JP2008096680A - Curable composition for color filter, color filter and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for color filters having high sensitivity, good pattern forming property and excellent adhesion to a substrate even when a colorant is contained at high concentration, and to provide a color filter and a method for manufacturing the same. <P>SOLUTION: The curable composition for color filters contains at least one of the sulfonium salts represented by general formulae (1) and (2), a photopolymerizable compound and a colorant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition for a color filter used for a liquid crystal display element (LCD), a solid-state image sensor (CCD, CMOS, etc.), a color filter, and a method for producing the same.

A color filter is an indispensable component for a liquid crystal display.
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.

Liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor applications. That is, improvement in contrast and color purity. In order to improve contrast, a curable composition for producing a color filter is required to have a finer particle size of a colorant (organic pigment or the like) to be used.
Further, in order to improve color purity, a higher content of the colorant (organic pigment) in the solid content of the curable composition for producing a color filter is required.

On the other hand, in the color filter for a solid-state image sensor, further higher definition is desired. However, in the curable composition to which the conventional pigment dispersion system is applied, there are problems such as color unevenness because the pigment is relatively coarse particles, and it is difficult to further improve the resolution. It was not suitable for applications requiring a fine pattern such as a solid-state imaging device. Therefore, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 1).
In addition, for color filters for solid-state imaging devices, there is a demand for thin color patterns, and in order to make thin films with the same color density as before, the use of colorants in curable compositions for color filter production It is required to increase the content rate.

As described above, in both cases for liquid crystal displays and solid-state imaging devices, the curable composition for producing a color filter contains a colorant, and thus is a component necessary for curing the curable composition. The content of a certain photopolymerization initiator and photopolymerizable compound is limited, resulting in insufficient strength, or insufficient curability and insufficient adhesion to a hard surface serving as a substrate. There were problems such as.
Furthermore, in recent years, with an increase in substrate size, there is a demand for a highly sensitive curable composition that maintains a pattern shape for a long time even in a developing solution in a developing process and does not have any chipping or peeling in the pattern.

Regarding a curable composition for producing a color filter, when the composition is applied onto a substrate and exposed and cured, a photopolymerization initiator having a higher sensitivity that can sufficiently achieve a curing reaction even near the bottom of the coating film. Development is being attempted.
Conventionally, as a curable composition for producing a color filter, for example, a radiation-sensitive composition in which a binder polymer containing a carboxyl group, a polyfunctional acrylate such as pentaerythritol hexaacrylate, and a photopolymerization initiator are combined. 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole as a highly sensitive photopolymerization initiator in such a radiation-sensitive composition, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like have been proposed (see, for example, Patent Documents 2 and 3).

  In addition, as a photopolymerization initiator applicable to the curable composition, 2,2′-bis (2-chlorophenyl) is used as a photopolymerization initiator applicable to a radiation-sensitive composition used for a printing plate or a photoresist. ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- Tetra (trialkoxyphenyl) biimidazole and the like have been proposed (see, for example, Patent Documents 4 and 5).

However, the sensitivity of any of the above curable compositions is not yet satisfactory, and it is necessary to irradiate with high energy radiation when curing. When a colored pattern of a color filter is formed using such a curable composition, if the irradiation amount is insufficient, problems such as missing or missing patterns, a remaining film rate or a decrease in pixel strength, etc. are caused. In the coloring pattern of the obtained color filter, there arises a problem that the resolution and the adhesion between the support and the support are lowered.
As described above, even when the colorant is contained at a high concentration, the curable composition for color filters that cures with high sensitivity and has good pattern forming properties, and the adhesion between the resolution and the support. Although a color filter having an excellent coloring pattern is desired, it has not yet been provided.
JP-A-2-127602 JP-A-6-75372 JP-A-6-75373, etc. Japanese Patent Publication No. 48-38403 JP-A-62-174204

The present invention has been made in view of the above-described problems, and an object thereof is to achieve the following objects.
That is, the object of the present invention is to cure with high sensitivity, have good pattern forming properties, and excellent adhesion to a hard surface as a substrate even when the colorant is contained in a high concentration. The object is to provide a curable composition for a color filter.
Another object of the present invention is to provide a color filter having a color pattern that is formed using the curable composition for a color filter and has excellent resolving power and adhesion to a support, and a high color filter. An object of the present invention is to provide a manufacturing method that can be manufactured with productivity.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by a curable composition for a color filter containing a specific compound, and have completed the present invention. That is, the means for solving the above problems are as follows.

<1> (A) at least one selected from a sulfonium salt represented by the following general formula (I) and a sulfonium salt represented by the following general formula (II); (B) a photopolymerizable compound; (C) A curable composition for color filters, comprising a colorant.

In the general formula (I), R ¹ , R ² , and R ³ each independently represent a substituent, at least one of R ¹ , R ² , and R ³ represents an electron-withdrawing group, and a1 is 0 Represents an integer of ˜5, a2 and a3 each independently represent an integer of 1 to 5, and (X ¹ ) ⁻ represents an anion. When a1, a2, or a3 represents an integer of 2 or more, a plurality of R ¹ , R ² , or R ³ may be the same or different.
In general formula (II), R ⁴ , R ⁵ , and R ⁶ each independently represent a substituent, at least one of R ⁴ , R ⁵ , and R ⁶ represents an electron-withdrawing group; 5 represents an integer of 5, a5 and a6 each independently represent an integer of 0 to 4, and all of a4 to a6 do not represent 0. (X ¹ ) ⁻ represents an anion. When a4, a5, or a6 represents an integer of 2 or more, a plurality of R ⁴ , R ⁵ , or R ⁶ may be the same or different.

<2> The curable composition for a color filter according to <1>, wherein the sum of Hammett values of the electron-withdrawing groups of the sulfonium salt is 0.46 or more and 4.0 or less.
<3> The curable composition for color filters according to <1> or <2>, wherein the electron-withdrawing group is a halogen atom or a group containing a halogen atom.
<4> A color filter having a colored pattern formed using the curable composition for a color filter according to any one of <1> to <3> on a support.
<5> A step of forming a colored curable composition layer by applying the curable composition for a color filter according to any one of <1> to <3> on a support, and the colored curable composition A method for producing a color filter, comprising: exposing a composition layer through a mask; and developing the colored curable composition layer after exposure to form a colored pattern.

According to the present invention, even when the colorant is contained in a high concentration, the color filter is cured with high sensitivity, has a good pattern forming property, and has excellent adhesion to a hard surface as a substrate. A curable composition can be provided.
In addition, according to the present invention, a color filter that is formed by using the curable composition for a color filter and has a coloring pattern excellent in resolving power and adhesion to a support, and high productivity of the color filter. The manufacturing method which can be manufactured with can be provided.

  Hereinafter, the curable composition for color filters of the present invention, the color filter formed using the curable composition for color filters, and the production method thereof will be described in detail.

<Curable composition for color filter>
The curable composition for a color filter of the present invention includes (A) at least one selected from a sulfonium salt represented by the following general formula (I) and a sulfonium salt represented by the following general formula (II): (B) A photopolymerizable compound and (C) a colorant are contained.

In the general formula (I), R ¹ , R ² , and R ³ each independently represent a substituent, at least one of R ¹ , R ² , and R ³ represents an electron-withdrawing group, and a1 is 0 Represents an integer of ˜5, a2 and a3 each independently represent an integer of 1 to 5, and (X ¹ ) ⁻ represents an anion. When a1, a2, or a3 represents an integer of 2 or more, a plurality of R ¹ , R ² , or R ³ may be the same or different.
In general formula (II), R ⁴ , R ⁵ , and R ⁶ each independently represent a substituent, at least one of R ⁴ , R ⁵ , and R ⁶ represents an electron-withdrawing group; 5 represents an integer of 5, a5 and a6 each independently represent an integer of 0 to 4, and all of a4 to a6 do not represent 0. (X ¹ ) ⁻ represents an anion. When a4, a5, or a6 represents an integer of 2 or more, a plurality of R ⁴ , R ⁵ , or R ⁶ may be the same or different.

  Hereinafter, each component contained in the curable composition for a color filter of the present invention (hereinafter, appropriately referred to as “specific curable composition”) will be sequentially described.

((A) at least one selected from sulfonium salts represented by general formula (I) and sulfonium salts represented by general formula (II))
The specific curable composition comprises a sulfonium salt represented by the following general formula (I) (hereinafter referred to as “specific polymerization initiator-I” as appropriate) and a sulfonium salt represented by the following general formula (II) ( In the following, the specific polymerization initiator-I and the specific polymerization initiator-II will be described in detail.
[Sulfonium salt represented by general formula (I)]
The specific polymerization initiator-I is a polymerization initiator having a triarylsulfonium salt structure represented by the following general formula (I), and the structure has one or more aryl skeletons having an electron-withdrawing group.

In the general formula (I), R ¹ , R ² , and R ³ each independently represent a substituent, at least one of R ¹ , R ² , and R ³ represents an electron-withdrawing group, and a1 is 0 Represents an integer of ˜5, a2 and a3 each independently represent an integer of 1 to 5, and (X ¹ ) ⁻ represents an anion. When a1, a2, or a3 represents an integer of 2 or more, a plurality of R ¹ , R ² , or R ³ may be the same or different.

