JP2008065161A - Curable composition for color filter, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for color filters which cures with high sensitivity, has good pattern forming property and excels in adhesion to a hard surface which is a substrate, even when the composition contains a colorant at high concentration, a color filter with a colored pattern excellent in resolution and adhesion to a support by use of the curable composition for color filters, and a production method by which the color filter can be produced with high productivity. <P>SOLUTION: The curable composition for color filters contains (A) a diaryl iodonium salt having a total of three or more electron-donating groups on one or two aryl rings, (B) a photopolymerizable compound and (C) a colorant. The color filter using the curable composition for color filters and the method for producing the same are also provided. <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 (for example, see 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 has 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 formation properties, and excellent adhesion to a hard surface as a substrate even when containing a colorant at a high concentration. Color filter curable composition, color filter using color filter curable composition, and color filter having a coloring pattern excellent in resolving power and adhesion to a support, and high productivity of the color filter It is providing the manufacturing method which can be manufactured by.

  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 color comprising (A) a diaryliodonium salt having three or more electron donating groups on the aryl ring, (B) a photopolymerizable compound, and (C) a colorant. Curable composition for filter.
<2> The curable composition for a color filter according to <1>, wherein all of the electron donating groups are alkoxy groups.

<3> A color filter comprising a colored pattern formed using the curable composition for a color filter according to <1> or <2> on a support.

<4> A step of applying a curable composition for a color filter according to <1> or <2> on a support to form a colored curable composition layer, and the colored curable composition layer as a mask And a step of developing the colored curable composition layer after the 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.
Furthermore, by using the curable composition for color filters of the present invention, a color filter having a colored pattern excellent in resolving power and adhesion to a support, and a production method capable of producing the color filter with high productivity Can be provided.

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

<Curable composition for color filter>
The curable composition for a color filter of the present invention comprises (A) a diaryl iodonium salt having three or more electron donating groups on the aryl ring, (B) a photopolymerizable compound, (C) a colorant, It is characterized by containing.
Hereinafter, each component contained in the curable composition for color filters of the present invention (hereinafter sometimes simply referred to as “specific curable composition”) will be sequentially described.

((A) Diaryliodonium salt having a total of 3 or more electron donating groups on the aryl ring)
The specific curable composition contains a diaryl iodonium salt having a total of three or more electron donating groups on the aryl ring (hereinafter, sometimes simply referred to as “specific polymerization initiator”).
Conventionally, iodonium salts have been used as radical polymerization initiators or cationic polymerization initiators, and sufficient sensitivity can be obtained, but their stability over time has been insufficient, making them difficult to use. In the present invention, when an iodonium salt used as a polymerization initiator is a diaryl iodonium salt into which an electron donating group is introduced, it is decomposed by water or a nucleophile over time or used in combination with a dye. It is considered that stability over time, particularly thermal stability, is improved by suppressing electron transfer due to heat. Furthermore, the specific polymerization initiator used in the present invention is a compound having a diaryliodonium skeleton from the viewpoint of stability, and an iodonium salt compound having a total of three or more electron donating groups on the aryl ring.

The electron donating group in the specific polymerization initiator may be introduced into any one of the two aryl rings of the diaryl iodonium salt structure or may be introduced into both of the two aryl skeletons.
Further, groups on the aryl ring of the specific polymerization initiator may be bonded to form a ring if possible.

  The electron donating group is preferably an alkyl group, an alkoxy group, an amino group, a urea group, an alkoxyalkyl group, an acyloxyamino group, a cycloalkyl group, or an allyl group. These groups have an electron donating property. The alkyl group, alkenyl group, alkynyl group, aryl group, hydroxyl group, alkoxy group, thiol group, thioalkoxy group, amino group, halogen atom and the like may be substituted as long as they are not lost. Moreover, these substituents may be further substituted with these substituents, and may be bonded to form a ring if possible.

A preferred substitution position of the electron donating group is preferably a para position or an ortho position with respect to the iodonium group on the aryl ring.
The preferred electron donating group is preferably an alkyl group or an alkoxy group, and the most preferred substituent is an alkoxy group.

  The specific polymerization initiator preferably has a total of 3 or more electron donating groups on the aryl ring, and all the electron donating groups are preferably alkoxy groups. The specific polymerization initiator preferably has a total of 3 or more alkoxy groups, and more preferably has a total of 4 or more alkoxy groups.

