JP2007316445A - Curable composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition having good pattern forming property and excellent in adhesion to a hard surface as a base, even when a colorant is contained at a high concentration, a color filter obtained by forming a high-resolution colored pattern, and a method for producing the same. <P>SOLUTION: The curable composition contains (A) a radical polymerizable compound having an ethylenically unsaturated double bond and a group adhesive to a hard material within a molecule and (B) a photopolymerization initiator. The group adhesive to a hard material in the polymerizable compound is preferably one or more selected from the group consisting of an acid group, an acid ester group, an acid onium salt, an acid metal salt, a substituent forming a silanol group by hydrolysis, an onium group, a phenolic hydroxyl group, a zwitterionic group and a chelating group. The curable composition is useful to form a colored pattern of a color filter. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition, a color filter, and a production method thereof suitable for producing a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.) and the like.

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
A liquid crystal display is more compact than a CRT as a display device and is equivalent or better in terms of performance, and is thus being replaced by a CRT as a television screen, a personal computer screen, or other display device. In recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen has a relatively small area to TV applications where a large screen and high image quality are required.

  In color filter applications for liquid crystal displays (LCDs), the substrate size is increasing for large TV production, and low energy curing is desired to improve productivity when large substrates are used. In addition, liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor use. That is, improvement in contrast and color purity. In order to improve the contrast, the curable composition used for the production of the color filter is required to have a finer particle size of the colorant (organic pigment or the like) used. (For example, refer to Patent Document 1.) Along with this, the amount of dispersant added for dispersing the pigment tends to increase. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of a curable composition for color purity improvement. 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, curing with low energy is also desired in color filter applications for solid-state imaging devices. Moreover, the pattern thinning is progressing and the pigment density | concentration in a composition is improving with this. Furthermore, in the pigment-based color filter, the proportion of the pigment dispersant in the composition tends to increase as the pigment becomes finer. In addition, in order to cope with problems such as color unevenness that occurs because the pigment is relatively coarse particles, a technique using an organic solvent-soluble dye instead of the pigment as a colorant has been proposed (for example, Patent Documents). 4). However, in dye-based color filters, with the increase in dye concentration, the problem of the polymerization inhibition effect derived from dyes has become prominent. Due to such factors, the content of the photopolymerization initiator and the photopolymerizable monomer, which are components necessary for curing the curable composition, is limited in both cases for liquid crystal displays and solid-state imaging devices. In addition, since the colorant concentration is high, there are problems such as low sensitivity and insufficient curing, insufficient adhesion to the substrate, and extremely difficult pattern formation. It was. As a countermeasure against this problem, a technique of introducing a silane coupling agent (for example, refer to Patent Documents 2 and 3) has been proposed in order to improve the substrate adhesion.
JP 2006-30541 A JP-A-11-38226 Japanese Patent No. 2874091 JP-A-2-127602

The present invention has been made in consideration of the above-mentioned problems, and the object of the present invention is to cure with high sensitivity even when the colorant is contained in a high concentration, and has a good pattern forming property, It is providing the curable composition excellent in adhesiveness with the hard surface which is a base material.
Furthermore, another object of the present invention is to provide a color filter having a coloring pattern excellent in resolving power and adhesion to a support using the curable composition of the present invention, and producing the color filter with high productivity. It is to provide a manufacturing method that can be used.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by using a specific polymerizable compound, and has completed the present invention. That is, the means for solving the above problems are as follows.

<1> Curing characterized by containing (A) a radically polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to a hard material in the molecule, and (B) a photopolymerization initiator. Sex composition.
<2> The adhesive group to the hard material in the radical polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to the hard material in the molecule (A) is an acid group, an ester group of an acid, an acid <1>, which is at least one selected from the group consisting of onium salts, acid metal salts, substituents that generate silanol groups by hydrolysis, onium groups, phenolic hydroxyl groups, zwitterionic groups, and chelating groups Curable composition.
<3> The hard material is a glass substrate or a silicon substrate, and (A) adhesion to the hard material in the radical polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to the hard material in the molecule (A) The curable composition according to claim 1, wherein the functional group is a substituent that generates a silanol group by hydrolysis.
<4> The radically polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to a hard material in the molecule (A) has a plurality of ethylenically unsaturated double bonds in the molecule. The curable composition according to any one of <1> to <3>.
<5> 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.
<6> A color filter having a colored pattern using the curable composition according to <5> on a support.
<7> On the support, a step of applying the curable composition according to <5> to form a curable composition layer, a step of exposing the curable composition layer through a mask, and an exposure Developing the subsequent curable composition layer to form a colored pattern, and a method for producing a color filter.