Here, the electron-withdrawing group means a substituent having a Hammett value (Hammet substituent constant σ) larger than 0. The total Hammett value of R ¹ , R ² , or R ³ that is a substituent bonded to the aryl skeleton is preferably 0.18 or more, more preferably 0.46 or more, from the viewpoint of increasing sensitivity. 0.60 or more is more preferable.
Further, the Hammett value represents the degree of electron withdrawing property of the cation of the specific polymerization initiator-I, and there is no particular upper limit from the viewpoint of increasing sensitivity, but the viewpoint of reactivity and stability. Therefore, the sum of the Hammett values of R ¹ , R ² , and R ³ that are substituents bonded to the aryl skeleton is preferably in the range of 0.46 to 4.0, and preferably 0.50 to 3.5. The following range is more preferable, and the range of 0.60 to 3.0 is particularly preferable.

  Here, Hammett's substituent constant represented by the Hammett value will be described. Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo), edited by Naoki Inamoto, Chemistry seminar 10 Hammett's rule-structure and reactivity-(1983, published by Maruzen Co., Ltd.).

In addition, the Hammett value does not mean that it can be found in the above-mentioned book, but is limited only to a substituent having a known value in the literature, and when the value is unknown based on Hammett's law Of course, it also includes substituents that would be included within the scope. The Hammett values in the present invention are as follows: Naoki Inamoto, Chemistry Seminar 10 Hammett's Law-Structure and Reactivity-(1983, published by Maruzen Co., Ltd.), Chemical Society of Japan, Chemistry Handbook, Basic Revised 5th Edition ( (2004, issued by Maruzen Co., Ltd.)).
Below, the substituent which the sulfonium salt represented by general formula (I) has is explained in full detail.

In the general formula (I), R ¹ , R ² and R ³ each independently represent a substituent, and at least one of R ¹ , R ² and R ³ is. Examples of the electron withdrawing group include a trifluoromethyl group, a halogen atom, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxyl group, and a carbonyl group. The Hammett values of these electron withdrawing groups are shown below. A trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), a halogen atom [eg, —F (m: 0.34, p: 0.06), —Cl (m: 0. 37, p: 0.23), -Br (m: 0.39, p: 0.23), -I (m: 0.35, p: 0.18)], an ester group (for example, -COCH ₃ , O: 0.37, p: 0.45), sulfoxide group (for example, —SOCH ₃ , m: 0.52, p: 0.45), cyano group (—CN, m: 0.56, p: 0.66), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxy group (—COOH, m: 0.37, p: 0.45), a carbonyl group (— CHO, m: 0.36, p: (043)) and the like. The parentheses indicate the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett when the substituent is introduced at the meta position (m position). Indicates that the value is 0.50.
Among these substituents, nonionic substituents such as halogen atoms and halogenated alkyl groups are preferred from the viewpoint of improving thermal stability or solubility in polymerizable compounds, and from the viewpoint of improving solubility. Is more preferably —F, —CF ₃ , —Cl, or —Br, and —Cl is particularly preferable from the viewpoint of reactivity.

The substituent may be introduced into any one of the aryl skeletons in the general formula (I), or may be introduced into two or more aryl skeletons in the general formula (I). Moreover, when a1, a2, or a3 in general formula (I) represents an integer of 2 or more, a plurality of R ¹ , R ² , or R ³ may be the same or different. The number of substituents that can be introduced into the specific polymerization initiator-I is arbitrary. For example, only one substituent having a particularly large Hammett value (for example, a Hammett value of 0.46 or more alone) may be introduced into one position of the aryl skeleton having a triarylsulfonium salt structure. Further, for example, a plurality of substituents may be introduced and the sum of the Hammett values may be 0.46 or more.
In addition, since the Hammett value of the substituent varies depending on the position of introduction, the sum of Hammett values of the specific polymerization initiator-I in the present invention is determined by the type of substituent, the introduction position, and the number of introductions. Become. In the present invention, as an index of the electron-withdrawing group, the substituent effect at the o-position is calculated as the same value as the p-position. The substitution position of the substituent of the specific polymerization initiator-I in the present invention is preferably m-position and p-position, and most preferably p-position, from the viewpoint of synthesis.

The specific polymerization initiator-I in the present invention is preferably a sulfonium salt having three or more substitutions by a halogen atom, and each aryl skeleton is a sulfonium salt having a halogen atom or a group containing a halogen atom as a substituent. More preferred is a sulfonium salt in which each aryl skeleton is substituted with a halogen atom, and especially preferred is tri-substituted with a chloro group.
Specifically, each of the three aryl skeletons preferably has a halogen atom substituted, more preferably has a triarylsulfonium salt structure in which a chloro group is introduced into each of the three aryl skeletons. Particularly preferred are those in which each of the aryl skeletons has a chloro group substituted in the p-position.

The specific polymerization initiator-I is preferably composed of a cation having a triarylsulfonium salt structure and an anion represented by (X ¹ ) ⁻ and is electrically neutral.
Examples of the anion represented by (X ¹ ) ⁻ include a polymer type anion from the viewpoint of stability. For example, sulfonate anion (for example, alkyl sulfonate anion, aryl sulfonate anion), benzoyl formate anion, PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , carboxylate anion (for example, alkyl carboxylate anion, Aryl carboxylate anion, aralkyl carboxylate anion), sulfinate anion, sulfate anion, borate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methyl anion, halogen anion, polymer sulfonate anion , Polymer type carboxylate anion, and tetraarylborate anion.
Among these, non-nucleophilic anions are preferable. The non-nucleophilic anion is an anion having an extremely low ability to develop a nucleophilic reaction, and is an anion capable of suppressing degradation with time due to intramolecular nucleophilic reaction.
Preferred examples of the non-nucleophilic anion include PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methyl anion, and tetraarylborate anion. Can be mentioned.

  In the present invention, the sulfonium salt having a cation represented by the general formula (I) may have a plurality of triarylsulfonium salt structures as counter cations in the polymer type anion.

  The alkyl moiety in the alkyl sulfonate anion may be an alkyl group or a cycloalkyl group, and preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms, such as a methyl group or an ethyl group. Group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group and the like.

  The aryl group in the aryl sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

  Examples of the substituent of the alkyl group, cycloalkyl group and aryl group in the alkylsulfonate anion and arylsulfonate anion include, for example, a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, Hydroxyl group, amino group, cyano group, alkoxy group (preferably 1 to 5 carbon atoms), cycloalkyl group (preferably 3 to 15 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably May include 2 to 7 carbon atoms, an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  Examples of the alkyl moiety in the alkylcarboxylate anion include the same alkyl group and cycloalkyl group as in the alkylsulfonate anion. Examples of the aryl group in the arylcarboxylate anion include the same aryl groups as in the arylsulfonate anion. The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and the like.

  Examples of the alkyl group, cycloalkyl group, aryl group and aralkyl group substituent in the alkylcarboxylate anion, arylcarboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom, alkyl group as in the arylsulfonate anion, A cycloalkyl group, an alkoxy group, an alkylthio group, etc. can be mentioned.

Examples of the sulfonylimide anion include saccharin anion.
The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. Examples of the substituent for these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, and an alkylthio group.
Examples of the borate anion include B (n—C ₄ H ₉ ) (C ₆ H ₅ ) ₃ ^— .
The tetraarylborate anion, for ^{_{example, B (C 6 F 5)}} 4 -, B (C 6 H 5) 4 -, B (C 6 H 4 CF 3) 4 - and the like.

The cation in the anionic, high sensitivity, which is the effect of the present invention, good patterning property, and on achieving the high adhesion to a hard surface which is a base material, a preferable combination, as the cation, R ¹ is Represents a halogen atom, R ² represents a halogen atom, R ³ represents a halogen atom, a1 is 0 to 2, a2 is 1 to 2, a3 is 1 to 2, an anion is PF _{6 ^{-, B (C 6 F 5}} ) 4 -, and the like to be a perfluoroalkyl sulfonic acid.
Further, when the anion is a divalent or higher anion, it can have two or more cations.

  Specific preferred examples of specific polymerization initiator-I in the present invention (Exemplary compounds (A-1) to (O-3), (P-1) to (P-17), (Q-1) to (Q V-16), but not limited to these, Exemplified compounds (P-1) to (P-17) are examples of compounds having a polymer type anion.

The method for synthesizing the specific polymerization initiator-I in the present invention is described, for example, in J. Org. Amer. Chem. Soc. 112 (16), 1990; 6004-6015, J.A. Org. Chem. 1988; It can be easily synthesized by the methods described in 5571-5573, WO02 / 081439A1 pamphlet, or European Patent (EP) No. 1113005.
Hereinafter, a synthesis example of the specific example will be described in detail.

[Synthesis Example 1: Synthesis of Exemplified Compound (B-4)]
1. Synthesis of tris (4-chlorophenyl) sulfonium bromide In a nitrogen atmosphere, 16.3 g (0.06 mol) of di (4-chlorophenyl) sulfoxide was dissolved in 250 ml of dichloromethane, and 10.8 g (0.10 mol) of trimethylchlorosilane at 0 to 5 ° C. ) And stirred at 0 ° C. for 30 minutes, while the reaction vessel was cooled with 0-10 ° C. ice water, the Grignard reagent tetrahydrofuran (THF) prepared in a conventional manner from 4-bromochlorobenzene (0.18 mol). 200 g of the solution was added dropwise over 30 minutes. After stirring at 0-10 ° C. for 1 hour and at room temperature for 1 hour, the reaction solution was slowly poured into a 12% aqueous solution of hydrogen bromide and an aqueous solution containing ice, extracted with 250 ml of dichloromethane, and dried over sodium sulfate. Went.
Remove the solvent, add 100 ml of methanol and stir for 30 minutes to precipitate a solid. The solid was removed by filtration and the filtrate was concentrated, further washed twice with 100 ml of ethyl acetate, solidified in ethyl acetate under reflux, and 12.0 g (44%) of a white solid (tris (4-chlorophenyl) sulfonium bromide). )
2. Synthesis of Exemplary Compound (B-4) In an aqueous solution in which 4.95 g of hexafluorophosphate potassium salt was dissolved in 100 ml of distilled water, 10.0 g of tris (4-chlorophenyl) sulfonium bromide obtained as described above was added to 50 ml of methanol. Charge the dissolved solution and stir for 1 hour. The precipitated crystals are filtered and vacuum dried at 40 ° C. for 6 hours to obtain 8.65 g (yield 70.2%) of a solid. When the structure of this solid was confirmed by NMR, it was confirmed to be the exemplified compound (B-4).