  The specific polymerization initiator has a sum of Hammett values of all substituents with respect to the iodonium group in the two aryl rings, preferably −0.5 or less, more preferably −0.8 or less, and still more preferably −1.0. It is as follows. The total substituents for the iodonium group refer to all substituents bonded to the aryl skeleton in the diaryl iodonium salt structure. However, iodonium group is excluded. The Hammett value of the substituent is based on the iodonium group in each aryl skeleton.

  Here, Hammett's substituent constant σp value used in this specification 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 the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this is limited to only a substituent having a known value that can be found in the above-mentioned book. Needless to say, it also includes substituents that would be included in the range when measured based on Hammett's rule even if the value is unknown. 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.)).

The Hammett value is usually used in the m-th and p-th values. The Hammett value used in the present invention is calculated as an electronic effect, and the o-th value is calculated as the same value as the p-th value.
The specific polymerization initiator may be substituted with an electron withdrawing group on the aryl ring, but the sum of Hammett values of all substituents with respect to the iodonium group is preferably 0 or less. However, the value of —OCH ₃ is used for the alkoxy group, and the value of —CH ₃ is used for the alkyl group.

The counter anion of the specific polymerization initiator can be used without limitation as long as it has an anion structure. Examples of the counter anion include a carboxylate anion, a sulfonate anion, a sulfonamide anion, a borate anion, a phosphate anion, a sulfinate anion, a sulfate anion, PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ and a halogen anion. Among these, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ and SbF ₆ ⁻ are preferable from the viewpoints of stability and sensitivity.

  The specific polymerization initiator may have a diaryl iodonium salt structure and may be a low molecular weight compound as long as a substituent is introduced into the aryl skeleton under specific conditions. It may have a plurality of diaryliodonium salt structures.

  Preferred specific examples (exemplary compounds: (I-1) to (I-41)) of diaryliodonium salts having (A) an aryl ring having a total of 3 or more electron donating groups on the aryl ring are listed below. It is not limited to. In some of the following exemplary compounds, the hydrocarbon chain is described by a simplified structural formula in which symbols of carbon (C) and hydrogen (H) are omitted. Table 1 shows the sum of Hammett values of all substituents with respect to the iodonium groups of the exemplary compounds (I-1) to (I-41).

  Moreover, the compound which combined the cation in the said compound of (I-1)-(I-41) and the anion ((E-1)-(E-16)) shown below can also be illustrated preferably (above-mentioned (I -1) to (I-41) are included.)

  (A) The production method of the diaryl iodonium salt having 3 or more electron donating groups in total on the aryl ring is not particularly limited, and a known diaryl iodonium salt synthesis method can be used. And the methods described in European Patent No. 104143, US Pat. No. 4,837,124, JP-A-2-150848, JP-A-2-96514 and the like.

In the specific curable composition, (a) the specific polymerization initiator may be used alone or in combination of two or more.
It is preferable that content of the photoinitiator contained in the curable composition of this invention is 0.5-30 mass% with respect to the total solid of a curable composition, More preferably, it is 1-20 mass. %. Within this range, good sensitivity and pattern formability can be obtained.

-Other polymerization initiators-
In addition to the specific polymerization initiator, other known polymerization initiators can be used in combination with the specific curable composition as long as the effects of the present invention are not impaired. Other known polymerization initiators that can be used in combination include, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, and azide compounds. , Metallocene compounds, biimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

((B) Photopolymerizable compound)
The specific curable composition contains the (B) photopolymerizable compound.
The photopolymerizable compound used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. . Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.

  Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.

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

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in JP-A-5-241 and JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

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

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

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(In the general formula (A), R ⁴ and R ⁵ represent H or CH _3. )

  Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 And urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

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

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

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

In the present invention, the following cationic polymerizable compound may be used as the photopolymerizable compound to form a cationic polymerization system or a hybrid of a radical polymerization system and a cationic polymerization system.
The cationically polymerizable compound refers to a compound that is polymerized or cross-linked by a radiation sensitive cationic polymerization initiator activated by irradiation with actinic radiation.

  The cationic polymerizable compound that can be used in the present invention is not particularly limited as long as it is a compound that initiates a polymerization reaction by a cationic polymerization initiating species generated from a specific polymerization initiator and cures, and is known as a photo cationic polymerizable compound. Various known cationically polymerizable compounds 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, vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526.

  Examples of the epoxy compound include aromatic epoxides, alicyclic epoxides, aliphatic epoxides, etc. As the aromatic epoxide, a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin, Di- or polyglycidyl ether produced by the reaction of, for example, di- or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, di- or polyglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and A novolac type epoxy resin and the like can be mentioned. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned preferably.