  Here, if it mentions about the preferable aspect of the curable composition of this invention of <1> description, the curable composition of this invention is useful for manufacture of the coloring pattern in a color filter, From that viewpoint, it is as a support body. Hard materials used include inorganic materials such as glass and silicon substrates, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate In addition, those selected from the group consisting of resin materials such as polyvinyl acetal are preferred, and the adhesive group capable of adhering to a support formed of such a hard material includes a covalent bond, an ion between the surface of the hard material. Bond, hydrogen bond, polar interaction, van der Wa Functional groups capable of forming an interaction selected from the group consisting of pulse interaction.

  Adhesive groups for general-purpose glass and resin material surfaces as color filter supports include acid groups such as sulfonic acid groups, phosphonic acid groups, and carboxyl groups; ester groups of these acids; metal salts of these acids; these metals Onium salts; ammonium groups, pyridinium groups and other onium groups; alkoxysilyl groups and other hydrolytic substituents that produce silanol groups; phenolic hydroxyl groups, N-oxide groups and other zwitterionic groups; iminodiacetic acid, etc. A group selected from chelating groups is preferred.

According to the present invention, even when the colorant is contained at a high concentration, it is cured with high sensitivity, has good pattern forming properties, and has excellent adhesion with a hard surface as a substrate. A composition can be provided.
Furthermore, according to the present invention, by using the curable composition of the present invention, a color filter having a colored pattern excellent in resolving power and adhesion between the support and the color filter is produced with high productivity. A possible manufacturing method can be provided.

Hereinafter, the curable composition of the present invention, a color filter using the curable composition, and a production method thereof 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 and an adhesive group to a hard material in the molecule (hereinafter referred to as (A) a specific polymerizable compound as appropriate. ) And (B) a photopolymerization initiator.
First, the components (A) and (B), which are essential components of the curable composition of the present invention, will be described.

<(A) Radical polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to a hard material in the molecule>
The specific polymerizable compound (A) that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has an adhesive group to a hard material in the molecule. A compound.
Ethylenically unsaturated bonds include vinyl groups, unsaturated carboxylic acids (eg (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), unsaturated phosphonic acid esters and amides, styrene, Examples thereof include vinyl ether, and (meth) acrylic acid is preferable.
The specific polymerizable compound (A) of the present invention has at least 1, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, most preferably 5 or more of the above ethylenically unsaturated bonds. It is a compound that has at least one adhesive group to a hard material described in detail below.
That is, (A) the specific polymerizable compound has, in addition to the ethylenically unsaturated double bond group, an adhesive group that can improve the adhesion to the hard material surface to which the curable composition of the present invention is applied. It is characterized by having.

The hard material is a material that becomes a support substrate to which the curable composition of the present invention can be applied. For example, inorganic materials such as glass and silicon substrate, or cellulose diacetate, cellulose triacetate, and propionic acid. Organic resin materials such as cellulose, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. can be mentioned, and the curable composition of the present invention can be used for forming a color filter coloring pattern. When used, those selected from a transparent hard material or a silicon substrate are mentioned, and among these, a glass or a silicon substrate is preferable.
(A) The specific polymerizable compound is appropriately selected as to what adhesive group is introduced depending on the characteristics of the hard material to which the curable composition is applied.

  Such an adhesive 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 the hard material surface. Specifically, from the group consisting of acid groups, acid ester groups, acid onium salts, acid metal salts, substituents that generate silanol groups upon hydrolysis, onium groups, phenolic hydroxyl groups, zwitterionic groups, chelating groups Examples thereof include groups having at least one selected partial structure.

Examples of preferable adhesive groups include, for example, 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 silanol groups that are generated by hydrolysis. Examples include functional groups selected from the group consisting of substituents. Among them, an ammonium group, a substituent that generates a silanol group by hydrolysis, a phosphonic acid group, and an ester group thereof are preferable.
Among these, from the viewpoint of the strength of interaction, a substituent capable of forming an ionic bond, a multipoint hydrogen bond, or a covalent bond is preferable. Among them, it has a functional group selected from the group consisting of an ammonium group, a phosphonic acid group and its ester group, and an alkoxysilyl group, in addition to the substrate adhesion derived from the strength of the interaction with the substrate, unexposed. From the viewpoint of the developability of the part and the film strength of the exposed part.

  Examples of the polymerizable compound (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 an adhesive group to a hard material.

  In the general formula (A), M represents a site having an ethylenically unsaturated double bond, L represents an n + 1 valent organic linking group, and X represents an adhesive 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 (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.). In addition, an addition reaction between an isocyanate group, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group, and a monofunctional or polyfunctional alcohol, amine, or thiol, a halogen group, Examples thereof include a structure formed by a substitution reaction of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. Of these, a (meth) acryloyl group, styrene, and a vinyl ether structure are preferable. Furthermore, a structure having a (meth) acryloyl group is preferred.