[Synthesis Example 2: Synthesis of Exemplary Compound (B-31)]
Exemplified compound in the same manner as Exemplified compound (B-4) except that tetrakis (pentafluorophenylborate) potassium salt was used instead of hexafluorophosphate potassium salt in the synthesis of exemplified compound (B-4). (B-31) was obtained. When the structure of this solid was confirmed by NMR, it was confirmed to be the exemplified compound (B-31).

[Synthesis Example 3: Synthesis of Exemplary Compound (B-32)]
Except for using tetrakis [3,5-bis (trifluoromethyl) phenyl] borate sodium salt instead of hexafluorophosphate potassium salt in the synthesis of the exemplary compound (B-4), the exemplary compound (B- Exemplified compound (B-32) was obtained in the same manner as 4). When the structure of this solid was confirmed by NMR, it was confirmed to be the exemplified compound (B-32).

[Synthesis Example 4: Synthesis of Exemplary Compound (I-2)]
Exemplified compound (B-4) was synthesized in the same manner as exemplified compound (B-4) except that di (4-trifluoromethylphenyl) was used instead of di (4-chlorophenyl) sulfoxide in the synthesis of compound (B-4). I-2) was obtained. When the structure of this solid was confirmed by NMR, it was confirmed to be Exemplified Compound (I-2).

[Synthesis Example 5: Synthesis of Exemplary Compound (B-17)]
A solution prepared by dissolving 4.46 g of tris (4-chlorophenyl) sulfonium bromide in 50 ml of dichloromethane is added to an aqueous solution obtained by dissolving 4.60 g of 2-naphthalenesulfonic acid sodium salt in 100 ml of distilled water, followed by stirring for 1 hour. The organic layer is extracted and the organic layer is washed with 100 ml of water. After drying the organic layer with sodium sulfate, the organic layer is concentrated, and 100 ml of ethyl acetate is added to the concentrated organic layer and stirred for 30 minutes under reflux. After cooling, the mixture was filtered while washing with ethyl acetate, and vacuum dried at 40 ° C. for 6 hours to obtain 5.07 g (yield 88%) of a solid containing 5.7% by mass of ethyl acetate. When the structure of this solid was confirmed by NMR, it was confirmed to be the exemplified compound (B-17).

[Synthesis Example 6: Synthesis of Exemplified Compound (Q-4)]
In the synthesis of the exemplary compound (B-4), the synthesis was performed in the same manner as the exemplary compound (B-4) except that 1-bromo-3,5-dichlorobenzene was used instead of 4-bromochlorobenzene. . When the structure of the obtained solid was confirmed by NMR, it was confirmed to be the exemplified compound (Q-4).

[Synthesis Example 7: Synthesis of Exemplified Compound (R-4)]
In the synthesis of the exemplary compound (B-4), the synthesis was performed in the same manner as the exemplary compound (B-4) except that 1-bromo-3,5-bistrifluoromethylbenzene was used instead of 4-bromochlorobenzene. went. When the structure of the obtained solid was confirmed by NMR, it was confirmed to be the exemplified compound (R-4).

  The specific synthesis examples 1 to 7 of the specific polymerization initiator-I have been described above, but other specific polymerization initiators other than those listed above can be synthesized in the same manner as described above.

[Sulfonium salt represented by general formula (II)]
The specific polymerization initiator-II is a polymerization initiator having a structure represented by the following general formula (II), and the structure has one or more aryl skeletons each having an electron-withdrawing group as a substituent.

In general formula (II), R ⁴ , R ⁵ , and R ⁶ each independently represent a substituent, at least one of R ⁴ , R ⁵ , and R ⁶ represents an electron-withdrawing group; 5 represents an integer of 5, a5 and a6 each independently represent an integer of 0 to 4, and all of a4 to a6 do not represent 0. (X ¹ ) ⁻ represents an anion. When a4, a5, or a6 represents an integer of 2 or more, a plurality of R ⁴ , R ⁵ , or R ⁶ may be the same or different.

The anion (anion) represented by R ⁴ , R ⁵ , R ⁶ , and (X ¹ ) ⁻ in the specific polymerization initiator-II is R ¹ , R ² , R in the specific polymerization initiator-I. ³ and (X ¹ ) ⁻ are the same as the anion represented by ( ⁻ ), and each preferred embodiment, the substitution position of the electron-withdrawing group, the number, the Hammett value, and the anion also represent the same embodiment.

In the cation represented by the structure having R ⁴ , R ⁵ and R ⁶ in the general formula (II), and the anion represented by (X ¹ ) ⁻ , high sensitivity and good pattern which are the effects of the present invention In terms of formability and high adhesion to a hard surface as a substrate, a preferred combination is that, as a cation, R ⁴ represents a halogen atom, R ⁵ represents a halogen atom, and R ⁶ represents a halogen atom. A4 is 0-2, a5 is 1-2, a6 is 1-2, and the anion is PF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , perfluoroalkylsulfonic acid. Can be mentioned.
Further, when the anion is a divalent or higher anion, it can have two or more cations.

  Although the preferable specific example of the cation of the specific polymerization initiator-II in this invention is given to the following, it is not limited to these.

  Although the preferable specific example of the anion of the specific polymerization initiator-II in this invention is given to the following, it is not limited to these.

  The above cations and anions can be used in any combination and can be appropriately selected according to the purpose.

  Although the preferable specific example of specific polymerization initiator-II in this invention is given to the following, it is not limited to these.

The specific polymerization initiator-II in the present invention is synthesized by the following method. In the sulfonium salt having a cation of the compound represented by the general formula (I-2), a cyclic sulfide compound is introduced with a halogen with a halogenating agent, oxidized with hydrogen peroxide to form a sulfoxide, and the diphenyl sulfoxide compound is present in the presence of an acid catalyst. The reaction is carried out to synthesize a triphenylsulfonium salt structure. Then, specific polymerization initiator-II is compoundable by carrying out salt exchange to the desired anion.
Hereinafter, a synthesis example of the specific example will be described in detail.

[Synthesis of sulfonium salt B]
-Synthesis of 2,8-dichlorodibenzothiophene oxide-
To 7.3 g of 2,8-dichlorodibenzothiophene, 150 ml of methylene chloride and 100 ml of trifluoromethanesulfonic acid were added and stirred at 0 ° C. 3.3 g of 30 w% hydrogen peroxide solution was added dropwise over 10 minutes, and the temperature was raised from 0 ° C. to room temperature. After stirring at room temperature for 1 hour, the mixture was poured into 200 ml of ice water, extracted with 100 ml of methylene chloride, and the aqueous layer was extracted twice with 50 m of methylene chloride, and then washed with saturated brine. The organic layer was concentrated, and the resulting solid was suspended in 100 ml of methanol for 1 hour. After filtration, the obtained crystal was vacuum-dried to obtain 7.1 g (yield 92%) of 2,8-dichlorobenzothiophene oxide.

1.5 g of 2,8-dichlorodibenzothiophene oxide and 10 ml of chlorobenzene were added and stirred. 2.2 g of aluminum chloride was added and stirred at an internal temperature of 133 ° C. for 6 hours. Thereafter, the mixture was poured into 50 ml of ice water, extracted with 20 ml of ethyl acetate, and the aqueous layer was further extracted twice with 20 ml of ethyl acetate, and then washed with saturated brine. The organic layer was concentrated, 50 ml of acetone was added, and the solution was slowly added dropwise to 90 ml of 0.5N KPF ₆ solution. Then, it stirred at room temperature for 1 hour and produced | generated solid was filtered. Furthermore, after washing twice with 50 ml of water and recrystallizing with isopropanol, 1.5 g (yield 53%) of the following sulfonium salt B was obtained.

The structure of the obtained sulfonium salt B was confirmed by NMR.
NMR 400 MHz DMSO-d6 7.68 (s, 4H); 7.88 (d, 2H, J = 8.8); 8.40 (d, 2H, J = 8.8); 8.80 (s, 2H).

-Synthesis of sulfonium salt C-
1.8 g of 2,8-dichlorodibenzothiophene oxide was added to 50 ml of toluene and stirred. Maintained at 0 ° C., 2.7 g of trifluoroacetic anhydride was slowly added dropwise thereto, stirred at 0 ° C. for 30 minutes, 3.6 g of nonafluorobutanesulfonic acid was slowly added dropwise, and stirred at 0 ° C. for 3 hours. Then, it was poured into 50 ml of water, extracted with 20 ml of toluene, and the aqueous layer was further extracted with 20 ml of toluene. The organic layer was washed with saturated brine. The organic layer was concentrated, 30 ml of N-methylpyrrolidone was added, and the solution was slowly added dropwise to 90 ml of 0.5N KPF6 solution. Thereafter, the mixture was stirred at room temperature for 1 hour, and the resulting solid was filtered, further washed twice with 50 ml of water, and further recrystallized with acetonitrile, whereby 1.7 g of the following sulfonium salt E (yield 52%) was obtained. Obtained.