  Examples of the aliphatic epoxide include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or 1 Of diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or its adduct of alkylene oxide Dialkylidyl ether, polypropylene glycol, or polyalkylene glycol jig represented by diglycidyl ether of its alkylene oxide adduct Glycidyl ether and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The monofunctional and polyfunctional epoxy compounds that can be used in the present invention are exemplified in detail.
Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide. 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. It is done.

  Examples of the polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S di Glycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 -Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene Oxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxy cyclooctane, and the like.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  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, Di- or trivinyl ether compounds such as trimethylolpropane 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 Propyl vinyl ether, isopropyl vinyl ether, 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 the monofunctional vinyl ether include 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-methyl Cyclohexylmethyl 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 ether , 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, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, and the like.

  Examples of the polyfunctional vinyl ether 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 alkylene oxide. Divinyl ethers such as divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Savinyl 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 compound that can be used in the present invention refers to a compound having at least one oxetane ring, and is known as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. These oxetane compounds can be arbitrarily selected and used.
The compound having an oxetane ring that can be used in the present invention is preferably a compound having 1 to 4 oxetane rings in its structure. By using such a compound, it becomes easy to maintain the viscosity of the radiation-sensitive composition within a favorable range of handling properties, and when used as an ink composition, High adhesion can be obtained.

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

In 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.

In the formulas (1) to (3), 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, or a group having 2 to 6 carbon atoms. An alkylcarbonyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms are represented. 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.

In formulas (1) to (3), R ^a3 is a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, or a carbonyl group. Or an alkylene group containing a carbonyl group, an alkylene group containing a carboxyl group, 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.

In formulas (1) to (3), 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, or a halogen atom. , A nitro group, a cyano group, a mercapto group, 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 following formula, 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.

  Examples of the compound represented by the formula (1) include 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: manufactured by Toagosei Co., Ltd.). Examples of the compound represented by the formula (3) include bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: manufactured by Toagosei Co., Ltd.).

  As a compound which has 3-4 oxetane rings, the compound shown by following formula (4) is mentioned, for example.

In the formula (4), R ^a1 is synonymous with R ^a1 in the formula (1). In addition, as R ^a9 which is a polyvalent linking group, for example, a branched polyalkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a 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 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 the formula (5), R ^a1 and R ^a8 have 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 a compound having an oxetane ring is described in detail in JP-A No. 2003-341217, paragraphs 0021 to 0084, and the compound described herein can be suitably used in the present invention. In addition, oxetane compounds described in JP-A-2004-91556 can also be used in the present invention. This is described in detail in paragraphs 0022 to 0058.
Among the oxetane compounds that can be used in the present invention, it is preferable to use a compound having one oxetane ring from the viewpoint of the viscosity and tackiness of the composition of the present invention.

  The cationically polymerizable compound that can be used in the present invention may be used alone or in combination of two or more, but from the viewpoint of effectively suppressing shrinkage during curing, an oxetane compound and It is preferable to use an epoxy compound in combination.

  In addition, as the cationic polymerizable compound, for example, a cationic polymerization-based photocurable resin is known, and recently, a photocationic polymerization-based photocurable resin sensitized to a visible light wavelength region of 400 nm or more, For example, they are disclosed in JP-A-6-43633 and JP-A-8-324137.

Examples of the photo-cationic polymerization type photocurable resin include epoxy resins.
The epoxy resin that can be used in the present invention is not particularly limited as long as it has ion polymerizability, but has an epoxy group, and may further have a hydroxyl group. Examples of the epoxy group include compounds having terminal epoxy such as glycidyl ether and glycidyl ester, compounds having internal epoxy, and alicyclic epoxy groups.

  The epoxy resin is specifically exemplified below, but these can be used by mixing from the viewpoint of heat resistance, adhesiveness, and surface hardness. Examples of the epoxy resin include bisphenol type, novolak type, bromide type and the like. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, DPP A novolac type epoxy resin, a tris-hydroxyphenylmethane type epoxy resin, other polyfunctional type epoxy resins, a tetrabromobisphenol A type epoxy resin, etc. can be used according to the purpose.