In the general formula (A), L represents an n + 1 valent organic linking group determined by the number (n) of partial structures having an ethylenically unsaturated double bond, and in the structure, an oxygen atom, a nitrogen atom, A partial structure selected from the group consisting of a sulfur atom or a hydrocarbon ring structure having 3 to 10 carbon atoms, aromatic ring, heterocycle, urethane bond, thiourethane bond, ester bond, amide bond, urea bond, thiourea bond These are n + 1 valent linking groups which are constituted singly or in combination.
Such a linking group may further have a substituent. Examples of the substituent that can be introduced into the L linking group include an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, and a hydroxyl group. , Thiol group, cyano group, nitro group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic thio group, aromatic thio group, heterocyclic thio group, aliphatic sulfonamide group, aromatic sulfonamide Group, heterocyclic sulfonamido group, acyl group, acyloxy group, acylamino group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, hetero Ring oxycarbonylamino group, aliphatic thiocarbonylamino group, aromatic thiocarbonylamino group, heterocyclic thiocarbonylamino group Group, aliphatic aminocarbonylamino group, aromatic aminocarbonylamino group, heterocyclic aminocarbonylamino group, carbamoyl group, carbamoyloxy group, carbamoylamino group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, fat Aromatic oxyamino group, aromatic oxyamino group, heterocyclic oxyamino group, silyl group, aliphatic oxysilyl group, silyloxy group, aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group, heterocyclic oxycarbonyloxy group, sulfur Famoyloxy group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, anilino group, aliphatic azo group, aromatic azo group, heterocyclic azo group, aliphatic sulfinyl group, aromatic sulfinyl group, heterocyclic sulfinyl group, An aliphatic sulfonyloxy group, Aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, a sulfo group, a phosphonyl group, and a phosphinoylamino group.

[Specific examples of (A) specific polymerizable compound]
Specific examples [(M-1) to (M-11)] in the case where an acryloyl group is used as the ethylenic double bond group in the structure represented by M are shown below, but are not limited thereto. It is not a thing. Furthermore, the acryloyl group can be replaced with a substituent other than the above acryloyl group. In addition, the structure represented by M may have two or more different ethylenic double bond groups.

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

In the above formula, R ^{11 to} R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkynyl group, or an alkenyl group, and M ¹ and M ² each independently represent a hydrogen atom, a metal atom, or onium. Represents a group, and X ⁻ represents a counter anion.
X in the general formula (A) is preferably selected from the group consisting of divalent functional groups represented by the following formula when m is 2.

In the above formula, R ^{12 to} R ¹³ each independently represents 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 Represents a counter anion.
X in the general formula (A) is preferably selected from the group consisting of trivalent functional groups represented by the following formulas when m is 3.

In the above formula, each 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 the counter anion X ⁻ include a halogen anion such as a fluorine anion, a chlorine anion, a bromine anion, and an iodine anion; Fluoroacetate anion, sulfate anion, hydrogen sulfate anion, methanesulfonate anion, trifluoromethanesulfate anion, perchlorate anion, tetrafluoroborate anion, hexafluorophosphate anion, hexachloroantimonate anion, hexafluoroantimonate anion, etc. be able to. Among these, halogen anion, trifluoromethanesulfonate anion, methanesulfonate anion, sulfate anion, hydrogen sulfate anion, tetrafluoroborate anion, hexafluorophosphate anion and the like are preferable from the viewpoint of solubility and stability of the compound. . As the counter anion X ⁻ , the same one is exemplified even if m is any of 1 to 3.

[(A) Method for synthesizing specific polymerizable compound]
Next, although the example of the synthesis | combining method of (A) specific polymerizable compound represented by general formula (A) is shown, a synthesis method is not limited to this.
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 an adhesive group Addition reaction with monofunctional or polyfunctional alcohols, amines, and thiols having an alkyl group, and an unsaturated carboxylic acid ester or amide having a leaving group such as a halogen group or a tosyloxy group, and an adhesive group And a substitution reaction with monofunctional or polyfunctional alcohols, amines, and thiols having the above. In addition, a compound having an electrophilic substituent such as an isocyanate group or an epoxy group and an adhesive group, a hydroxyl group, an amino group, or a mercapto group, and at least one ethylenic double group An addition reaction with a compound having a bond can be mentioned. Furthermore, the specific polymerizable compound (A) represented by the general formula (A) is obtained by Michael addition reaction of an amine having an adhesive group or a thiol to a compound having two or more ethylenic double bonds. Can also be synthesized.

  As an example of the polymerizable compound (A) of the present invention, the structure of M in the general formula (A) is the exemplified structure (M-6), and an adhesive group X to a hard material is introduced into the structure. Examples [Exemplified compounds (1) to (20)] are shown below, but the structure of M in the general formula (A) can be appropriately changed to the above (M-1) to (M-11), etc. Both can be synthesized by existing synthesis methods. The present invention is not limited to these.

