.

&Lt; Substrate adhesion property &

?: No pattern defect was observed at all.

DELTA: The pattern defect was hardly observed, but a partial defect was observed.

X: Pattern defects were remarkably observed.

[Examples 2 to 9]

A coloring pattern was obtained in the same manner as in Example 1, except that Example Compound (1), which is a specific polymerizable compound (A), was used instead of the exemplified compounds shown in Table 1 below in the curable composition of Example 1, Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Example 10]

(1), which is a specific polymerizable compound (A), was replaced with the exemplified compound shown in the following Table 1, and the substrate was placed on a polyethylene terephthalate substrate of the same size PET substrate "), and the post-baking step was changed to an irradiation step of 10000 mJ / cm 2 in a high-pressure mercury lamp, a coloring pattern was obtained in the same manner as in Example 1, . The results are shown in Table 1.

[Comparative Example 1]

All of the curable compositions of Example 1 were prepared in the same manner as in Example 1, except that (A) the specific polymerizable compound, Exemplified Compound (1), was used instead of the comparative polymerizable compound shown in Table 1 below. The results are shown in Table 1.

[Comparative Example 2]

(1), which is a specific polymerizable compound (A), was replaced with the exemplified compound shown in the following Table 1, and the glass substrate was changed to a polyethylene terephthalate substrate of the same size as the substrate in the curable composition of Example 1 And the post-baking step was changed to an irradiation step of 10000 mJ / cm 2 in a high-pressure mercury lamp, the same procedure as in Example 1 was repeated to obtain a coloring pattern, and the same evaluations as in Example 1 were carried out. The results are shown in Table 1.

From the results shown in Table 1, it can be seen that the colored curable composition of the embodiment using the curable composition of the present invention is excellent in storage stability in the solution, and when an image is formed on a support, the polyfunctional acrylate type comparative polymerizable compound The substrate adhesion, and the cross-sectional shape of the pattern. Further, by improving the double bond density in the vicinity of the substrate and the substrate adhesion, erosion by the developer is suppressed, and as a result, the exposure sensitivity is improved.

Hereinafter, an example in which a curable composition containing a colorant (dye) is prepared for forming a color filter for a solid-state image sensor will be described.

(Example 11)

[Preparation of resist solution]

The components of the following composition were mixed and dissolved to prepare a resist solution.

<Composition>

· Propylene glycol monomethyl ether acetate ... Section 19.20

   (PGMEA: solvent)

· Ethyl ... 36.67 parts

· Binder Polymer ... 30.51 part

  [Benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate

   40% PGMEA solution of a copolymer (molar ratio = 60/22/18)

· Dipentaerythritol hexaacrylate ... 12.20 part

  (Photopolymerizable compound)

· Polymerization inhibitor (p-methoxyphenol) ... 0.0061 part

· Fluorine surfactant ... 0.83 part

  (F-475, manufactured by Dainippon Ink and Chemicals, Inc.)

· Photopolymerization initiator ... 0.586 part

  (TAZ-107 (trihalomethyl triazine based photopolymerization initiator), Midorikagaku)

[2. Preparation of silicon substrate with undercoat layer]

A 6-inch silicon wafer was heated in an oven at 200 캜 for 30 minutes. Subsequently, the resist solution was coated on the silicon wafer so that the dry film thickness became 2 탆, and further heated and dried in an oven at 220 캜 for one hour to form a water-repellent layer, thereby obtaining a silicon wafer substrate having a water-repellent layer.

3. Preparation of colorant-containing curing composition (dye-based)

The following compound A-1 was mixed and dissolved to prepare a colored photosensitive resin composition A-1.

<Composition A-1>

· Cyclohexanone (solvent) ... 80 parts

· Valifast Yellow 1101 (Dye (C)) ... 5.0 parts

· Acid Red 57 (Dye (C)) ... 5.0 parts

· Dipentaerythritol hexaacrylate

  General Radical Polymerizable Compound (E) having no Adhesion Group 5.0 parts

· Exemplified Compound (1) [(A) Specific Polymerizable Compound] 2.0 parts

· Photopolymerization initiator (B) ... 2.5 parts

  (CGI-124, manufactured by Ciba Specialty Chemicals, oxime-type photopolymerization initiator)

· Glycerol propoxylate ... 0.5 part

 (Number average molecular weight Mn: 1,500, molar extinction coefficient? = 0, colorless compound)

5. Production and Evaluation of Color Filter Using Colored Photosensitive Resin Composition [

- Formation of pattern and evaluation of sensitivity -

The colorant-containing curable composition A-1 prepared in the above 3. was coated on the undercoating layer of the silicon wafer substrate having the undercoat layer obtained in the above 2. to form a curable composition layer (coating film). Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 0.9 탆.