  In addition, as the epoxy resin, alicyclic type, and as other, glycidyl methacrylate, 2-methyl-glycidyl methacrylate, epoxidized isoprenyl methacrylate, 3,4-epoxy widely used as (meth) acrylate having an epoxy group (Meth) acrylic acid ester of cyclohexanemethanol (meth) acrylate, ε-caprolactone modified product of 3,4-epoxycyclohexanemethanol (eg, Daicel Chemical Industries, Ltd., Cyclomer M100 (epoxy equivalents 196 to 213), A200 (epoxy equivalents 182 to 195), M101 (epoxy equivalents 326 to 355)) and the like can be used alone or copolymerized with other copolymerizable polymerizable monomers.

  Other copolymerizable polymerizable monomers include, for example, (meth) acrylic acid alkyl ester, hydroxyl group-containing (meth) acrylic acid alkyl ester, alicyclic (meth) acrylic acid ester, acrylic acid aromatic ester, Unsaturated fatty acid esters such as alicyclic methacrylates containing tertiary carbon in the ring and having 7 to 20 carbon atoms; styrene, α-methylstyrene, α-ethylstyrene, chlorostyrene, vinyltoluene, t-butyl Examples thereof include aromatic vinyl compounds such as styrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; N-substituted maleimides such as N-alkyl group-substituted maleimide, N-cycloalkyl-substituted maleimide, and N-phenylmaleimide. An initiator can be used when (meth) acrylate having an epoxy group or the like is polymerized alone or with other copolymerizable polymerizable monomers.

  Initiators include potassium persulfate, ammonium persulfate, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide. , Cumene hydroperoxide, t-butyl hydroperoxide, acetyl peroxide, methyl ethyl ketone peroxide, succinic acid peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, AIBN (2,2′-azobisiso Butyronitrile), ABN-E (2,2′-azobis (2-methylbutyronitrile)), ABN-V (2,2′-azobis (2,4-dimethylvaleronitrile)), perbutyl O (t -Butylperoxy 2-ethylhexanoate) It can be.

  The polymerization temperature is 50 to 150 ° C, preferably 90 to 130 ° C, and more preferably 100 to 120 ° C. When the polymerization temperature is higher than the above range, the polymerization becomes unstable and a large amount of a high molecular weight compound is formed. Another epoxy resin (A) can also be used for the solvent used at the time of the said superposition | polymerization. Moreover, after synthesizing a polymer using a solvent having no usual ion polymerizability, after removing the solvent, it can be diluted with the epoxy resin (A) to obtain a resin composition. Examples of the solvent having no ionic polymerizability include aromatic solvents such as toluene and xylene, methyl ethyl ketone, methyl isobutyl ketone, methoxypropylene glycol acetate, and the like. These may be used alone or in combination. it can.

  Examples of the epoxy resin include CEL-2021P (3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate, epoxy equivalent 128-140, viscosity 200-350 cP / 25 ° C.), CEL-2021A (3 , 4-epoxycyclohexylmethyl 3′4′-epoxycyclohexanecarboxylate, epoxy equivalent 130-145, viscosity 200-450 cP / 25 ° C., CEL-2000 (1-vinyl-3,4-epoxycyclohexane, 1.5 cP / 25 ° C.), CEL-3000 (1,2,8,9-diepoxy limonene, epoxy equivalent 93.5 or less, viscosity 5 to 20 cP / 25 ° C.) (manufactured by Daicel Chemical Industries), Denacol EX-421, 201 (Resorcin diglycidyl ether), 211 (ne Neopentyl glycol diglycidyl ether), 911 (propylene glycol diglycidyl ether), 701 (adipic acid diglycidyl ester) (can be added more Nagase Chemicals Ltd.) and the like.

Furthermore, vinyl ether which is a compound having ionic polymerizability, oxetane, or the like can be used in combination with the epoxy resin. When these vinyl ethers and oxetane are blended, it is desirable that the amount is 30% by mass or less with respect to 100% by mass in total of the epoxy resin and the vinyl ether or oxetane.
The ratio of the compound having these epoxy groups in the resin composition comprising an epoxy resin is 20 to 90% by mass, preferably 40 to 80% by mass.

((C) Colorant)
The specific curable composition contains (C) a colorant.
There is no restriction | limiting in particular in the coloring agent contained in a specific curable composition, 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 of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable. Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

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

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

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

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

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 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 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 of this invention, it is preferable that it is 25-95 mass% in the total solid of a curable composition, and 30-90 mass% is more. Preferably, 40-80 mass% is still more preferable.
If the amount of the colorant is too small, there is a tendency that an appropriate chromaticity cannot be obtained when a color filter is produced with the curable composition of the present invention. On the other hand, if the amount is too large, the photocuring does not proceed sufficiently and the strength as a film is lowered, 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.