  As an example of the polymerizable compound (A) of the present invention, the structure of M in the general formula (A) is changed to the above (M-1) to (M-11) other than the exemplary structure (M-6). Examples [Exemplary compounds (21) to (30)] are shown, but are not limited thereto.

About these (A) specific polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design and use of a curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.

As an adhesive group to hard materials, for example, when a glass plate is used as a support, there are many silanol groups and hydroxyl groups on the glass surface, so these groups form covalent interactions. It is preferable to introduce a dialkylalkoxysilyl group, an alkyldialkoxysilyl group, a trialkoxysilyl group, an ammonium group that can form an ionic dipole interaction, a phosphonic acid that can form a multipoint hydrogen bond, or an ester group thereof. .
In order to use cellulosic materials such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, etc., adhesive groups such as ammonium groups, phosphonic acid or ester groups thereof, When a synthetic resin such as terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, or polyvinyl acetal is used as the hard material, it is preferable to select an adhesive group such as phosphonic acid or an ester group thereof.

  In addition, the addition / polymerization compound selection / compatibility with other components (for example, initiators, colorants (pigments, dyes, etc.), binder polymers, etc.) and dispersibility are also included in the curable composition. The method of use is an important factor. For example, the compatibility may be improved by the use of a low-purity compound or a combination of two or more. In addition, a specific structure other than the introduction of the adhesive group may be selected for the purpose of improving the adhesiveness with a substrate or the like.

  In the present invention, in addition to (A) the specific polymerizable compound, a general radical polymerizable compound (E) having no adhesive group as described above in the molecule is used as long as the effects of the present invention are not impaired. Can be used together. Examples of the general radical polymerizable compound having no adhesive group include those having no adhesive group in the molecule in the specific polymerizable compound (A). Moreover, you may use individually or may use 2 or more types together. Next, a general radical polymerizable compound (E) having no adhesive group will be described.

<General radical polymerizable compound (E) having no adhesive group>
As a general radical polymerizable compound (E) having no adhesive group that can be used in the present invention, a compound widely known as a compound having an ethylenically unsaturated double bond in the industrial field is not particularly limited. Can be used. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, etc. . Moreover, the EO modified body of these compounds, or PO modified body is also mentioned.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane 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-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (E) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 1)}} COOCH 2 CH (R 2) OH (E)
(However, R ¹ and R ² represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a curable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  In the present invention, when adding a general radical polymerizable compound (E) having no adhesive group, it preferably contains two or more ethylenically unsaturated bonds from the viewpoint of curing sensitivity. It is more preferable to contain. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 are commercially available products. (Manufactured by Kyoeisha) is more preferred.

  Further, from the viewpoint of the curable composition of the present invention, curing sensitivity, developability of unexposed areas, and strength of exposed areas, in addition to the specific polymerizable compound (A), a general radical polymerizable compound having no adhesive group It is preferable to contain (E) in the following ratio. (E) Mass ratio of (A) specific polymerizable compound to total mass of (A) specific polymerizable compound and other polymerizable compound having ethylenic double bond [(A) / (A) + (E) ] Is preferably 0.01 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, further preferably 0.01 or more and 0.3 or less, and 0.01 or more and 0 or less. Most preferably, it is 15 or less. When [(A) / (A) + (E)] is less than 0.1, sufficient substrate adhesion cannot be obtained.

The total mass of (E) the other polymerizable compound having an ethylenic double bond and (A) the specific polymerizable compound is preferably 1 to 90% in the solid content in the composition of the present invention. 1 to 80% is more preferable, and 1 to 70% is still more preferable.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content is preferably 5 to 50%, more preferably 7 to 40%. More preferably, it is -35%.
In addition, (B) photopolymerization initiator mass ratio [(B) / (A) + ((B) / (A) + (E) to the total mass of the polymerizable compound having an ethylenic double bond] and (A) the specific polymerizable compound. E)] is preferably 0.1 or more and 0.8 or less, more preferably 0.2 or more and 0.7 or less, and most preferably 0.3 or more and 0.6 or less.
These (A) component and (E) other radical polymerizable compounds can be arbitrarily selected in terms of the structure inhibition, inhibition of oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. Can be selected.

<(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 that is decomposed by light and initiates and accelerates the polymerization of the specific radical polymerizable compound (A), and preferably has absorption in a wavelength region of 300 to 500 nm. . Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  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, hexaaryes. Examples include rubiimidazole 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 Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

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

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include mbenzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate, and the like.