The structure of the obtained sulfonium salt C was confirmed by NMR.
NMR 400 MHz DMSO-d ₆ 2.34 (s, 3H); 7.40 (d, 2H)
, J = 8.4); 7.54 (d, 2H, J = 8.4); 7.86 (d, 2H, J = 8.4); 8.36 (d, 2H, J = 8. 4); 8.79 (s, 2H,).

-Synthesis of sulfonium salt D-
In the synthesis method of 2,8-dichlorodibenzothiophene oxide, instead of 2,8-dichlorobenzothiophene, 2,8-dibromodibenzothiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and further, by the same synthesis method as sulfonium salt C, sulfonium 1.2 g (yield 65%) of salt D was obtained.

  The structure of the obtained sulfonium salt D was confirmed by NMR.

-Synthesis of sulfonium salt E-
In the synthesis method of 2,8-dichlorobenzothiophene oxide, 2,8-dibromodibenzothiophene (manufactured by Tokyo Kasei) is used in place of 2,8-dichlorodibenzothiophene, and sulfonium salt E is synthesized by the same synthesis method as sulfonium salt B. 1.5 g (yield 60%) was obtained.

  The structure of the obtained sulfonium salt E was confirmed by NMR.

-Synthesis of sulfonium salt F-
In the method of synthesizing 2,8-dichlorodibenzothiophene oxide, instead of 2,8-dichlorodibenzothiophene, 2-chlorodibenzothiophene (synthesized by the method described in Bull. Chem. Soc. Jpn. 1981, 54, 2374-2378) In addition, 1.2 g (yield 40%) of sulfonium salt F was obtained by the same synthesis method as sulfonium salt B.

  The structure of the obtained sulfonium salt F was confirmed by NMR.

  The specific synthesis example of the specific polymerization initiator-II has been described above, but other specific polymerization initiators other than those listed above can be synthesized in the same manner as described above.

  Among the compounds represented by specific polymerization initiator-I and specific polymerization initiator-II, particularly preferred embodiments (Exemplary Compound 1 to Exemplary Compound 6) are shown below.

  In the curable composition for a color filter of the present invention, the specific polymerization initiator-I and the specific polymerization initiator-II may be used alone or in combination of two or more.

  In the present invention, the content of the specific polymerization initiator-I and / or the specific polymerization initiator-II is preferably 0.01% by mass to 30% with respect to the total mass of the color filter curable composition of the present invention. It is suitable to contain in the range of 0.5% by mass, more preferably 0.5% by mass to 20% by mass. Further, when the specific polymerization initiator-I and the specific polymerization initiator-II are used in combination, the mass ratio is preferably 10: 1 to 1:10, and more preferably 5: 1 to 1: 5. Specific polymerization initiator-I and / or specific polymerization initiator-II are in a mass ratio with respect to the sensitizer described later (specific polymerization initiator-I and / or specific polymerization initiator-II): It is preferable that the sensitizer is contained in an amount of 200: 1 to 1: 200, more preferably 50: 1 to 1:50, and still more preferably 20: 1 to 1: 5.

-Other polymerization initiators-
In addition to the specific polymerization initiator-I or the specific polymerization initiator-II, the curable composition for a color filter of the present invention includes other known polymerization initiators as long as the effects of the present invention are not impaired. Can be used together. Examples of other known polymerization initiators that can be used in combination include known radical polymerization or cationic polymerization photopolymerization initiators used in radiation-curable color filter curable compositions. Other photopolymerization initiators that can be used in combination with the present invention undergo a chemical change through the action of light or interaction with the electronically excited state of the sensitizer, and are at least one of radicals, acids, and bases. A compound that produces one species. As the specific photopolymerization initiator, those known to those skilled in the art can be used without limitation. Specifically, for example, Bruce M. et al. Monroe et al., Chemical Review, 93, 435 (1993). R. S. By Davidson, Journal of Photochemistry and biologic A: Chemistry, 73.81 (1993). J. P. Fausier "Photoinitiated Polymerization-Theory and Applications": Rapra Review vol. 9, Report, Rapra Technology (1998). M. Tsunooka et al. , Prog. Polym. Sci. , 21, 1 (1996). Many are described. In addition, there are many chemical amplification type photoresists and compounds used for cationic photopolymerization described in (Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187-192). Has been. Further, F.I. D. Saeva, Topics in Current Chemistry, 156, 59 (1990). G. G. Maslak, Topics in Current Chemistry, 168, 1 (1993). H., et al. B. Shuster et al, JACS, 112, 6329 (1990). , I. D. F. Eaton et al, JACS, 102, 3298 (1980). A group of compounds that undergo oxidative or reductive bond cleavage through interaction with the electronically excited state of the sensitizer as described in the above.

-Radical polymerization initiator-
In the present invention, the radical polymerization initiator that can be used in combination with the specific polymerization initiator-I or the specific polymerization initiator-II includes (a) aromatic ketones, (b) aromatic onium salt compounds, and (c) organic. Peroxide, (d) thio compound, (e) hexaarylbiimidazole compound, (f) ketoxime ester compound, (g) borate compound, (h) azinium compound, (i) metallocene compound, (j) active ester Preferred examples include compounds, (k) compounds having a carbon halogen bond, and (l) alkylamine compounds. These radical polymerization initiators may be used alone or in combination with the above compounds (a) to (l). The radical polymerization initiator in the present invention is preferably used alone or in combination of two or more.

-Cationic polymerization initiator-
In the present invention, the cationic polymerization initiator (photoacid generator) that can be used in combination with the specific polymerization initiator-I or the specific polymerization initiator-II is used for, for example, a chemically amplified photoresist or photocationic polymerization. (Refer to the organic electronics materials study group, “Organic materials for imaging”, Bunshin Publishing (1993), pages 187 to 192). Examples of the cationic polymerization initiator suitable for the present invention are listed below.
First, mention may be made of B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ and CF ₃ SO ₃ ⁻ salts of aromatic onium compounds such as diazonium, ammonium, iodonium and phosphonium. it can. Secondly, sulfonated products that generate sulfonic acid can be mentioned. Thirdly, a halide that generates hydrogen halide can also be used. Fourthly, an iron allene complex can be mentioned.
When other polymerization initiators described above are used in combination, the content thereof is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total mass of the curable composition for color filters. It is preferable to contain in the range of%.

(B) Photopolymerizable compound The curable composition for a color filter of the present invention contains (B) a photopolymerizable compound.
Examples of the photopolymerizable compound in the present invention include a radical polymerizable compound or a cationic polymerizable compound. Examples of the radical polymerizable compound are described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011 and the like. And a photocurable polymerizable compound used in the photopolymerizable composition. As the cationic polymerizable compound, for example, a polymerizable compound applied to a cationic polymerization type photocurable resin is known. For example, photocationic polymerization type light sensitized to a visible light wavelength region of 400 nm or more is used. Examples of the polymerizable compound applied to the curable resin include polymerizable compounds described in JP-A-6-43633 and JP-A-8-324137.
Hereinafter, the radically polymerizable compound and the cationically polymerizable compound that can be used in the present invention will be described in more detail.

(B-1) Radical polymerizable compound The radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization and having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. Any type may be used, including those having chemical forms such as monomers, oligomers, and polymers. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties. In addition, a polyfunctional compound having two or more functional groups is preferable to a monofunctional compound. More preferably, two or more polyfunctional compounds are used in combination for controlling performance such as reactivity and physical properties.

Examples of the polymerizable compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and salts thereof, Examples thereof include radically polymerizable compounds such as anhydrides having a saturated group, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.
Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate More specifically, Yamashita Junzo, “Cross-linking agent handbook” (1981, Taiseisha); Kato Kiyomi, “UV / EB curing handbook (raw material)” (1985, Polymer) Radtech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) ) And the like, or radically polymerizable or crosslinkable monomers known in the industry, Oligomers and polymers can be used.

-Preferred radical polymerizable compound-
As the photopolymerizable compound in the present invention, a (meth) acrylic monomer or prepolymer, or a urethane monomer or prepolymer is preferably used. More preferably, they are the following compounds.

  2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalate neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalate, methoxy-polyethylene glycol acrylate, tetramethylol Methane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol EO adduct acrylate, modified glycerin triacrylate Bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxy-polyethylene Glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, bisphenol A PO adduct diacrylate, bisphenol A EO adduct diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer, lactone Modified flexible acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, penta Erythritol triacrylate hexamethylene di Socia sulfonates urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate.

  These acrylate compounds have less skin irritation and sensitization (rash) than conventional polymerizable compounds used in UV curable inks, can relatively reduce viscosity, and provide stable ink ejection properties. Further, the polymerization sensitivity and the adhesion to the recording medium are also good. In the present invention, when the acrylate compound is used as the polymerizable compound, the content of the acrylate compound is preferably 20 to 95% by mass with respect to the total mass of the color filter curable composition of the present invention. Preferably it is 50 mass%-95 mass%, More preferably, you may be 70 mass%-95 mass%.

Monomers listed as photopolymerizable compounds in the present invention have low sensitization even at a low molecular weight, and have high reactivity, low viscosity, and excellent adhesion to a recording medium. .
Furthermore, in order to further improve the sensitivity, bleeding, and adhesion to the recording medium, the above monoacrylate is used in combination with a polyfunctional acrylate monomer or polyfunctional acrylate oligomer having a molecular weight of 400 or more, preferably 500 or more. It is preferable in terms of improving adhesion. Furthermore, it is particularly preferable to use a monofunctional, bifunctional, or trifunctional or higher polyfunctional monomer in combination. While maintaining safety, sensitivity, bleeding, and adhesion to the recording medium can be further improved, which is preferable. As the oligomer, an epoxy acrylate oligomer and a urethane acrylate oligomer are particularly preferable.