[Sensitizing dye]
The specific curable composition preferably contains a sensitizing dye for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
As the sensitizing dye that can be used in the present invention, a sensitizing dye that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.
Examples of the sensitizing dye that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred 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 the basicity of the dye in combination with the adjacent A ¹ and the adjacent carbon atom. Represents a nonmetallic atomic group forming a nucleus, 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 W may represent 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 —, where L ² represents —O— or —S—. In addition, W is synonymous with that shown in 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 the 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 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 —, and 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. And R ⁶⁰ and R ⁶¹ each independently represents a monovalent non-metallic atomic group, or can be bonded to each other to form an aliphatic or aromatic ring.)

The content of the sensitizing dye in the curable composition of the present invention is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency, and is 0. More preferably, the content is 5 to 15% by mass.
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 (e) sensitizing dye, the compound represented by the following general formula (II) and the following general formula (III) The at least 1 type selected from a compound is mentioned. These may be used individually by 1 type, and may use 2 or more types together.

In general 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. To express. 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 general formula (II), the isomer by the double bond is not limited to either one.

The compound represented by the general 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} or more is more preferable, and 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.

Although the preferable specific example of a compound represented by general formula (II) is illustrated below, this invention is not limited to these.
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 general 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 ) —, and 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 general 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 general 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 general 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.

The compound represented by the general formula (III) according to the present invention can be further subjected to various chemical modifications for improving the properties of the curable composition.
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 of the present invention, the compound represented by the general formula (II) or (III) may be used alone or in combination of two or more.

  The compound represented by the above general formula (II) or (III) has a very high colorant concentration in the curable composition, and the light transmittance of the formed colored pattern (photosensitive layer) is extremely low. In this case, 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 is remarkably exhibited. Is done. Particularly, among the above-mentioned general formula (II) or (III), the compound represented by the general 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 diaryl iodonium salt having a total of three or more electron donating groups on the aryl ring, (B) a photopolymerizable compound, (C) a colorant, and You may further contain the arbitrary component explained in full detail below with a sensitizing dye as needed. Hereinafter, optional components that can be contained in the curable composition of the present invention will be described.

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

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

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

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

As content of the dispersing agent in this invention, it is preferable that it is 1-80 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, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

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

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

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, 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 specific curable composition preferably also contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

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

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

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

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

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, 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.

  The specific curable composition is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to hard material surfaces, such as a board | substrate which applies a curable composition, is shown.

<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 the present invention can be manufactured by forming a pattern film as follows.
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 a curable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is further 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 of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition has excellent development resistance. It is possible to form a high-resolution pattern that is excellent in sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” is based on mass.
<Synthesis of specific polymerization initiator>
Below, the specific synthesis example of the compounds 1-6 which are specific polymerization initiators is given, and a detail is demonstrated.

(Synthesis Example 1)
6.62 g of octyloxyiodobenzene (iodoaryl compound) was dissolved in 20 ml of acetic acid and stirred. The temperature was maintained at 30 ° C., and 0.25 g of picolinic acid (a compound having an amino group and a carboxylic acid group in the molecule) was added thereto, followed by stirring at room temperature for 10 minutes. Adjust the temperature to 30 ° C, slowly add 8.0 g of 38-39% peracetic acid / acetic acid solution over 1 hour, stir at 30 ° C-35 ° C for 6 hours, leave at room temperature for 12 hours, add 30 ml of acetonitrile dropwise. Then, cool to ice so that the internal temperature is 5 ° C. or less, add 3.20 g of 1,3,5-trimethoxybenzene (aromatic compound), and dissolve 5.5 g of KPF _{6 in} 50 ml of distilled water. It was dripped. afterwards,
The mixture was stirred at 5 ° C. or lower for 2 hours, then poured into 500 ml of ice water, extracted with 500 ml of dichloromethane, and the aqueous layer was further extracted with 200 ml of dichloromethane. The organic layer was washed with an aqueous solution in which 75.6 g of sodium sulfite was dissolved in 500 ml of water, and the organic layer was further washed twice with 300 ml of water. The organic layer is concentrated until the amount of the solvent becomes 1/10, 100 ml of ethyl acetate is added, the mixture is concentrated again, and left to stand to give the following compound A (I-38) (exemplary compound: (I-38)) 7 .05 g (yield: 53%) was obtained. The HPLC purity was 98.7%.