  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-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

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

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. Organoborates described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, and organic boron oxosulfonium complexes, JP-A-6-175554 No. 6, JP-A-6-175553 Organoboron iodonium complexes described in JP-A-9-188710, organoboron phosphonium complexes described in JP-A-9-348710, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (B) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  The content of the (B) photopolymerization initiator contained in the curable composition of the present invention is preferably 0.1 to 50% by mass, more preferably 0, based on the total solid content of the curable composition. 0.5 to 30% by mass, particularly preferably 1 to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(C) Colorant>
By using a colorant in the curable composition of the present invention, a colored cured body composed of the curable composition can be formed, and can be applied to the formation of a colored pattern of an image forming material or a color filter.
There is no restriction | limiting in particular in the coloring agent added by necessity to the curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. As the colorant,
From the viewpoint of durability such as heat resistance and light resistance, a pigment is preferable.

  As the pigment that can be used in the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable. Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

As the organic pigment, for example,
CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
CI Pigment Orange 36, 38, 43, 71;
CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
CI pigment violet 19, 23, 32, 39;
CI Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CI Pigment Green 7, 36, 37;
CI Pigment Brown 25, 28;
CI pigment black 1, 7;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an influence.

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

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CI Pigment Orange 36, 71,
CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
CI Pigment Violet 19, 23, 32,
CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CI Pigment Black 1

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is less than 100: 4, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. When the ratio is 100: 51 or more, the dominant wavelength becomes shorter than the short wavelength, and the deviation from the NTSC target hue may increase. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 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 pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, as the pigment for the 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, still more preferably 10 to 50 nm, from the viewpoint of color unevenness and contrast. Most preferred is ˜40 nm.

Moreover, when using the composition of this invention for color filters, it is preferable to use the dye which melt | dissolves uniformly in a composition from a viewpoint of uneven color 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 conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and / or dye in the light non-irradiated part by development.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

  The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, other in the composition. It is selected in consideration of all the required performances such as interaction with the components, light resistance and heat resistance.

Hereinafter, although the specific example of an acidic dye is given, in this invention, it is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma 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 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 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, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 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 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 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, 204, 207, 211, 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, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 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;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes mentioned above, 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;
Dyes such as Acid Green 25 and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.

  Among these, as the colorant (C), triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo A colorant selected from pyrazole azo, anilino azo, pyrazolotriazole azo, pyridone azo, and anthrapyridone is preferable.

As content in the case of using a coloring agent for the curable composition of this invention, it is preferable that it is 5-80 mass% in the total solid of a curable composition, 10-70 mass% is more preferable, 20 -70 mass% is still more preferable.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the colorant is preferably 20% by mass or more in the range of the content, and more preferably, 30% by mass or more.
When the amount of the colorant is too small, there is a tendency that an appropriate chromaticity cannot be obtained when a color filter is produced with the curable composition of the present invention. On the other hand, if the amount is too large, the photocuring does not proceed sufficiently and the strength as a film is lowered, and the development latitude during alkali development tends to be narrow.

  The curable composition of the present invention may further contain optional components described in detail below, if necessary, in addition to the components (A) and (B) described above and the component (C) added as desired. Good. Hereinafter, optional components that can be contained in the curable composition of the present invention will be described.

<(D) Dispersant>
When the curable composition of this invention contains a pigment as (C) a coloring agent, it is preferable to add (D) a dispersing agent from a viewpoint of improving the dispersibility of this pigment.

Dispersants (pigment dispersants) that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified polymers. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred 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 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  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 polymer dispersant.

As content of the dispersing agent in this invention, it is preferable that it is 1-100 mass% with respect to a pigment, 3-100 mass% is more preferable, and 5-80 mass% is still more preferable.
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment. In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

  In the present invention, when using a pigment and a dispersant as a colorant, the total content of the colorant and the dispersant is based on the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass or less, and further 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 photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.
Further, European Patent No. 568,993, US Patent No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11- And the compounds described in Japanese Patent No. 271969.

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

(In Formula (I), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents the basic nucleus of the dye in combination with the adjacent A ² and the adjacent carbon atom. Represents a non-metallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. 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 are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (XIV).)

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

(In 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 represents a substituted or unsubstituted alkyl group, substituted Or an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye together with adjacent A ³ , A ⁴ and an adjacent carbon atom; ⁶⁰ and R ⁶¹ are each independently a monovalent non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.)

(In the formula (V), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ may be bonded together to form an aliphatic or aromatic ring, respectively. it can.)

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

A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the sensitizer in the curable composition of the present invention is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency, and is 0. More preferably, the content is 5 to 15% by mass.

<(G) Binder polymer>
In the curable composition of the present invention, a binder polymer can be further used as necessary for the purpose of improving the film properties. It is preferable to use a linear organic polymer as the binder. As such a “linear organic polymer”, a known one 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 water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (13).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(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, α-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-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups as described in JP 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer that can be used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more. More preferably, it is the range of 2,000-250,000. 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 any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used in synthesizing the binder polymer that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.