Subsequently, the pattern was exposed at various exposure amounts of 100 to 1600 mJ / cm &lt; 2 &gt; through an island pattern mask having a wavelength of 365 nm and a 2 mu m square each using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.).

Thereafter, the silicon wafer substrate on which the coated film was irradiated was placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by KEMITRONICS Co., Ltd.), and CD-2000 (FUJIFILM Electronics Matrix Paddle development was performed at 23 DEG C for 60 seconds to form a colored pattern on a silicon wafer substrate.

The silicon wafer substrate on which the coloring pattern was formed was fixed to the horizontal rotary table by a vacuum chucking method and the silicon wafer substrate was rotated at a rotation speed of 50 rpm by a rotary device while pure water was sprayed from a spray nozzle Followed by rinsing, followed by spray drying. Thereafter, the size of the colored pattern was measured using a measurement SEM "S-9260A" (manufactured by Hitachi High-Technologies Corporation). The exposure amount at which the pattern line width became 2 탆 was evaluated as the exposure sensitivity. The smaller the value of the exposure sensitivity, the higher the sensitivity. The results of the measurement evaluation are shown in Table 2 below.

In the exposure process, the presence or absence of a residue of a region where light was not irradiated (unexposed portion) was observed and the developability was evaluated.

<Developability>

○: No residues were observed in minerals.

?: A little residue was left on the unexposed portion, but there was no practical problem.

X: Remnant was remarkably confirmed in the unexposed area.

Sectional shape of the formed pattern was observed. The cross-sectional shape of the pattern is preferably a rectangular shape, and reverse tapering is not preferable.

As an evaluation of the substrate adhesion, it was observed whether a pattern defect occurred or not. These evaluation items were evaluated based on the following criteria

&Lt; Substrate adhesion property &

?: No pattern defect was observed at all.

DELTA: The pattern defect was hardly observed, but a partial defect was observed.

X: Pattern defects were remarkably observed.

(Examples 12 to 15)

A coloring pattern was obtained in the same manner as in Example 11 except that the compound shown in the following Table 2 was used instead of the exemplified compound (1) used in the above-mentioned [3. Preparation of colorant-containing curing composition] Evaluation was carried out in the same manner as in Example 11. The results are shown in Table 2.

[Comparative Example 3]

Except that the comparative polymerizable compound shown in the following Table 2 was used instead of the exemplified compound (1) used in the above-mentioned [3. Preparation of the colorant-containing curable composition of Example 11] Respectively. The results are shown in Table 2.

(Example 16)

Preparation of a curing composition (pigment system) for a color filter for use in a solid-state image sensor

1-1. Pigment kneading dispersion treatment

First, each of the following components was kneaded and dispersed with two rolls.

C.I. Pigment Red 254 22 parts by mass

C.I. Pigment Yellow 139 8 parts by mass

· Resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl

   Methacrylate copolymer, molar ratio: 80/10/10,

   Mw: 10000, solvent: propylene glycol methyl ether acetate

   60%, resin solid content concentration: 40%) 40 parts by mass

Solvent: 20 parts by mass of propylene glycol methyl ether acetate

Dispersing agent: 2 parts by mass (trade name: BY-161, manufactured by BYK)

Further, the following components were added to the dispersion obtained above, and finely dispersed overnight with a sand mill.

Solvent: propylene glycol methyl ether acetate (PGMEA)

                                                 200 parts by mass

1-2 Preparation of curable composition (coating liquid)

The following components were further added to the dispersion-treated pigment and mixed with stirring to prepare a curable composition solution.

12 parts by mass of the above-mentioned Exemplified Compound (1) [(A) specific polymerizable compound]

· 4-Benzoxorane-2,6-di (trichloromethyl) -s-triazine

   [(B) Photopolymerization initiator] 0.5 parts by mass

- 0.2 parts by mass of a surfactant (trade name: Tetronic 150R1, BASF)

Solvent: PGMEA 100 parts by weight

The application, exposure, development, and performance evaluation of the curable composition of the item "preparation of a curable composition (dye system) for a color filter for a solid-state imaging element application" for use in the above-mentioned coating liquid were performed. The results are summarized in Table 2.

[Comparative Example 4]

Except that Exemplary Compound (1) used in the above-mentioned [1-2. Preparation of Curable Composition (Coating Liquid)] of Example 16 was changed as shown in the following Table 2, Respectively. The results are summarized in Table 2.

From the results shown in Table 2, the colored curable composition of the example using the curable composition of the present invention was excellent in storage stability in its solution form as in the case of using a pigment as a colorant even when a dye was used as a colorant.