(Synthesis Example 2)
In Synthesis Example 1, 1,3,5-trimethoxybenzene was changed to 1,3,5-trimethylbenzene, and the reaction was carried out. As a result, the following iodonium salt B (I-39) (Exemplary compound: (I-39 )) Was obtained in a yield of 65%. The HPLC purity was 97.8%.

<Synthesis Example 3>
In Synthesis Example 1, when 4-octyloxyiodobenzene was changed to iodobenzene and the reaction was carried out, the following iodonium salt C (I-4) (exemplary compound: (I-4)) was obtained in a yield of 61%. It was. The HPLC purity was 98.4%.

<Synthesis Example 4>
In Synthesis Example 1, when 4-octoxyoxyiodobenzene was changed to 4-butoxyiodobenzene and the reaction was carried out, the following iodonium salt D (I-2) (exemplary compound: (I-2)) was obtained in a yield of 68. %. The HPLC purity was 99.0%.

<Synthesis Example 5>
In Synthesis Example 1, when KPF ₆ was changed to the following compound X (manufactured by Aldrich) and the reaction was carried out, the following iodonium salt E (I-40) (exemplary compound: (I-40)) was obtained in a yield of 58%. Was obtained. The HPLC purity was 97.0%.

<Synthesis Example 6>
In Synthesis Example 1, when KPF ₆ was changed to the following compound Y (manufactured by Tokyo Chemical Industry Co., Ltd.) and the reaction was carried out, the following iodonium salt F (I-41) (exemplary compound: (I-41)) was obtained. Obtained in a yield of 64%. The HPLC purity was 96.0%.

  The compounds obtained in the above Synthesis Examples 1 to 6 were converted to Compounds 1 to 6 as described in Tables 2 and 3, and used in the following Examples together with Comparative Compounds 1 and 2 described in Table 3.

Hereinafter, the color filter of the present invention and the method for producing the same will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
<Example 1-1>
[1. Preparation of curable composition]
1-1. Preparation of pigment dispersion C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of a 30/70 (mass ratio) mixture with Pigment Yellow 219, and 10 parts by mass (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 obtained 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-polyfunctional monomer dipentaerythritol hexaacrylate: 60 parts by mass
・ Polymerization initiator (compound 1, details are listed in Table 2): 60 parts by mass ・ Propylene glycol monomethyl ether acetate: 1000 parts by mass ・ Surfactant (trade name: Tetranic 150R1, BASF): 1 part by mass Sensitizer (postscript A1): 40 parts by mass-thiol compound (postscript S1): 20 parts by mass-γ-methacryloxypropyltriethoxysilane: 5 parts by mass,

[2. (Production of color filter)
2-1. Formation of the curable composition layer The curable composition containing the pigment obtained as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate by slit coating under the following conditions, and then waited for 10 minutes as it was. It apply | coated to the glass substrate and vacuum-dried and prebaked (prebaking (100 degreeC80 second)), and formed the curable composition coating film (curable composition layer).

(Slit application conditions)
Gap at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure and development Thereafter, the photocurable coating film 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, exposure sensitivity of the curable composition coating film (colored layer) formed on the glass substrate using the colored curable composition, and substrate adhesion Property, developability, and pattern cross-sectional shape were evaluated as follows. The results are shown in Table 4.

3-1. Storage stability of curable composition After the colored 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.

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:

-Board adhesion-
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

<Examples 1-2 to 1-14>
In the curable composition of Example 1-1, a coloring pattern was formed in the same manner as in Example 1-1 except that the polymerization initiator, thiol compound, and sensitizer were replaced with the compounds shown in Table 4 below. Obtained and evaluated in the same manner as in Example 1-1. The results are shown in Table 4. The details of D1 to D3, A1 to 4, and S1 to 3 in Table 4 are as follows.

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-phenyl mercaptobenzimidazole S2: Mercaptobenzthiazole S3: 2-mercapto-5-methyltriazole A1: 4,4-bisdiethylaminobenzophenone

<Comparative Example 1-1>
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-polyfunctional monomer dipentaerythritol hexaacrylate: 60 parts by mass
Polymerization initiator (Irgacure OXE-01): 140 parts by mass Propylene glycol monomethyl ether acetate: 1000 parts by mass Surfactant (trade name: Tetranic 150R1, BASF): 1 part by mass In Example 1-1, A colored pattern was obtained in the same manner as in Example 1-1 except that the curable composition was changed to the curable composition obtained above, and the same evaluation as in Example 1-1 was performed. The results are shown in Table 4.