<(H) Co-sensitizer>
The curable composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. Preferably, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

<(I) Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
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-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  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, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Other additives>
Furthermore, in the present invention, a known additive such as an inorganic filler, a plasticizer, or a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added to improve the physical properties of the cured film. Good.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

  The curable composition of the present invention is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to hard material surfaces, such as a board | substrate which applies a curable composition, is shown. Accordingly, the curable composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, inks, paints, adhesives, and coating agents.

[Color filter and manufacturing method thereof]
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed 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 its manufacturing method (color filter manufacturing method of the present invention).

A step of applying the curable composition of the present invention on a support to form a curable composition layer (hereinafter abbreviated as “curable composition layer forming step” as appropriate), and the curable composition. A step of exposing the layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and a step of developing the curable composition layer after exposure to form a colored pattern (hereinafter referred to as “development step” as appropriate). Abbreviated as “.”).
Hereafter, each process in the manufacturing method of this invention is demonstrated.

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

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, an image sensor, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

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

  As a coating film thickness of a curable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is further more preferable.

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

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed through a mask having a predetermined mask pattern.
In this step, the pattern of the coating film is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, developed with a developer, and each color (three colors or four colors). This can be done by forming a pattern-like film consisting of these pixels. As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.
If the color filter of the present invention is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is for a solid-state imaging device, more preferably 30~1500mJ / cm ² is preferably 50~1000mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

<Development process>
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4, 0] -7-undecene and the like, and an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Is preferably used as a developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried, followed by heat treatment (post-bake). Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured.
Thereby, a color filter is obtained.
The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicon substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  In the production method of the present invention, after performing the above-described curable composition layer forming step, exposure step, and development step, if necessary, the formed colored pattern is cured by heating and / or exposure. A process may be included.

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

  The application of the curable composition of the present invention has been described mainly with respect to the application to the pixels of the color filter, but it goes without saying that it can also be applied to a black matrix provided between the pixels of the color filter. The black matrix is patterned exposure and alkaline development in the same manner as the above pixel manufacturing method 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. Further, after that, post-baking can be performed to promote the curing of the film.

  Since the color filter of the present invention uses the curable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance. It is possible to form a high-resolution pattern that is excellent in exposure sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.
Below, the specific synthesis | combining method of the said exemplary compound (1) is shown. Other (A) specific polymerizable compounds that can be used in the present invention can also be synthesized by the same scheme. The synthesis method is not limited to the following method.

[Synthesis Example 1]: Synthesis of Exemplary Compound (1) After adding 20 ml of acetonitrile to 12 g (0.023 mol) of dipentaerythritol pentaacrylate and dissolving, 0.16 g (0 of bismuth tris (2-ethylhexanoate) .25 mmol) and 5.9 g (0.23 mol) of triethoxy (3-isocyanatopropyl) silane were added and stirred at 55 to 65 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, then added with 50 ml of n-hexane and washed three times, and the lower layer was separated. The solvent was distilled off to obtain 17 g (0.022 mol (yield: 95%)) of compound (1).

  The structure of the compound (1) obtained above was confirmed by NMR. 1H-NMR (400 MHz, solvent: deuterated chloroform, standard substance: tetramethylsilane) δ 6.40 (5H, dd), 6.10 ppm (5H, 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) 3.81 ppm (6H, q), 3.48 ppm (2H, s), 3.45 ppm (2H, s), 3.15 ppm (2H, m), 1.62 ppm (2H, m), 1.23 ppm ( 9H, t) and 0.63 ppm (2H, m).

Examples The curable composition of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
Example 1
[1. Preparation of curable composition]
Here, an example in which a curable composition containing a colorant (pigment) is prepared for forming a color filter for use in a liquid crystal display element will be described.
1-1. First, the following components were kneaded and dispersed with two rolls.
・ C. I. Pigment Red 254 22 parts by mass I. Pigment Yellow 139 8 parts by mass Resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10,
Mw: 10,000, solvent: propylene glycol methyl ether acetate 60%, resin solid content concentration: 40%) 40 parts by mass-solvent: propylene glycol methyl ether acetate 20 parts by mass-dispersant: (trade name: BY-161, BYK) 2 parts by mass

Furthermore, the following components were added to the dispersion obtained above and finely dispersed in a sand mill for a whole day and night.
・ 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, followed by stirring and mixing to prepare a curable composition solution.
-Exemplified compound (1) [(A) specific polymerizable compound] 12 parts by mass-4-Benzoxolane-2,6-di (trichloromethyl)-
s-Triazine [(B) photopolymerization initiator] 0.5 parts by mass Surfactant (trade name: Tetranic 150R1, BASF) 0.2 parts by mass Solvent: PGMEA 100 parts by mass

[2. (Production of color filter)
2-1. Formation of the curable composition layer The curable composition containing the pigment as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and pre-baking ( prebake) (100 ° C., 80 seconds) to form a curable composition coating film (curable composition layer).
(Slit application conditions)
Gap at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure and development Thereafter, the photocurable coating film is exposed in a pattern using a test mask with a line width of 20 μm using a 2.5 kw ultra high pressure mercury lamp, and after the exposure, the entire surface of the coating film is organically developed. The sample was covered with a 10% aqueous solution (trade name: CD, manufactured by Fuji Film Arch Co., Ltd.) and left stationary for 60 seconds.