When recording on a flexible recording medium such as a PET film or PP film, a combination of a monoacrylate selected from the above compound group and a polyfunctional acrylate monomer or polyfunctional acrylate oligomer gives the film flexibility and adhesion. It is preferable because the film strength can be increased while improving the properties. As monoacrylate, stearyl acrylate, isoamyl acrylate, isomystil acrylate, and isostearyl acrylate have high sensitivity and low shrinkage to prevent curling, and are preferable in terms of prevention of bleeding, odor of printed matter, and cost reduction of irradiation device. .
In addition, methacrylate has better skin irritation than acrylate.
Among the above compounds, when alkoxy acrylate is used in an amount of less than 70% by mass and the remainder is acrylate, it is preferable because it has good sensitivity, bleeding characteristics, and odor characteristics.

(B-2) Cationic polymerizable compound As the cationic polymerizable compound that can be used in the present invention, various known cationic polymerizable monomers known as photocation polymerizable monomers can be used. Examples of the cationic polymerizable monomer include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and 2001-2001. Examples thereof include epoxy compounds (oxirane group-containing compounds), vinyl ether compounds, oxetane compounds (oxetane group-containing compounds) and the like described in each publication such as No. 220526.

  The oxirane group-containing compound can be appropriately selected from compounds containing at least one oxirane group (oxiranyl group) having an oxirane ring in the molecule, specifically those usually used as epoxy resins. Any of an oligomer and a polymer may be sufficient.

  Specific examples of the oxirane group-containing compound include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Here, the epoxy resin refers to a monomer, an oligomer, or a polymer.

  Suitable aromatic epoxy resins include di- or poly-glycidyl ethers produced by the reaction of polyphenols having at least one aromatic nucleus or their alkylene oxide adducts with epichlorohydrin. For example, di- or poly-glycidyl ether of bisphenol A or its alkylene oxide adduct, di- or poly-glycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and novolak type epoxy resin. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As a preferred alicyclic epoxy resin, a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring is epoxidized with an appropriate oxidizing agent such as hydrogen peroxide or peracid. And cyclohexene oxide-containing compounds or cyclopentene oxide-containing compounds. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.

  Preferred examples of the aliphatic epoxy resin include di- or poly-glycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. For example, diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, di- or tri-glycidyl of glycerin or its alkylene oxide adduct Polyglycidyl ether of polyhydric alcohol such as ether, diglycidyl ether of polyethylene glycol or its alkylene oxide adduct, diglycidyl ether of polyalkylene glycol such as polypropylene glycol or diglycidyl ether of its alkylene oxide adduct, and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the oxirane group-containing compound, in addition to the above-mentioned compounds, monoglycidyl ethers of aliphatic higher alcohols that are monomers having one oxirane ring in the molecule, monoglycidyl ethers of phenols, cresols or alkylene oxide adducts thereof, etc. Can be mentioned.
In addition, the oxirane group-containing compound can be used in combination of two or more, in addition to being used alone.

  Hereinafter, preferable specific examples (exemplary compounds (i) to (viii)) of the oxirane group-containing compound are listed. However, the present invention is not limited to these.

  Of the oxirane group-containing compounds, exemplary compound (i) and exemplary compound (v) are preferred.

  Examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylol. Di- or trivinyl ether compounds such as propane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-pro Vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

Below, monofunctional vinyl ether and polyfunctional vinyl ether are illustrated in detail.
Examples of monofunctional vinyl ethers include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4 -Methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl D Ter, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloro Examples thereof include ethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether and the like.

  Examples of polyfunctional vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F. Divinyl ethers such as alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition Examples thereof include polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.

  As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

The oxetane group-containing compound that can be used in the present invention is a compound containing at least one oxetane group (oxetanyl group) in the molecule, and JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. Any known oxetane compound can be arbitrarily selected and used.
As the compound having an oxetane ring that can be used in the curable composition for a color filter of the present invention, a compound having 1 to 4 oxetane rings in its structure is preferable. By using such a compound, it becomes easy to maintain the viscosity of the curable composition for a color filter in a favorable handling property range, and high adhesion of the cured ink to a recording medium is achieved. Obtainable.

  Examples of the compound having 1 to 2 oxetane groups in the molecule include compounds represented by the following formulas (1) to (3).

R ^a1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. When two R ^a1 are present in the molecule, they may be the same or different.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any hydrogen of these alkyl groups is substituted with a fluorine atom.
R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxycarbonyl group, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkenyl group include a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, and 2-methyl-2. -Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like. Examples of the group having an aromatic ring include phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group and the like. Can be mentioned. As the alkylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, etc., as an alkoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, etc., as an N-alkylcarbamoyl group, Examples thereof include an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group. R ^a2 may have a substituent, and examples of the substituent include an alkyl group of 1 to 6 and a fluorine atom.

R ^a3 is a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or an alkylene group containing a carbonyl group, a carboxyl group Represents an alkylene group containing, an alkylene group containing a carbamoyl group, or a group shown below. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

When R ^a3 is the above polyvalent group, R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, Represents a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.
R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .
R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and n is an integer of 0 to 2,000. R ^a7 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a monovalent group having the following structure.

In the monovalent group, R ^a8 is an alkyl group having 1 to 4 carbon atoms or an aryl group, and m is an integer of 0 to 100.

  As a compound represented by the formula (1), 3-ethyl-3-hydroxymethyloxetane (OXT-101: manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (OXT) -212: manufactured by Toagosei Co., Ltd.) and 3-ethyl-3-phenoxymethyloxetane (OXT-211: manufactured by Toagosei Co., Ltd.). Examples of the compound represented by the formula (2) include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (OXT-121: Toagosei Co., Ltd.). ), Bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: Toagosei Co., Ltd.) is exemplified.

  Examples of the compound having 3 to 4 oxetane groups in the molecule include compounds represented by the following formula (4).

In Formula (4), R ^a1 has the same ^meaning as in Formula (1). Other examples of Ra ⁹ as a linking group include branched alkylene groups having 1 to 12 carbon atoms such as groups represented by the following ACs, and branched poly ( An alkyleneoxy) group or a branched polysiloxy group such as a group represented by E below. j is 3 or 4.

In the above A, R ^a10 represents a methyl group, an ethyl group, or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Another embodiment of the oxetane group-containing compound that can be suitably used in the present invention includes a compound represented by the following formula (5) having an oxetane ring in the side chain.

In Formula (5), R ^a1 has the same ^meaning as in Formula (1). R ^a8 has the same ^{meaning as} in the above formula. R ^a11 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

Such oxetane group-containing compounds are described in detail in paragraphs [0021] to [0084] of JP-A No. 2003-341217, and the compounds described therein can be suitably used in the present invention. .
Oxetane compounds described in JP 2004-91556 A can also be used in the present invention. It is described in detail in paragraph numbers [0022] to [0058] of the publication.
Among the oxetane group-containing compounds used in the present invention, it is preferable to use a compound having one oxetane group from the viewpoint of the viscosity and tackiness of the curable composition for color filters.

  Hereinafter, preferable specific examples [Exemplary compounds 1 to 37 and (a) to (f)] of the oxetane group-containing compound are listed. However, the present invention is not limited to these.

  Of the compounds having an oxetane ring, exemplary compound (a), exemplary compound (b), exemplary compound (d), and exemplary compound (f) are preferable.

The cationically polymerizable compound that can be used in the present invention may be used alone or in combination of two or more. From the viewpoint of reducing the ink curing rate and the ink viscosity, an oxetane group-containing / oxirane group is used. It is preferable to use a containing compound in combination.
The curable composition for color filters of the present invention preferably contains at least one oxetane group-containing compound and / or at least one oxirane group-containing compound as the cationic polymerizable compound, and preferably contains at least one oxetane. More preferably, the group-containing compound and at least one oxirane group-containing compound are included. These compounds are polymerized upon irradiation with active energy rays by the action of the polymerization initiator and cure themselves, and since the curing reaction can be carried out in a short time, the photo-fading dye is easily cured (polymerization reaction) and It is particularly effective in preventing fading in an image after curing, and can form an image having excellent hue (hue), color density, and sharpness, and light resistance comparable to that of a pigment.

  In the present invention, it is preferable that both the oxetane group-containing compound and the oxirane group-containing compound are used in combination. However, as an aspect of the combination, for example, exemplified compound (a) and exemplified compound (i) The aspect which combined and the aspect which combined exemplary compound (b) and exemplary compound (v) are especially preferable at the point which can improve light resistance more effectively.

  When the oxetane group-containing compound (p) and the oxirane group-containing compound (q) are used in combination, the content ratio (mass ratio) p / q is 50 in that the light resistance of the image after curing can be more effectively improved. / 50 to 95/5 is preferable, and 67/33 to 90/10 is particularly preferable.

  The content of the photopolymerizable compound in the curable composition for a color filter of the present invention is preferably 10% by mass to 80% by mass, more preferably 15 to 70%, based on the total mass of the curable composition for a color filter. It is in the range of 20% by mass to 60% by mass, more preferably 20% by mass.

<(C) Colorant>
The curable composition for a color filter of the present invention contains (C) a colorant.
There is no restriction | limiting in particular in the coloring agent contained in the curable composition for color filters of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of light resistance.

  As the pigment that can be used in the curable composition for a color filter of the present invention, various conventionally known 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 an organic pigment, for example,
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
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 the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

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

  These organic pigments 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 100: 4 or less, 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 is shorter than the short wavelength, and the deviation from the NTSC target hue may be large. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment 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. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. When the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may increase. 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. If it is 100: 61 or more, the dispersion stability may decrease.