<Comparative Examples 1-2 to 1-3>
In the curable composition of Example 1-1, all were performed in the same manner as in Example 1-1 except that the polymerization initiator, the thiol compound, and the sensitizer were replaced with the compounds shown in Table 4. The results are shown in Table 4.

<Example 2-1>
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-Polyfunctional monomer dipentaerythritol hexaacrylate: 20 parts by mass-Polymerization initiator (compound 1, details are given in Table 2): 60 parts by mass-Propylene glycol monomethyl ether acetate: 1000 parts by mass- Surfactant (trade name: Tetranic 150R1, BASF): 1 part by mass / 9,10-dibutoxyanthracene (sensitizer, A5): 40 parts by mass / γ-methacryloxypropyltriethoxysilane: 5 parts by mass -Celoxide 201P (Daicel Chemical): 20 parts by mass-Oxetane OXT-221 (Toagosei): 20 parts by mass

  In Example 1-1, a colored pattern was obtained in the same manner as in Example 1-1 except that the curable composition was changed to the curable composition obtained above, and the same as in Example 1-1. Was evaluated. The results are shown in Table 5.

<Example 2-2, Comparative Examples 2-1 to 2-2>
In the curable composition of Example 2-1, a coloring pattern was obtained in the same manner as in Example 2-1, except that the polymerization initiator was changed as shown in Table 5 below. The same evaluation was performed. The results are shown in Table 5.

  From the results of Table 5, the colored curable compositions of the examples using the curable composition of the present invention are excellent in storage stability in the solution state, and when an image is formed on the support, it is out of the scope of the present invention. It turns out that exposure sensitivity is high with respect to the comparative example using a polyfunctional acrylate type comparative polymerizable compound, and it is excellent in all of developability, board | substrate adhesiveness, and pattern cross-sectional shape.

<Example 3-1>
1) Preparation of resist solution for undercoating A component having the following composition was mixed and dissolved to prepare a resist solution.
<composition>
Propylene glycol monomethyl ether acetate: 19.20 parts by mass (PGMEA)
-Ethyl lactate: 36.67 parts by mass-Resin: 30.51 parts by mass [40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18) ]
Dipentaerythritol hexaacrylate: 12.20 parts by mass (photopolymerizable compound)
Polymerization inhibitor (p-methoxyphenol): 0.0061 parts by mass Fluorosurfactant: 0.83 parts by mass (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
Photopolymerization initiator: 0.586 parts by mass (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)

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

3) Preparation of curable composition The compound of the following composition A-1 was mixed and melt | dissolved, and curable composition A-1 was prepared.
<Composition A-1>
Cyclohexanone: 80 parts by mass Colorant CI Acid Blue 108: 7.5 parts by mass Colorant CI Solvent Yellow 162: 2.5 parts by mass Radical polymerizable monomer: 7.0 parts by mass [tetramethylolpropane triacrylate and di 3: 7 mixture with pentaerythritol hexaacrylate]
Polymerization initiator (compound 1, details are listed in Table 2): 1 part by mass Sensitizer 4,4-bisdiethylaminobenzophenone (A1): 0.7 part by mass Thiol compound (S2): 0.4 part by mass Part Glycerol propoxylate: 0.5 part (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0, colorless compound according to the present invention)

Performance evaluation 4) Coating solution storage stability (storage stability)
After the coating solution was stored at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
<Criteria>
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

5) Exposure / development and evaluation of curable composition-Pattern formation and sensitivity evaluation-
The curable composition A-1 prepared in 3) above was applied onto the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in 2) above 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 Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  A silicon wafer substrate on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 rpm by a rotating device, while being pure from above the rotation center. Water was supplied in a shower form from the ejection nozzle to perform rinsing, and then spray-dried. 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 exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. Moreover, the size (pattern size A) of the coloring pattern was measured using length measuring SEM "S-9260A" (made by Hitachi High-Technologies Corporation) in that case. The closer the pattern size is to 2 μm, the better the curability and the better the sensitivity. Moreover, developability, pattern cross-sectional shape, and substrate adhesion were evaluated in the same manner as in Example 1-1. The results are shown in Table 6.

<Examples 3-2 to 3-15, Comparative Examples 3-1 to 3-6>
In Example 3-1, except that the polymerization initiator, thiol compound, and sensitizer in Composition A-1 used for the preparation of curable composition A-1 were each changed as shown in Table 6, Example A colored pattern was formed and evaluated in the same manner as in 3-1. The results are shown in Table 6.
Further, the following curable compositions B-1 to D-1 were prepared, and the curable compositions B-1 were changed in the polymerization initiator, thiol compound, and sensitizer as shown in Table 6. A composition was prepared, and a colored pattern was formed in the same manner as in Example 3-1, except that curable compositions B-1 to D-1 were used instead of curable composition A-1. Evaluation was performed. The results are shown in Table 6.