2-3. Heat treatment After standing still, pure water was sprayed in a shower to wash away the developer, and the coating film subjected to the photocuring treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, a colored resin film (color filter) was formed on the glass substrate.

[3. (Performance evaluation)
Storage stability of the colored curable composition coating solution prepared above, exposure sensitivity of the curable composition coating film (colored layer) formed on the glass substrate using the colored curable composition, and substrate adhesion Property, developability, and pattern cross-sectional shape were evaluated as follows. The results are shown in Table 1.

3-1. Storage stability of coating solution After the coating solution was stored at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
<Criteria>
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

3-2. Exposure sensitivity of coating film (colored layer),
Exposure was performed by changing the exposure dose to various exposure doses of 10 to 100 mJ / cm ² , and the exposure dose at which the pattern line width after post-baking was 20 μm was evaluated as exposure sensitivity. A smaller exposure sensitivity value indicates higher 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 method by optical microscope and SEM photograph observation.
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
<Developability>
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred.
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. These evaluation items were evaluated based on the following criteria <Board adhesion>
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

[Examples 2 to 9]
In the curable composition of Example 1, (A) Except having replaced the exemplary compound (1) which is a specific polymerizable compound with the exemplary compound shown in Table 1 below, the same procedure as in Example 1 was followed. And the same evaluation as in Example 1 was performed. The results are shown in Table 1.
Example 10
In the curable composition of Example 1, (A) Exemplified compound (1) which is a specific polymerizable compound is replaced with the exemplified compound shown in Table 1 below, and the substrate is a polyethylene terephthalate substrate having the same size as the glass substrate. (It is described as “PET substrate” in the table), and the post-baking process was changed to an irradiation process of 10000 mJ / cm ² with a high-pressure mercury lamp. Evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Comparative Example 1]
In the curable composition of Example 1, (A) Exemplified compound (1) which is a specific polymerizable compound was replaced with the comparative polymerizable compound shown in Table 1 below, and all the procedures were performed in the same manner as in Example 1. . The results are shown in Table 1.
[Comparative Example 2]
In the curable composition of Example 1, (A) Exemplified compound (1), which is a specific polymerizable compound, was replaced with the exemplified compound shown in Table 1 below, and a glass substrate was used as the substrate, and the same size polyethylene terephthalate A colored pattern was obtained in the same manner as in Example 1 except that the substrate was changed and the post-baking step was changed to an irradiation step of 10000 mJ / cm ² with a high-pressure mercury lamp, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

  From the results in Table 1, the colored curable compositions of the examples using the curable composition of the present invention are excellent in storage stability in the solution state, and when an image is formed on a support, it is out of the scope of the present invention. It turns out that it is excellent in all of developability, board | substrate adhesiveness, and pattern cross-sectional shape with respect to the comparative example using a polyfunctional acrylate type comparative polymeric compound. It can also be seen that the double bond density in the vicinity of the substrate and the adhesion to the substrate are improved, so that 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 use in a solid-state imaging device will be described.
(Example 11)
[1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
<composition>
Propylene glycol monomethyl ether acetate ... 19.20 parts (PGMEA: solvent)
-Ethyl lactate ... 36.67 parts-Binder polymer ... 30.51 parts [Benzyl methacrylate / methacrylic acid / methacrylic acid-2-
40% PGMEA solution of hydroxyethyl copolymer (molar ratio = 60/22/18)]
Dipentaerythritol hexaacrylate 12.20 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol): 0.0061 part ・ Fluorosurfactant: 0.83 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator: 0.586 parts (TAZ-107 (trihalomethyltriazine-based photopolymerization initiator),
(Midori Chemical Co., Ltd.)

[2. Production of silicon substrate with undercoat layer]
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

[3. Preparation of colorant-containing curable composition (dye system)]
A compound of the following composition 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 has no adhesive group General radical polymerizable compound (E): 5.0 parts ・ Exemplary compound (1) [(A) specific polymerizable compound]: 2.0 parts ・ Photopolymerization initiator (B): 2.5 parts ( CGI-124, manufactured by Ciba Specialty Chemicals;
Oxime-based photopolymerization initiator)
Glycerol propoxylate: 0.5 part (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0, colorless compound)

[5. Preparation and evaluation of color filter using colored photosensitive resin composition]
-Pattern formation and sensitivity evaluation-
3 above. The colorant-containing curable composition A-1 prepared in the above 2. The curable composition layer (coating film) was formed by coating on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1). Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.9 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon, Inc.), exposure was performed at various exposure doses of 100 to 1600 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  A silicon wafer substrate on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the center of rotation to the shower nozzle to perform a rinsing treatment, and then spray-dried. Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure amount at which the pattern line width was 2 μm was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. The results of measurement evaluation are shown in Table 2 below.

In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
<Developability>
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is preferably rectangular, and reverse taper is not preferable.
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. These evaluation items were evaluated based on the following criteria <Board adhesion>
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

(Examples 12 to 15)
[3. A colored pattern was obtained in the same manner as in Example 11 except that Exemplified Compound (1) used in Preparation of Colorant-Containing Curable Composition] was replaced with the compound shown in Table 2 below. The same evaluation was performed. The results are shown in Table 2.
[Comparative Example 3]
[3. The same procedure as in Example 11 was conducted except that the exemplified compound (1) used in the preparation of the colorant-containing curable composition] was replaced with the comparative polymerizable compound shown in Table 2 below. The results are shown in Table 2.

(Example 16)
1. Preparation of curable composition for color filter (pigment type) for solid-state imaging device 1-1. First, the following components were kneaded and dispersed with two rolls.
・ C. I. Pigment Red 254 22 parts by mass I. Pigment Yellow 139 8 parts by mass Resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10,
Mw: 10,000, solvent: propylene glycol methyl ether acetate 60%, resin solid content concentration: 40%) 40 parts by mass-solvent: propylene glycol methyl ether acetate 20 parts by mass-dispersant: (trade name: BY-161, BYK) 2 parts by mass

Furthermore, the following components were added to the dispersion obtained above and finely dispersed in a sand mill for a whole day and night.
・ 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, followed by stirring and mixing to prepare a curable composition solution.
-Exemplified compound (1) [(A) specific polymerizable compound] 12 parts by mass-4-Benzoxolane-2,6-di (trichloromethyl)-
s-Triazine [(B) photopolymerization initiator] 0.5 parts by mass Surfactant (trade name: Tetranic 150R1, BASF) 0.2 parts by mass Solvent: PGMEA 100 parts by mass

Coating / exposure / development and performance evaluation carried out in Example 11 of the curable composition described in the section “Preparation of curable composition for color filter (dye system) for use in solid-state imaging device” using the coating solution Carried out. The results are summarized in Table 2.
[Comparative Example 4]
[1-2. All were performed in the same manner as in Example 16 except that the exemplified compound (1) used in Preparation of curable composition (coating liquid) was changed as shown in Table 2 below. The results are summarized in Table 2.

From the results of Table 2, the colored curable compositions of the examples using the curable composition of the present invention are similar to the case where the pigment is used as the colorant even when the dye is used as the colorant. The solution was excellent in storage stability.
In addition, even when an image is formed on a support, any one of developability, substrate adhesion, and pattern cross-sectional shape can be used as compared with a comparative example using only a polyfunctional acrylate-based comparative polymerizable compound outside the scope of the present invention. It turns out that it is excellent. Furthermore, it can be seen from these results that the double bond density in the vicinity of the substrate and the substrate adhesion were improved, so that erosion by the developer was suppressed, and as a result, the exposure sensitivity was improved.

Claims (7)

  A curable composition comprising (A) a radically polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to a hard material in the molecule, and (B) a photopolymerization initiator. .   The adhesive group to the hard material in the radical polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to the hard material in the molecule (A) is an acid group, an ester group of an acid, an acid onium salt, 2. The curable composition according to claim 1, which is at least one selected from the group consisting of acid metal salts, substituents that generate silanol groups by hydrolysis, onium groups, phenolic hydroxyl groups, zwitterionic groups, and chelating groups. object.   The hard material is a glass substrate or a silicon substrate, and (A) the radically polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to the hard material in the molecule has an adhesive group to the hard material. The curable composition according to claim 1, which is a substituent that generates a silanol group by hydrolysis.   The (A) radically polymerizable compound having an ethylenically unsaturated double bond and an adhesive group to a hard material in the molecule has a plurality of ethylenically unsaturated double bonds in the molecule. The curable composition according to any one of claims 1 to 3.   The curable composition according to any one of claims 1 to 4, further comprising (C) a colorant having a maximum absorption in a visible wavelength region of 400 nm to 700 nm.   A color filter comprising a colored pattern formed by using the curable composition according to claim 5 on a support.   A step of forming a colored curable composition layer by applying the curable composition according to claim 5 on a support, a step of exposing the curable composition layer through a mask, and a post-exposure step And a step of developing the curable composition layer to form a colored pattern.