In the present invention, when the colorant is a dye, it can be uniformly dissolved in the composition to obtain a curable composition.
The dye that can be used as the colorant contained in the curable composition for a color filter 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 includes 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, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.
Specific examples of the acid dye are shown below, but are not limited thereto. For example,
acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5 , 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18 , 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 0, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216 217,249,252,257,260,266,274; acid violet 6B, 7,9,17,19; acid yellow 1,3,7,9,11,17,23,25,29,34,36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

Among these, acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63 , 74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17, 25, 29, 34 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 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.

The colorant that can be used in the present invention is a dye or a pigment having an average particle size r (unit: nm) satisfying 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. desirable. By using such a pigment having an average particle diameter r, red and green pixels having a high contrast ratio and a high light transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments optionally used (average particle size is usually above 300 nm), preferably with a dispersant and a solvent. The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

As content of (C) coloring agent contained in the curable composition for color filters of this invention, it is preferable that it is 25-95 mass% in the total solid of a curable composition, and is 30-90 mass. % Is more preferable, and 40-80 mass% is still more preferable.
When there are too few colorants, when a color filter is produced with the curable composition for a color filter of the present invention, there is a tendency that an appropriate chromaticity cannot be obtained. On the other hand, if the amount is too large, the photocuring does not proceed sufficiently and the strength as a film is lowered, or the development latitude during alkali development tends to be narrow, but the specific sensitizer according to the present invention has a light absorption efficiency. Since it is high, even if it is a case where a coloring agent is contained in a high concentration in a curable composition, the sensitivity improvement effect is exhibited notably.

  Various additives can be used in combination with the curable composition for color filters of the present invention depending on the purpose. Hereinafter, these optional components will be described.

(D) Sensitizing dye The curable composition for a color filter of the present invention preferably contains (d) a sensitizing dye for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength. .
The sensitizing dye (d) that can be used in the present invention is preferably a sensitizing dye that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism.
Examples of the sensitizing dye (d) 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.
Preferred examples of (d) sensitizing dyes 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.
More preferable examples of the sensitizing dye include compounds represented by the following general formulas (e-1) to (e-4).

In formula (e-1), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ¹ represents a basic nucleus of the dye in combination with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. May be. W represents an oxygen atom or a sulfur atom.

In formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ² —. Here, L ² represents —O— or —S—. Moreover, W is synonymous with what was shown to Formula (e-1).

In formula (e-3), A ² represents a sulfur atom or NR ⁵⁹ , L ³ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a carbon atom, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a group of a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (e-4), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, Represents a substituted or unsubstituted aryl group, and L ⁴ and L ⁵ each independently represents a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ⁴ and adjacent carbon atoms. , R ⁶⁰ and R ⁶¹ each independently represent a monovalent non-metallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.

The content of the (d) sensitizing dye in the color filter curable composition of the present invention is 0.1% by mass to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. %, Preferably 0.5% by mass to 15% by mass.
A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

  Moreover, as a preferable sensitizing dye which can be contained in the specific curable composition, in addition to the above-mentioned (e) sensitizing dye, a compound represented by the following formula (II) and a compound represented by the following formula (III) There is at least one selected. These may be used individually by 1 type, and may use 2 or more types together.

In formula (II), R ¹¹ and R ¹² each independently represent a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. . n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹¹ may be the same or different. When n ′ is 2 or more, a plurality of R ¹² may be the same or different. In the formula (II), the isomer by the double bond is not limited to either one.

The compound represented by the formula (II) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and ε at a wavelength of 365 nm of 3000 mol ⁻¹ · L · cm ^−1. More preferably, ε at a wavelength of 365 nm is most preferably 20000 mol ⁻¹ · L · cm ⁻¹ or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Preferred specific examples of the compound represented by formula (II) are illustrated below, but the present invention is not limited thereto.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents an n-butyl group, and Ph represents a phenyl group.

In the formula (III), A represents an aromatic ring or a hetero ring which may have a substituent, X ² represents an oxygen atom, a sulfur atom, or —N (R ²³ ) —, Y represents an oxygen atom, sulfur atom, or -N ^{(R 23)} - represents a. R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ²¹ , R ²² , and R ²³ are bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the formula (III), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ²¹ , R ²² and R ²³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

In the compound represented by the formula (III), Y is preferably an oxygen atom or —N (R ²³ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ²³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. Further, Y is most preferably —N (R ²³ ) —.

  Preferred specific examples (VI1) to (VI124) of the compound represented by the formula (III) are shown below, but the present invention is not limited thereto. Further, the isomer by the double bond connecting the acidic nucleus and the basic nucleus is not clear, and the present invention is not limited to either isomer.

With respect to the compound represented by the formula (III) in the present invention, various chemical modifications for improving the properties of the curable composition for color filters can be further performed.
For example, the sensitizing dye and an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. Unnecessary precipitation suppression of the sensitizing dye from the film after exposure can be performed.
In addition, partial structures having radical generating ability in the sensitizing dye and the above-described photopolymerization initiator (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, borate, amine, trimethylsilylmethyl) , An oxidatively cleavable site such as carboxymethyl, carbonyl, imine, etc.), the photosensitivity can be remarkably enhanced particularly in a state where the concentration of the starting system is low.

  In the curable composition for color filters of the present invention, the compounds represented by formula (II) or formula (III) may be used alone or in combination of two or more.

  The compound represented by the above formula (II) or formula (III) has a very high colorant concentration in the curable composition for color filters, and has a light transmittance of the formed colored pattern (photosensitive layer). When it is extremely low, specifically, when the light transmittance of 365 nm of the photosensitive layer when formed without adding a sensitizing dye is 10% or less, the effect can be obtained. Prominently demonstrated. In particular, among the above formula (II) or formula (III), the compound represented by formula (III) is most preferable, and specifically, the compounds of (VI56) to (VI122) are most preferable.

  The curable composition of the present invention comprises (A) the sulfonium salt represented by the general formula (I) and at least one selected from the sulfonium salt represented by the following general formula (II), In addition to B) a photopolymerizable compound, (C) a colorant, and (d) a sensitizing dye, an optional component described in detail below may be further contained as necessary. Hereinafter, optional components that can be contained in the curable composition of the present invention will be described.

[Dispersant]
When the curable composition for a color filter of the present invention contains a pigment as the colorant (C), it is preferable to add a dispersant from the viewpoint of improving the dispersibility of the 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 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, and 10-60 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.

[Binder polymer]
In the specific curable composition, 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 Resin in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride Etc. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxyl styrene. Examples of the monomer having an acid anhydride include 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 esters having an aliphatic hydroxyl group such as methacrylic esters.
(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, propargyl methacrylate and the like.
(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. Examples thereof include compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like.

  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.

[Co-sensitizer]
The curable composition for a color filter 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 sensitizer to actinic radiation or suppressing polymerization inhibition 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, N-phenylglycine and the like.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142773, and JP-A-56. And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethylphosphite, etc.), Si-- described in Japanese Patent Application No. 6-191605 H, Ge-H compound, etc. are mentioned.

[Polymerization inhibitor]
In the present invention, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of a curable composition for a color filter. It is desirable to do.
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, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying 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.

[Adhesion improver]
In the present invention, it is preferable to add an adhesion improver in order to improve adhesion to a hard surface (substrate) as a base material. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  0.5-30 mass% is preferable in the total solid of a curable composition, and, as for the addition amount of a contact | adherence improving agent, 0.7-20 mass% is more preferable.

[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 binder.

[Diluent]
The specific curable composition may be used by dissolving it in various organic solvents when it is applied on a support in the production of a color filter.
The organic solvent used here is acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. The concentration of the solid content in the organic solvent is preferably 2 to 60% by mass.

  As a means for preventing sensitivity deterioration due to the light-shielding effect of the colorant used in the color filter curable composition, a combination of a cationic polymerizable compound and a cationic polymerization initiator, and a combination of a radical polymerizable compound and a radical polymerization initiator In addition, it may be a radical / cation hybrid curable ink using these polymerizable compounds and a polymerization initiator in combination.

  In addition, a known compound can be added to the curable composition for a color filter of the present invention as necessary. For example, surfactants, leveling additives, matting agents, polyester resins for preparing film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes, and the like are appropriately selected and added. be able to. In order to improve the adhesion to a recording medium such as polyolefin or PET, it is also preferable to contain a tackifier that does not inhibit the polymerization. Specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, pages 5 to 6 (for example, (meth) acrylic acid and an alcohol having an alkyl group having 1 to 20 carbon atoms). Ester, (meth) acrylic acid and a C3-14 alicyclic alcohol ester, (meth) acrylic acid and a C6-14 aromatic alcohol ester copolymer), and polymerizability And low molecular weight tackifying resins having an unsaturated bond.

<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 on the support using the curable composition for color filters of the present invention.
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).

  The method for producing a color filter of the present invention comprises a step of applying a curable composition for a color filter of the present invention on a support to form a colored curable composition layer (hereinafter appropriately referred to as “colored curable composition layer”). Abbreviated as “formation step”), a step of exposing the colored curable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and the curable composition layer after exposure. And a step of forming a colored pattern by development (hereinafter abbreviated as “development step” as appropriate).

Specifically, a specific curable composition is applied directly or via another layer on a support (substrate) to form a photopolymerizable composition layer (colored curable composition layer forming step). By exposing through a predetermined mask pattern, only the coating film portion irradiated with light is cured (exposure process), and developed with a developer (development process), from each color (three colors or four colors) pixels The color filter of this invention can be manufactured by forming the pattern-like film | membrane which becomes.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

(Colored curable composition layer forming step)
In the colored curable composition layer forming step, the colored curable composition layer is formed by applying the curable composition of the present invention on the support.