The compound of the following composition B-1 was mixed and melt | dissolved, and curable composition B-1 was prepared.
<Composition B-1>
Cyclohexanone: 80 parts by weight Colorant CIPigmentRed 254: 6.0 parts by weight Colorant CIPigment Yellow 139: 4.0 parts by weight Radical polymerizable monomer: 7.0 parts by weight [tetramethylolpropane triacrylate and dipentaerythritol hexa 3: 7 mixture with acrylate]
Photopolymerization initiator (compound 1, details are listed in Table 2): 1 part by mass Sensitizer (A4): 0.7 part by mass Thiol compound (S1): 0.4 part by mass Glycerol propoxylate ( Number average molecular weight Mn: 1500): 0.5 part by mass

A compound having the following composition C-1 was mixed and dissolved to prepare a curable composition C-1.
<Composition C-1>
Cyclohexanone: 80 parts by mass Colorant CI Acid Blue 108: 7.5 parts by mass Colorant CI Solvent Yellow 162: 2.5 parts by mass Radical polymerizable monomer: 7.0 parts by mass [tetramethylolpropane triacrylate and di 3: 7 mixture with pentaerythritol hexaacrylate]
Photopolymerization initiator: 2.5 parts by mass (Irgacure OXE-01, manufactured by Ciba Specialty Chemicals; oxime photopolymerization initiator)
Glycerol propoxylate (number average molecular weight Mn: 1500): 0.5 part by mass

A compound having the following composition D-1 was mixed and dissolved to prepare a curable composition D-1.
<Composition D-1>
Cyclohexanone: 80 parts by weight Colorant CIPigmentRed 254: 6.0 parts by weight Colorant CIPigment Yellow 139: 4.0 parts by weight Radical polymerizable monomer: 7.0 parts by weight [tetramethylolpropane triacrylate and dipentaerythritol hexa 3: 7 mixture with acrylate]
Photopolymerization initiator: 2.5 parts by mass (Irgacure OXE-01, manufactured by Ciba Specialty Chemicals; oxime photopolymerization initiator)
Glycerol propoxylate: 0.5 parts by mass (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0, colorless compound according to the present invention)

<Examples 4-1 to 4-3, Comparative Examples 4-1 to 4-2>
The compound of the following composition Y-1 was mixed and melt | dissolved, and curable composition Y-1 was prepared.
<Composition Y-1>
Cyclohexanone: 80 parts by mass Colorant CI Acid Blue 108: 7.5 parts by mass Colorant CI Solvent Yellow 162: 2.5 parts by mass Radical polymerizable monomer: 0.2 parts by mass [tetramethylolpropane triacrylate and di 3: 7 mixture with pentaerythritol hexaacrylate]
-Celoxide 201P (Daicel Chemical); 0.4 parts by mass-Oxetane OXT-221 (Toagosei): 0.4 parts by mass-Polymerization initiator (compound 1, details are given in Table 2): 1 part by mass-Sensitization Agent: 9,10-dibutoxyanthracene (A5): 0.7 parts by mass Glycerol propoxylate: 0.5 parts (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0, colorless compound according to the present invention)

  In Example 3-1, Example 4-1 was performed in the same manner as Example 3-1, except that the curable composition A-1 was changed to the curable composition Y-1. Further, Examples 4-2 to 4-3 and Comparative Examples 4-1 to 4-2 were carried out in the same manner as Example 4-1, except that the polymerization initiator was changed to the compounds shown in Table 7. did. The results are shown in Table 7.

Claims (4)

  (A) A curing for a color filter comprising a diaryl iodonium salt having three or more electron donating groups on the aryl ring, (B) a photopolymerizable compound, and (C) a colorant. Sex composition.   The curable composition for a color filter according to claim 1, wherein all of the electron donating groups are alkoxy groups.   A color filter comprising a colored pattern formed using the curable composition for a color filter according to claim 1 or 2 on a support.   A step of applying a curable composition for a color filter according to claim 1 or 2 on a support to form a colored curable composition layer, and exposing the colored curable composition layer through a mask. A method for producing a color filter, comprising: a step; and a step of developing the colored curable composition layer after exposure to form a colored pattern.