In addition, even when an image is formed on a support, it can be seen that the comparative example using only the polyfunctional acrylate type comparative polymerizable compound outside the range of the present invention is excellent in developability, substrate adhesion, and pattern cross-sectional shape. From these results, it can be seen that the erosion by the developer is suppressed by improving the double bond density in the vicinity of the substrate and the substrate adhesion, and as a result, the exposure sensitivity is improved.

According to the present invention, even when a colorant is contained at a high concentration, it is possible to provide a curable composition which is cured with high sensitivity, has good pattern forming properties, and is excellent in adhesion to a hard surface as a base material.

Further, according to the present invention, by using the curable composition of the present invention, it is possible to provide a color filter having a coloring pattern excellent in resolution and adhesion to a support, and a manufacturing method capable of producing the color filter with high productivity .

Claims (17)

(A) a curable composition containing a radically polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group to a hard material, and (B) a photopolymerization initiator, The ethylenically unsaturated double bond is an ester or amide structure of (meth) acrylic acid, The adhesion group to the hard material may be selected from the group consisting of an acid group, an ester group of an acid, an acid salt of an acid, an acid metal salt, a substituent which generates a silanol group by hydrolysis, an onium group, a phenolic hydroxyl group, a positive ionic group, A group having one or more partial structures selected, The photopolymerization initiator (B) is at least one compound selected from the group consisting of a trihalomethyltriazine compound, an? -Aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound &Lt; / RTI &gt; delete The curable composition according to claim 1, wherein the hard material is a glass substrate or a silicon substrate, and the adhesive group to the hard material is a substituent group that generates a silanol group by hydrolysis. The curable composition according to claim 1, wherein (A) the radically polymerizable compound having an ethylenically unsaturated double bond and a bonding group to a hard material in the molecule has a plurality of ethylenically unsaturated double bonds in the molecule. delete The curable composition according to claim 3, wherein the (A) radically polymerizable compound having an ethylenically unsaturated double bond and a bonding group to a hard material in the molecule has a plurality of ethylenically unsaturated double bonds in the molecule. delete The curable composition according to any one of claims 1, 3, and 4, further comprising (C) a colorant having a maximum absorption in a visible wavelength range of from 400 nm to 700 nm. A color filter having a coloring pattern formed by using the curable composition according to claim 8 on a support. A step of forming a colored curable composition layer by applying the curable composition of claim 8 on a support, a step of exposing the curable composition layer through a mask, a step of developing the curable composition layer after exposure to form a colored pattern Wherein the step of forming the color filter comprises the steps of: The curable composition according to claim 1, wherein the adhesive group to the hard material is a substituent group that generates a silanol group by hydrolysis. The acrylic pressure-sensitive adhesive composition according to claim 1, which is at least one member selected from the group consisting of bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) iso (A) further comprises a compound selected from the group consisting of a cyanurate, a pentaerythritol tetraacrylate EO-modified product, and a dipentaerythritol hexaacrylate EO-modified product, (A) / (A) + (E)] of the radical polymerizable compound (A) is 0.01 or more and 0.3 or less. The acrylic pressure-sensitive adhesive composition according to claim 1, which is at least one member selected from the group consisting of bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) iso (A) further comprises a compound selected from the group consisting of a cyanurate, a pentaerythritol tetraacrylate EO-modified product, and a dipentaerythritol hexaacrylate EO-modified product, (A) / (A) + (E)] of the radically polymerizable compound is from 0.01 to 0.15. The curable composition according to claim 1, wherein the (A) radically polymerizable compound has four or more ethylenically unsaturated double bonds. The curable composition according to claim 1, wherein the (A) radically polymerizable compound has five or more ethylenically unsaturated double bonds. The curable composition according to claim 1, wherein the (A) radically polymerizable compound is represented by the following formula (A).

In the general formula (A), M represents a group selected from the following (M-1) to (M-11), L represents an oxygen atom, a nitrogen atom, a sulfur atom, Having a partial structure selected from the group consisting of a structure, an aromatic ring, a heterocycle, a urethane bond, a thiourethane bond, an ester bond, an amide bond, an urea bond and a thiourea bond, and X represents an organic linking group having a valence of n + 1, and X represents an acid group, an ester group, an acid salt, an acid metal salt of an acid, a substituent that generates a silanol group by hydrolysis, an onium group, a phenolic hydroxyl group, And n represents an integer of 1 to 5, and m represents an integer of 1 to 3.

The curable composition according to claim 1, wherein the (B) photopolymerization initiator is a oxime-based compound.