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 the curable composition for color filters in this invention, 0.1 micrometer-10 micrometers are preferable, 0.2 micrometer-5 micrometers are more preferable, 0.2 micrometer-3 micrometers are still more preferable.

  The curable composition applied on the support is usually dried at 70 to 110 ° C. for about 2 to 4 minutes to form a colored curable composition layer.

(Exposure process)
In the exposure step, the colored curable composition layer formed in the colored curable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1000 mJ, and most preferably 10 mJ to 800 mJ.

(Development process)
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated portion in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part 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 alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. ] -7- An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. 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.

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

  Since the color filter of the present invention uses the curable composition for color filters of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance. Therefore, it is possible to form a high-resolution pattern that has excellent exposure sensitivity, 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, “%” is based on mass.
<Example 1>
1. 1. Preparation of curable composition 1-1. Preparation of pigment dispersion (P1) (C) As a pigment, C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of a 30/70 (weight ratio) mixture with CI Pigment Yellow 219, and 10 parts by mass of a BYK2001 (Disperbyk: manufactured by BYK Corporation, solid content concentration: 45.1% by weight) as a dispersant (approximately 4. 51 parts by mass) and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).
With respect to the pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 200 nm.

1-2. Preparation of curable composition (coating liquid) The following composition was mixed to prepare a curable composition.
-Pigment dispersion (P1) 600 parts by mass-Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000) 200 parts by mass (B) polyfunctionality Monomer dipentaerythritol hexaacrylate 60 parts by mass (A) Photopolymerization initiator: 60 parts by mass of the following exemplified compound 1 / surfactant (trade name: Tetranic 150R1, BASF) 1 part by mass / sensitizer (4 , 4′-bisdiethylaminobenzophenone (A1)) 40 parts by mass / Co-sensitizer (S1) 20 parts by mass / γ-methacryloxypropyltriethoxysilane 5 parts by mass / propylene glycol monomethyl ether acetate 1,000 parts by mass

2. 2. Production of color filter 2-1. Formation of curable composition layer A curable composition containing the above pigment was applied as a resist solution to a 550 mm x 650 mm glass substrate by slit coating under the following conditions, then allowed to stand for 10 minutes, and then applied to a new glass substrate. Then, vacuum drying and prebaking (100 ° C., 80 seconds) were performed to form a curable composition coating film (curable composition layer).
(Slit application conditions)
・ Gap at the opening of the coating head tip: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
-Application thickness (dry thickness): 2 μm
・ Application temperature: 23 ℃

2-2. Exposure and development Thereafter, the photocurable coating film was exposed in a pattern using a 2.5 kw ultra-high pressure mercury lamp, and after the exposure, the entire surface of the coating film was organic developer (trade name: CD, Fuji Film Arch Co., Ltd.) The product was covered with a 10% aqueous solution prepared in ()) and left still 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, and exposure sensitivity of a curable composition coating film (colored layer) formed on a glass substrate using the colored curable composition, Substrate adhesion, developability, and pattern cross-sectional shape were evaluated as follows. The results are shown in Table 2.

3-1. Storage Stability of Curable Composition (Coating Solution) After storing the curable composition coating solution 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),
The colored curable composition coating solution was coated on a glass substrate and dried to a thickness of 1.0 μm. The spin coating conditions were 300 rpm for 5 seconds, 800 rpm for 20 seconds, and the drying conditions were 100 ° C. for 80 seconds. Next, it exposed with the various exposure amount of 10-1600mJ / cm < ² > using the photomask for a test with a line | wire width of 2.0 micrometers. Next, it developed on 25 degreeC and the conditions for 60 second using the developing solution of 60% CD-2000 (made by Fuji Film Electronics Materials). Then, after rinsing with running water for 20 seconds, spray drying was performed to complete patterning. The minimum exposure amount in which the film thickness after development of the region irradiated with light in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

3-3. Developability, pattern cross-sectional shape, substrate adhesion After that, after post-heating at 200 ° C. for 5 minutes, the substrate surface and cross-sectional shape 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.
-Pattern cross-sectional shape-
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: Substrate 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 14>
In the curable composition of Example 1, except that the exemplified compounds, sensitizers, and co-sensitizers were replaced with the compounds shown in Table 2 below, the same procedure as in Example 1 was performed to obtain a colored pattern. Evaluation similar to Example 1 was performed. The results are shown in Table 2.

<Comparative Example 1>
Using the pigment dispersion (P1) prepared in Example 1, the following composition was uniformly stirred to prepare a coating solution.
-Pigment dispersion (P1) 600 parts by mass-Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000) 200 parts by mass-(B) polyfunctional Monomer dipentaerythritol hexaacrylate 60 parts by mass / radical polymerization initiator (1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime)) (IrgacureOXE-01) 140 parts by mass / solvent (propylene) Glycol monomethyl ether acetate) 1,000 parts by mass / surfactant (trade name: Tetranic 150R1, BASF) 1 part by mass <Comparative Examples 2 to 5>
In the curable composition of Example 1, all were performed in the same manner as in Example 2 except that the photopolymerization initiator, the sensitizer, and the co-sensitizer were replaced with the comparative compounds shown in Table 2 below. The results are shown in Table 2.

In the above table, A1, A2, A3, A4, D1, D2, D3, S1, S2, S3, Irgacure OXE-01, Irgacure 250, and UVI6992 represent the compounds shown below. Exemplary compounds 1 to 6 of the photopolymerization initiator represent particularly preferable exemplary compounds 1 to 6 of the sulfonium salt in the present invention.
A1: 4,4-Bisdiethylaminobenzophenone

D1: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole D2: 1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime)
D3: 4-Benzoxolane-2,6-di (trichloromethyl) -s-triazine S1: N-phenylmercaptobenzimidazole S2: Mercaptobenzthiazole S3: N-phenylglycine Irgacure OXE-01: Benzoyloxime compound Irgacure 250: Iodonium salt compounds (the following structural formula)
UVI6992: sulfonium salt compound (the following structural formula)

<Example 15>
Using the pigment dispersion (P1) prepared in Example 1, the following composition was uniformly stirred to prepare a coating solution.
-Preparation of curable composition (coating solution)-
-Pigment dispersion (P1) 600 parts by mass-Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000) 200 parts by mass-(B) polyfunctional Monomeric dipentaerythritol hexaacrylate 20 parts by mass (A) Photopolymerization initiator: 60 parts by mass of the exemplified compound 1 Solvent (propylene glycol monomethyl ether acetate) 1,000 parts by mass surfactant (trade name: Tetranic 150R1, BASF) 1 part by mass • Sensitizer 9,10-dibutoxyanthracene (compound A5) 40 parts by mass • γ-methacryloxypropyltriethoxysilane 5 parts by mass • Celoxide 201P (Daicel Chemical) 20 parts by mass Oxetane OXT-221 (Toagosei) 2 Except that the parts by mass The above composition are all performed in the same manner as in Example 1 to obtain a colored pattern was evaluated in the same manner as in Example 1. The results are shown in Table 3. In addition, the photoinitiators 1 and 5 in Table 3 represent the compounds described in the particularly preferred examples of the sulfonium salt in the present invention.

<Example 16, comparative examples 5-7>
In the curable composition of Example 1, it carried out similarly to Example 1 except having changed the photoinitiator and the sensitizer into the compound shown by following Table 3. The results are shown in Table 3.

＊ Ａ５：９，１０−ジブトキシアントラセン
Ｉｒｇａｃｕｒｅ２５０：ヨードニウム塩系化合物（上記構造式）
ＵＶＩ６９９２：スルホニウム塩系化合物（上記構造式）
光重合開始剤の例示化合物１、５は、本発明におけるスルホニウム塩の特に好ましい例示化合物１、５を表す。

* A5: 9,10-dibutoxyanthracene Irgacure 250: iodonium salt compound (the above structural formula)
UVI6992: sulfonium salt compound (the above structural formula)
Exemplary compounds 1 and 5 of the photopolymerization initiator represent particularly preferable exemplary compounds 1 and 5 of the sulfonium salt in the present invention.

  From the results of Tables 1 and 2, the curable composition of the present invention has excellent storage stability in the form of a solution, and when an image is formed on a support, a polyfunctional acrylate-based comparative polymerizable compound other than the sulfonium salt in the present invention. It was found that the exposure sensitivity was high compared to the comparative example using No. 1, and it was excellent in developability, substrate adhesion, and pattern cross-sectional shape.

Next, after forming an undercoat layer on the silicon wafer substrate, the curable composition for a color filter of the present invention was applied. Details are described below.
<Example 17>
1. Preparation of resist solution for undercoating ・ Propylene glycol monomethyl ether acetate (PGMEA) 19.20 parts ・ Ethyl lactate 36.67 parts ・ Resin (benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22/18) 40% PGMEA solution) 30.51 parts (B) Photopolymerizable compound (dipentaerythritol hexaacrylate) 12.20 parts Polymerization inhibitor (p-methoxyphenol) 0.0061 parts Fluorosurfactant (F-475, manufactured by Dainippon Ink & Chemicals, Inc.) 0.83 parts (A) Photopolymerization initiator (TAZ-107 (trihalomethyltriazine photopolymerization initiator), Midori Chemical 0.586 parts)

2. Production of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heated in an oven at 200 ° C. for 30 minutes. Next, the resist solution was 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 with an undercoat layer.

3. Preparation of curable composition (coating liquid) A curable compound having the following composition was prepared.
-Cyclohexanone 80 parts by mass-(C) Colorant (CI Acid Blue 108) 7.5 parts by mass-(C) Colorant C.I. I. Solvent Yellow 162 2.5 parts by mass (B) Radical polymerizable compound (3: 7 mixture of Exemplified Compound (M-2) and dipentaerythritol hexaacrylate) 7.0 parts by mass (A) Photopolymerization initiation Agent: 1 part by mass of the exemplified compound 1 / sensitizer (4,4-bisdiethylaminobenzophenone (A1)) 0.7 part by mass / co-sensitizer (S2) 0.4 part by mass / glycerol propoxylate (number average) Molecular weight Mn: 1500, molar extinction coefficient ε = 0, colorless compound according to the present invention) 0.5 parts by mass M-2: tetramethylolpropane triacrylate

4). Storage stability of coating solution After the curable composition (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.

5. Exposure / Development and Evaluation of Colored Photosensitive Resin Composition-Pattern Formation and Sensitivity Evaluation-
3 above. 2. The curable composition prepared in the above 2. It was applied on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1) to form a photocurable coating film. 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, irradiation was performed using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) at an exposure dose of 10 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), 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.

The silicon wafer substrate on which the 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 rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying. The minimum exposure amount in which the film thickness after development of the region irradiated with light in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. In addition, the size of the colored pattern was measured using a length measurement SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The closer the pattern size is to 2 μm, the better the curability and the better the sensitivity.
The results of measurement evaluation are shown in Table 4 below.

<Examples 18 to 29>
In Example 17, except that the photopolymerization initiator, sensitizer, and co-sensitizer used in the preparation of the curable composition were each changed as shown in Table 4 below, in the same manner as in Example 17, A curable composition was prepared, and a colored pattern was formed and evaluated. The results of measurement evaluation are shown in Table 4 below.

<Example 30>
Example 17-3. The composition of the curable composition described in 1 was changed to the following composition and stirred uniformly to obtain a curable composition.
-80 parts by mass of cyclohexanone-(C) Colorant (CI PigmentRed 254) 6.0 parts by mass-(C) Colorant (CI Pigment Yellow 139) 4.0 parts by mass-(B) Photopolymerizable Compound (3: 7 mixture of the exemplified compound (M-2) described above and dipentaerythritol hexaacrylate) 7.0 parts by mass. (A) Photopolymerization initiator: 1 part by mass of the exemplified compound 1 and sensitization. Agent (A4) 0.7 parts by mass Co-sensitizer (S1) 0.4 parts by mass Glycerol propoxylate (number average molecular weight Mn: 1500) 0.5 parts by mass

<Example 31>
In Example 30, a curable composition was prepared and colored in the same manner as in Example 30, except that the photopolymerization initiator, sensitizer, and co-sensitizer were each changed as shown in Table 4 below. Pattern formation and evaluation were performed. The results of measurement evaluation are shown in Table 4 below.

<Comparative Example 8>
• Cyclohexanone 80 parts • (C) Colorant (CI Acid Blue 108) 7.5 parts • (C) Colorant (CI Solvent Yellow 162) 2.5 parts • (B) Radical polymerizable compound (3: 7 mixture of the exemplified compound (M-2) described above and dipentaerythritol hexaacrylate) 7.0 parts Photopolymerization initiator (Irgacure OXE-01, manufactured by Ciba Specialty Chemicals; Oxime series) Photopolymerization initiator) 2.5 parts glycerol propoxylate (number average molecular weight Mn: 1500) 0.5 parts

<Comparative Examples 9-11>
In Comparative Example 8, a curable composition was prepared in the same manner as in Comparative Example 8, except that the photopolymerization initiator, the sensitizer, and the co-sensitizer were each changed as shown in Table 4 below. Formation and evaluation. The results of measurement evaluation are shown in Table 4 below.

<Comparative Example 12>
• Cyclohexanone 80 parts • (C) Colorant (CI Pigment Red 254) 6.0 parts • (C) Colorant (CI Pigment Yellow 139) 4.0 parts • (B) Radical polymerizable compound (previously) (7: 7 mixture of the exemplified compound (M-2) and dipentaerythritol hexaacrylate) 7.0 parts / photopolymerization initiator (Irgacure OXE-01, manufactured by Ciba Specialty Chemicals; Oxime-based photopolymerization) Initiator) 2.5 parts glycerol propoxylate 0.5 parts (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0, colorless compound according to the present invention)

<Comparative Examples 13 and 14>
In Comparative Example 12, a curable composition was prepared in the same manner as in Comparative Example 12 except that the photopolymerization initiator, sensitizer, and co-sensitizer were each changed as shown in Table 4 below, and a colored pattern was prepared. Formation and evaluation. The results of measurement evaluation are shown in Table 4 below.

表中、光重合開始剤１〜６、ＩｒｇａｃｕｒｅＯＸＥ−０１、ＵＶＩ−６９９２、Ｉｒｇａｃｕｒｅ２５０、Ｓ１〜Ｓ３、Ｄ１〜Ｄ３、Ａ１〜Ａ４は、表１で示した化合物と同様である。光重合開始剤の例示化合物１〜６は、本発明におけるスルホニウム塩の特に好ましい例示化合物１〜６を表す。

In the table, photopolymerization initiators 1 to 6, Irgacure OXE-01, UVI-6992, Irgacure 250, S1 to S3, D1 to D3, and A1 to A4 are the same as the compounds shown in Table 1. Exemplary compounds 1 to 6 of the photopolymerization initiator represent particularly preferable exemplary compounds 1 to 6 of the sulfonium salt in the present invention.

Next, in Example 17, the composition of the curable composition was changed to the following composition to prepare a coating solution.
<Example 32>
-Preparation of curable composition-
-80 parts by mass of cyclohexanone-(C) Colorant (CI Acid Blue 108) 7.5 parts by mass-(C) Colorant (CI Solvent Yellow 162) 2.5 parts by mass-(B) Radical Polymerizable compound (3: 7 mixture of the exemplified compound (M-2) described above and dipentaerythritol hexaacrylate) 0.2 parts by mass / Celoxide 201P (Daicel Chemical) 0.4 parts by mass / oxetane OXT-221 (Toagosei Co., Ltd.) 0.4 parts by mass. (A) Photopolymerization initiator: 1 part by mass of the exemplified compound 1. Sensitizer: (9,10-dibutoxyanthracene (A5)) 0.7 parts by mass. Glycerol propoxy Rate 0.5 part by mass (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0, colorless compound according to the present invention)
Except having changed to the said composition, all were performed like Example 17, the coloring pattern was obtained, and evaluation similar to Example 17 was performed. The results are shown in Table 5. In addition, the photoinitiators 1 and 5 in Table 5 represent the compounds described in the particularly preferred examples of the sulfonium salt in the present invention.

<Examples 33 and 34, Comparative Examples 15 and 16>
All of the curable composition of Example 32 was carried out in the same manner as in Example 32 except that the photopolymerization initiator and the sensitizer were replaced with the compounds shown in Table 5 below. The results are shown in Table 5.

Ａ５、Ｉｒｇａｃｕｒｅ２５０、ＵＶＩ６９９２は、前記表１と同じ化合物を表す。光重合開始剤の例示化合物１、３，５は、本発明におけるスルホニウム塩の特に好ましい例示化合物１、３，５を表す。

A5, Irgacure 250, and UVI6992 represent the same compounds as in Table 1 above. Exemplary compounds 1, 3, and 5 of the photopolymerization initiator represent particularly preferable exemplary compounds 1, 3, and 5 of the sulfonium salt in the present invention.

  From the results of Tables 3 and 4, the curable composition of the present invention is excellent in storage stability in a solution state, and when an image is formed on a support, a polyfunctional acrylate-based comparative polymerizable compound other than the sulfonium salt in the present invention. It was found that the exposure sensitivity was high compared to the comparative example using No. 1, and it was excellent in developability, substrate adhesion, and pattern cross-sectional shape.

Claims (5)

(A) at least one selected from a sulfonium salt represented by the following general formula (I) and a sulfonium salt represented by the following general formula (II), (B) a photopolymerizable compound, and (C) A curable composition for color filters, comprising a colorant.

[In the general formula (I), R ¹ , R ² , and R ³ each independently represent a substituent, at least one of R ¹ , R ² , and R ³ represents an electron-withdrawing group; It represents an integer of 0 to 5, a2, and a3 each independently represents an integer of 1~5, ^(X 1) ^- representing the anion. When a1, a2, or a3 represents an integer of 2 or more, a plurality of R ¹ , R ² , or R ³ may be the same or different.
In general formula (II), R ⁴ , R ⁵ , and R ⁶ each independently represent a substituent, at least one of R ⁴ , R ⁵ , and R ⁶ represents an electron-withdrawing group; 5 represents an integer of 5, a5 and a6 each independently represent an integer of 0 to 4, and all of a4 to a6 do not represent 0. (X ¹ ) ⁻ represents an anion. When a4, a5, or a6 represents an integer of 2 or more, a plurality of R ⁴ , R ⁵ , or R ⁶ may be the same or different. ]   2. The curable composition for a color filter according to claim 1, wherein the sum of Hammett values of electron-withdrawing groups of the sulfonium salt is 0.46 or more and 4.0 or less.   The curable composition for a color filter according to claim 1 or 2, wherein the electron-withdrawing group is a halogen atom or a group containing a halogen atom.   A color filter comprising a colored pattern formed using the curable composition for a color filter according to any one of claims 1 to 3 on a support.   The process of apply | coating the curable composition for color filters of any one of Claim 1 thru | or 3 on a support body, and forming a colored curable composition layer, The said colored curable composition layer And a step of developing the colored curable composition layer after the exposure to form a colored pattern. The method for producing a color filter comprising: