JP2008276130A - Curable composition for color filter, and color filter, and method for manufacturing same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for color filters which has high storage stability, ensures high sensitivity (a high cure degree at a small amount of light exposure) even in the case of a small amount of a polymerizable component in the presence of air, and has excellent developability. <P>SOLUTION: The curable composition for color filters comprises a compound having an oxetanyl group, a triarylsulfonium salt having at least one aryl skeleton having an electron withdrawing group as a substituent and/or a diaryliodonium salt having at least one aryl skeleton having an electron donating group as a substituent, an alkali-soluble resin and a colorant. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable composition for a color filter suitable for producing a color filter used for a solid-state imaging device or a liquid crystal display device, a color filter using the same, and a method for producing the same.

  In color filters for solid-state imaging devices, it is required to reduce the thickness of the colored pattern, and in order to reduce the thickness of the color pattern as before, the inclusion of the colorant in the curable composition used for the production of the color filter There is a demand for higher rates.

  In color filters for liquid crystal displays, higher image quality is required, and as one means for that purpose, improvement of color purity can be mentioned. In order to improve the color purity, it is required to increase the content of the colorant in the solid content of the curable composition.

  As described above, in any case for a solid-state imaging device or a liquid crystal display, in order to increase the content of the colorant in the curable composition, the photopolymerization initiator, which is necessarily a curing component, photopolymerizable Problems such as the content of the monomer and the alkali-soluble resin is limited, the strength is insufficient, or the curability is insufficient and the adhesion to the hard surface as the base material cannot be obtained sufficiently. There is. In recent years, there has been a demand for a curable composition that maintains a pattern shape for a long time even in a developing solution in a developing process, has no pattern chipping or peeling, and has a high sensitivity as the substrate size increases. In particular, in color filters for solid-state imaging devices that require thinning, the ratio of the polymerization component is low in order to keep the chromaticity constant, and when polymerizing in air, it is usually cured by radical polymerization that is generally used. Is getting harder.

  In recent years, therefore, development of a more sensitive curing system that can sufficiently cure the radiation-sensitive composition for color filters even in the air and under irradiation with low energy has been attempted. Among them, a curing system using a compound having an oxetanyl group has been reported. As an initiator for a color filter used in the curing system, a biimidazole compound, an acetophenone compound, a triazine compound (for example, a patent document) 1), benzophenone-based peracid compounds (see, for example, Patent Document 2), 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butan-1-one (for example, refer to Patent Document 3) and the like are disclosed.

In addition, an example is disclosed in which an oxetanyl group is provided as a reactive group in an alkali-soluble resin to improve the film strength and the solubility of the composition (see, for example, Patent Document 4).
Japanese Patent Laid-Open No. 2000-214592 JP 2003-255531 A JP 2003-131374 A JP 2006-301055 A

  However, even in the case of these radiation-sensitive compositions, the sensitivity is still not at a satisfactory level, and it is necessary to irradiate with high energy radiation. Alternatively, problems such as a decrease in pixel intensity, developability of the resulting film, and poor pattern shape remain. In order to solve these problems, development of a new photocuring system is desired.

  The present invention has been made in view of the above, has high storage stability, high sensitivity (high curing degree at low exposure) even with a small amount of polymerization components in the presence of air, and excellent developability, Curing for color filters that can form a pattern with good pattern profile (especially when the cut surface is tapered or rectangular when cut in a plane parallel to the normal direction of the pattern surface) and excellent adhesion to the pattern formation object Provided are a color filter excellent in substrate adhesion and having a good pattern profile (particularly, the cut surface is tapered or rectangular when cut in a plane parallel to the normal direction of the substrate) and a method for producing the same. It is an object to achieve this purpose.

Specific means for achieving the above object are as follows.
<1> (A) a compound having an oxetanyl group, (B) a triarylsulfonium salt having at least one aryl skeleton having an electron withdrawing group as a substituent, and / or an electron donating group as a substituent A curable composition for a color filter, comprising at least a diaryl iodonium salt having at least one aryl skeleton, (C) an alkali-soluble resin, and (D) a colorant.
<2> The curable composition for a color filter according to <1>, wherein the triarylsulfonium salt (B) has a sum of Hammett values of substituents bonded to the aryl skeleton of 0.46 or more. It is a thing.
<3> The color filter according to <1> or <2>, wherein the diaryl iodonium salt (B) has a sum of Hammett values of substituents bonded to an aryl skeleton of −0.2 or less. It is a curable composition.

<4> The curable composition for a color filter according to any one of <1> to <3>, further comprising (E) a radical polymerizable compound.
<5> The color according to any one of <1> to <4>, further comprising (F) a radical polymerization initiator other than (B) the triarylsulfonium salt and the diaryliodonium salt. It is a curable composition for filters.
<6> The curable composition for color filters according to <5>, wherein the (F) radical polymerization initiator is an oxime polymerization initiator.
<7> A color filter formed using the curable composition for a color filter according to any one of <1> to <6>.
<8> The curable composition for a color filter according to any one of <1> to <6> is applied onto a support, and the curable layer thus formed is exposed through a mask and developed. It is a manufacturing method of the color filter which forms a pattern.

According to the present invention, storage stability is high, high sensitivity (low curing amount and high degree of curing) can be obtained even with a small amount of polymerization components in the presence of air, excellent developability, and good pattern profile (especially pattern) To provide a curable composition for a color filter capable of forming a pattern excellent in adhesiveness with a pattern forming object having a cut surface of a taper shape or a rectangular shape when cut in a plane parallel to the normal direction of the surface. Can do. Also,
According to the present invention, a color filter having excellent substrate adhesion and a good pattern profile (particularly when the cut surface is a forward tapered shape or a rectangle when cut in a plane parallel to the normal direction of the substrate) and a method for manufacturing the same are provided. can do.

  Hereinafter, the curable composition for a color filter of the present invention will be described in detail, and the color filter of the present invention and the manufacturing method thereof will be described in detail through the description.

<Curable composition for color filter>
The curable composition for a color filter of the present invention (hereinafter sometimes simply referred to as “curable composition”) has (A) a compound having an oxetanyl group and (B) an electron withdrawing group as a substituent. A triarylsulfonium salt having at least one aryl skeleton, and / or a diaryliodonium salt having at least one aryl skeleton having an electron donating group as a substituent, (C) an alkali-soluble resin, and (D) at least a colorant. Preferably, it contains (E) a radical polymerizable compound and (F) a radical polymerization initiator. Moreover, it can comprise using another component as needed.

  The curable composition for a color filter of the present invention particularly includes a triarylsulfonium salt and / or diaryliodonium salt, a compound having an oxetanyl group, and an alkali-soluble resin (preferably having a carboxyl group). When the light is irradiated, an acid catalyst is generated and crosslinked between the oxetanyl group and the alkali-soluble resin (preferably a carboxyl group), and the high molecular weight of the alkali-soluble resin proceeds to form a film. At the same time, an alkali-soluble group (particularly a carboxyl group) of the alkali-soluble resin is converted into an alkali-insoluble ester group, so that a pattern having good developability and a good pattern shape can be formed. In addition, when a dye containing an acidic group is used as a colorant, since the dye is crosslinked with the oxetanyl group, high sensitivity can be obtained, curing can be performed well even at a low exposure amount, and high developability can be obtained. Therefore, a pattern having a good shape can be formed. When a pigment is used as a colorant, a dispersion resin is used at the same time, so that the acidic group and oxetanyl group of the dispersion resin are cross-linked, so that high sensitivity can be obtained, and curing can be performed well even at a low exposure amount. Since high developability is obtained, a pattern having a good shape can be formed as described above.

  (D) As the colorant, dyes and pigments are preferably used. Above all, when the concentration of the colorant is 40% by mass or more, the curable composition for a color filter of the present invention is preferably used. It is more preferably used when the concentration of is 50% by mass or more, and particularly preferably when the concentration of the colorant is 60% by mass or more.

Hereinafter, each component which comprises the curable composition for color filters of this invention is demonstrated in detail.
The curable composition for a color filter of the present invention can be suitably configured to form an exposed portion and a non-exposed portion by irradiating light in a pattern. In this case, the alkali is developed in the non-exposed portion. Since the soluble resin remains relatively low in molecular weight and has many alkali-soluble groups such as carboxyl groups, it is dissolved and removed. On the other hand, in the exposed area, an acid catalyst is generated, and polymerization of the oxetane and / or cross-linking of the oxetane group and an alkali-soluble group such as a carboxyl group progresses the polymerization of the alkali-soluble resin, and the carboxyl group becomes an ester. As a result, the solubility in the developer is lowered, and the film remains as a film constituting a pattern having a good pattern shape. In addition, when a dye containing an acidic group is used as the colorant, the dye is cross-linked with the oxetanyl group, so that a high molecular weight product is generated from the compound having the oxetanyl group, the acidic dye, and the alkali-soluble resin. Higher sensitivity and higher developability can be obtained, and a pattern having a good pattern shape can be formed. In addition, when a pigment is used as the colorant, since the dispersion resin is used at the same time, the acidic group or alkali-soluble group of the dispersion resin and the oxetanyl group are cross-linked, and higher sensitivity and higher developability are obtained. A pattern having a simple pattern shape can be formed. However, if only short-time light irradiation is not sufficient, the crosslinking density is insufficient, and it can withstand alkali development but is insufficient in terms of resistance to heat, light, and various solvents. It is possible to develop a high degree of stripping solution resistance and solvent resistance by thermal crosslinking with. Here, by selecting a polymerization initiator, a polymerization accelerator, etc., it can be configured so that photocuring can be performed using visible light, electron beam, etc. in addition to ultraviolet rays. In addition to using a circulation dryer, it can be performed by heating using a heating device such as far-infrared heating, a hot plate, or a high-frequency induction furnace.

-(A) Compound having oxetanyl group-
The curable composition for a color filter of the present invention contains at least one compound containing an oxetanyl group as the curable compound. This compound should just have a 4-membered ring structure which has an oxygen atom, and the compound which has two or more oxetanyl groups in a molecule | numerator is preferable. For example, known oxetane compounds described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217 can be arbitrarily selected and used.

  Examples of the compound having two or more oxetanyl groups in the molecule include compounds represented by the following formulas (1) to (6).

In the formula (1), R ^a1 and R ^a2 each independently represent a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, a fluoroalkyl group having 1 to 24 carbon atoms, an allyl group, an aralkyl group, an aryl group, hetero An aryl group, an amino group, an acyl group having 1 to 24 carbon atoms, an alkoxycarbonyl group having 2 to 24 carbon atoms, an aryloxycarbonyl group having 2 to 24 carbon atoms, an alkylcarbamoyl group having 2 to 24 carbon atoms, Or represents a carbamoyloxy group or the like. Two R ^a1 and R ^a2 present in the molecule may be the same or different.

  Examples of the alkyl group having 1 to 24 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, decane, cyclodecane and the like. Especially, a C1-C12 alkyl group is preferable and C1-C6 is especially preferable.

  The fluoroalkyl group having 1 to 24 carbon atoms is one in which at least one hydrogen of the alkyl group is substituted with a fluorine atom. For example, trifluoromethyl group, nonafluorobutyl group, nonafluorodecanyl, hexafluoro Isopropyl is mentioned. Especially, a C1-C12 fluoroalkyl group is preferable and a C1-C6 fluoroalkyl group is especially preferable.

  As said aralkyl group, a C1-C24 aralkyl group is preferable, for example, 3-phenylpropyl, 2-phenylbutyl, 4-naphthyl nonyl is mentioned. Especially, a C1-C12 aralkyl group is preferable and a C1-C8 aralkyl group is especially preferable.

  The aryl group is preferably an aryl group having 6 to 24 carbon atoms, and examples thereof include phenyl, p-fluorophenyl, naphthyl, and anthracenyl. Among them, an aryl group having 6 to 12 carbon atoms is preferable, and an aryl group having 6 to 8 carbon atoms is particularly preferable.

  The heteroaryl group is preferably a heteroaryl group having 1 to 24 carbon atoms, for example, a pyrrolyl group, a furyl group, a thiophenyl group, a benzopyrrolyl group, a benzofuryl group, a benzothiophenyl group, a pyrazolyl group, an isoxazolyl group, an isothiazolyl group, Indazolyl group, benzisoxazolyl group, benzisothiazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, pyridyl group, quinolinyl group, isoquinolinyl group, pyridazinyl group, pyrimidinyl Group, pyrazinyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, acridinyl group, phenanthridinyl group, phthalazinyl group, carbazolyl group, carbolinyl group, purinyl group, triazolyl , Oxadiazolyl group, thiadiazolyl group. Especially, a C2-C12 heteroaryl group is preferable and a C2-C8 heteroaryl group is especially preferable.

  Examples of the amino group include amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, and cyclohexylamino. Among these, an amino group having 24 or less carbon atoms is preferable.

  The acyl group having 1 to 24 carbon atoms is preferably an acyl group having 1 to 12 carbon atoms, and examples thereof include formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, and cyclohexanoyl. Among them, an acyl group having 1 to 8 carbon atoms is preferable, and an acyl group having 2 to 6 carbon atoms is particularly preferable.

  Examples of the alkoxycarbonyl group having 2 to 24 carbon atoms include methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, and cyclohexyloxycarbonyl. Among these, an alkoxycarbonyl group having 2 to 12 carbon atoms is preferable, and an alkoxycarbonyl group having 2 to 8 carbon atoms is particularly preferable.

  Examples of the aryloxycarbonyl group having 2 to 24 carbon atoms include phenoxycarbonyl and naphthoxycarbonyl. Among them, an aryloxycarbonyl group having 2 to 12 carbon atoms is preferable, and an aryloxycarbonyl group having 2 to 8 carbon atoms is particularly preferable.

  Examples of the alkyl carbamoyl group having 2 to 24 carbon atoms include carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, and N-phenylcarbamoyl. N-methyl-N-phenylcarbamoyl and N, N-dicyclohexylcarbamoyl. Among them, an alkylcarbamoyl group having 2 to 12 carbon atoms is preferable, and an alkylcarbamoyl group having 2 to 8 carbon atoms is particularly preferable.

  The carbamoyloxy group is preferably an alkoxycarbamoyl group having 2 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy. Is mentioned. Among these, an alkoxycarbamoyl group having 2 to 12 carbon atoms is preferable, and an alkoxycarbamoyl group having 2 to 8 carbon atoms is particularly preferable.

  In the formula (1), X represents a divalent organic group. Examples of divalent organic groups include linear or branched alkylene groups, linear or branched poly (alkyleneoxy) groups, linear or branched unsaturated hydrocarbon groups, alkylene groups including carbonyl groups, carboxyl groups Examples thereof include an alkylene group containing a group, an alkylene group containing a carbamoyl group, and the following linking groups (i) to (iii).

Examples of the linear or branched alkylene group include an ethylene group, a propylene group, a butylene group, a 2-ethylpropylene group, and a 2-phenylmethylbutylene group, and an alkylene group having 1 to 24 carbon atoms is preferable. An alkylene group having 1 to 12 carbon atoms is more preferable.
Examples of the linear or branched poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group, and a poly (alkyleneoxy) group having 1 to 24 carbon atoms is preferable. A poly (alkyleneoxy) group having 1 to 12 carbon atoms is more preferred.
Examples of the linear or branched unsaturated hydrocarbon group include propenylene, methylpropenylene, butenylene, 2-ethylpropenylene, 2-phenylbutynylene, and the like, and an unsaturated hydrocarbon having 1 to 24 carbon atoms. Group is preferable, and an unsaturated hydrocarbon group having 1 to 12 carbon atoms is more preferable.
Examples of the alkylene group containing a carbonyl group include 2-acetyl-propylene, 3-benzoyl-pentylene, decanylene-3-one, etc., an alkylene group having 1 to 24 carbon atoms is preferable, and an alkylene group having 1 to 12 carbon atoms. preferable.
Examples of the alkylene group containing a carboxyl group include 2-carboxyl-propylene, 3-carboxyl-butylene, 3-carboxyl-pentylene, etc., an alkylene group having 2 to 24 carbon atoms is preferable, and an alkylene group having 2 to 12 carbon atoms. An alkylene group is more preferred.
Examples of the alkylene group containing a carbamoyl group include 2-carbamoyl-propylene, 3-carbamoyl-pentylene, 3-carbamoyl-pentylene, etc., preferably an alkylene group having 2 to 48 carbon atoms, and having 2 to 24 carbon atoms. An alkylene group is more preferred.

R ^a3 in the linking group (i) is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, cyclohexyl, nonyl, decanyl), or an alkoxy group having 1 to 24 carbon atoms. (Eg, methoxy, ethoxy, butoxy), halogen atom (eg, chlorine atom, bromine atom, fluorine atom), nitro group, cyano group, mercapto group, alkyl carboxyl group (preferably an alkyl carboxyl group having 1 to 24 carbon atoms) Represents, for example, 3-carboxylpropyl, 2-carboxylpropyl, 6-carboxylnonyl), a carboxyl group, or a carbamoyl group. Among them, R ^a3 is preferably an alkyl carboxyl group or a carboxyl group from the viewpoint of high sensitivity and developability.

In the linking group (ii), R ^a4 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or the like, An atom and a methylene group are preferable.
In the linking group (iii), R ^a5 represents an alkoxy group having 1 to 24 carbon atoms (for example, a methoxy group, an ethoxy group, or a butoxy group), or an aryl group (preferably an aryl group having 6 to 24 carbon atoms, for example, Phenyl group, p-methoxyphenyl group, naphthyl group, anthracenyl group), and phenyl group and naphthyl group are preferable.
R ^a6 is an alkyl group having 1 to 24 carbon atoms (for example, a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, or a nonyl group), an aryl group (preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group). , P-methoxyphenyl group, naphthyl group, anthracenyl group) or a monovalent group (iv) having the following structure.
n is an integer of 0 to 2,000, preferably 0 to 500.

In the monovalent group (iv), R ^a7 represents an alkyl group having 1 to 24 carbon atoms or an aryl group having 6 to 24 carbon atoms, and m represents an integer of 0 to 100.
Examples of the alkyl group having 1 to 24 carbon atoms represented by R ^a7 include methyl, ethyl, isopropyl, cyclohexyl, octyl and the like, and methyl or ethyl is preferable.
Examples of the aryl group having 6 to 24 carbon atoms represented by R ^a7, for example, phenyl, p- methoxyphenyl, naphthyl, anthracenyl and the like, particularly preferably an aryl group having 6 to 12 carbon atoms.

Among the above, in the formula (1), in order to reduce the molecular weight and increase the number of moles for high sensitivity, R ^a1 is a methyl or ethyl group, R ^a2 is a hydrogen atom, and X is an oxygen atom Is particularly preferred.

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

In the present invention, the compound having an oxetanyl group is preferably a compound having three or more oxetanyl groups in its structure. By using such a compound, a cured film having high sensitivity and high resistance to heat and light can be obtained.
Among these, a compound having 3 to 12 oxetanyl groups is preferable.

  Examples of the compound having 3 or more oxetanyl groups include compounds represented by the following formula (2).

In the formula ^{(2), R a1} and ^{R a2} are the formula (1) in a ^{R a1} and ^{R a2} are each synonymous, preferable embodiments thereof are also the same.
R ^a8 is a polyvalent linking group, an alkylene group having 1 to 24 carbon atoms (eg, methylene, butylene, nonylene), an alkenylene group having 1 to 24 carbon atoms (eg, propenylene, blenylene, octenylene), arylene Groups (eg, phenylene, naphthylene, anthracenylene), arylalkylene groups (eg, phenyl-di-propane-diyl, phenyl-propane-butane-diyl, naphthalenyl-dietane-butane-triyl), many having 1 to 24 carbon atoms Alkylene group having a valent acyl group (for example, propylene-diacetyl, butylene-di-benzoyl, propylene-acetyl-benzoyl, octylene-triacetyl-benzoyl), polyvalent alkanepolyyl-oxy having 1 to 24 carbon atoms A carbonyl group (eg ethylene-di-oxy) Cicarbonyl, propylene-di-oxycarbonyl, butylene-dioxycarbonyl, nonane-tetrayl-tetraoxycarbonyl), polyvalent alkanepolyyl-carbamoyl group having 1 to 24 carbon atoms (for example, ethylene-di-carbamoyl, Propylene-di-carbamoyl, butylene-di-carbamoyl, nonane-tetrayl-tetra-carbamoyl), polyvalent alkanepolyyl-oxycarbamoyl groups having 1 to 24 carbon atoms (for example, ethylene-di-oxycarbamoyl, propylene-di) -Oxycarbamoyl, butylene-dioxycarbamoyl, nonane-tetrayl-tetraoxycarbamoyl) and the like, for example, groups represented by the following A to I (* represents a bond) and the like.
Y represents an oxygen atom or a sulfur atom. j is an integer of 2-12.

Among the above, in the formula (2), R ^a1 is a methyl group or an ethyl group, R ^a2 is a hydrogen atom, and R ^a8 is the C, F in terms of high sensitivity and low molecular weight. Particularly preferred is a group represented by H, H or I, wherein Y is an oxygen atom and j is 1 to 24.

In B, R ^a9 represents a methyl group, an ethyl group, a propyl group, or the like.
Moreover, in said E, p represents the integer of 1-12.

  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.).

  Moreover, the compound represented by following formula (3) is mentioned as a compound which has a some oxetanyl group.

In the formula (3), R ^a1 and R ^a2 are synonymous with R ^a1 and R ^a2 in the formula (1), and preferred embodiments are also the same. k is an integer of 2 to 24.

  Moreover, the compound represented by following formula (4) which has an oxetanyl group in a side chain can be mentioned as another aspect of the compound which has an oxetanyl group.

In the formula ^{(4), R a1} and ^{R a2,} and ^{R a7} is, ^{R a1} and ^{R a2} in the above formula (1), and have the same meaning as the ^{R a7,} preferable embodiments thereof are also the same. R ^a10 represents an alkyl group having 1 to 24 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a trialkylsilyl group. The trialkylsilyl group is preferably a C1-C24 trialkylsilyl group, and examples thereof include trimethylsilyl, triethylsilyl, and trinonylsilyl. l is an integer of 1 to 48.

Among the above, in the formula (4), R ^a1 is a methyl group or an ethyl group, R ^a2 is a hydrogen atom, and R ^a7 and R ^a10 are a methyl group or an ethyl group in terms of reducing the molecular weight. And the case where l is 1 to 12 is particularly preferable.

  Furthermore, examples of the compound having a plurality of oxetanyl groups include compounds represented by the following formula (5).

In said Formula (5), R ^{< a2>} is synonymous with R ^<a2> in said Formula (1), and its preferable aspect is also the same.
R ^a11 and R ^{a11 ′} are each independently an alkyl group having 1 to 24 carbon atoms (for example, methyl, ethyl, isopropyl, cyclohexyl, 3-ethyloctyl), an alkenyl group having 1 to 24 carbon atoms (for example, 2- Propenyl, 2-butenyl, 4,7-nonenyl), aryl groups having 6 to 24 carbon atoms (eg, phenyl, p-chlorophenyl, naphthyl), aralkyl groups (eg, 3-phenylpropyl, 4-naphthylbutyl, 3- Phenyloctyl), an acyl group having 1 to 24 carbon atoms (for example, formyl, acetyl, benzoyl, p-methoxybenzoyl), an alkoxycarbonyl group having 1 to 24 carbon atoms (for example, acetoxy, ethoxycarbonyl, butoxycarbonyl), An alkylcarbamoyl group having 1 to 24 carbon atoms (for example, N, N-dimethylcarba Yl, N- butylcarbamoyl, N- butyl -N- ethylcarbamoyl), or alkoxy carbamoyl group (e.g., N, N- dimethoxy carbamoyl, N- butoxy carbamoyl, N- butoxy, represents N- ethoxy ^{carbamoyl), R a11} And R ^{a11 ′} may form a ring via a linking group.
Among them, R ^a11 and R ^{a11 ′} are preferably each independently a methyl group or an ethyl group.

  In said formula (5), Y represents an oxygen atom or a sulfur atom. m is an integer of 2 to 24.

Among the above, in the formula (5), R ^a2 , R ^a11 and R ^{a11 ′} are methyl groups or ethyl groups and m is 1 to 12 in terms of high sensitivity and low molecular weight. Particularly preferred.

  Another embodiment of the compound having an oxetanyl group includes a compound represented by the following formula (6) having a calixarene moiety.

In the formula (6), R ^a1 and R ^a2 have the same meaning as R ^a1 and R ^a2 in the formula (1), and preferred embodiments thereof are also the same. n is an integer of 3-12.

  The compound having such an oxetanyl group is described in detail in paragraphs [0021] to [0084] of JP-A No. 2003-341217, and the compounds described herein can be suitably used in the present invention. In addition, compounds having an oxetanyl group described in paragraphs [0022] to [0058] of JP-A No. 2004-91556 can also be used in the present invention.

  Hereinafter, specific examples (exemplary compounds [O-1] to [O-41]) of compounds having an oxetanyl group are listed, but the present invention is not limited thereto.

  Among the compounds having an oxetanyl group, [O-25], [O-26], and [O-27] are particularly preferable from the viewpoint of polyfunctionalization for increasing sensitivity.

The compounds having an oxetanyl group may be used alone or in combination of two or more.
The content of the compound having an oxetanyl group in the curable composition is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and further preferably 1 to 50% by mass. is there.

-(B) Triarylsulfonium salt and diaryliodonium salt-
The curable composition for a color filter of the present invention has, as a polymerization initiator, a triarylsulfonium salt having at least one aryl skeleton having an electron withdrawing group as a substituent, and an electron donating group as a substituent. It contains at least one selected from the group consisting of diaryl iodonium salts having at least one aryl skeleton.

(B-1: Triarylsulfonium salt)
The triarylsulfonium salt in the present invention is a compound having at least one aryl skeleton having an electron-withdrawing group as a substituent, and polymerization starts with the sum of Hammett values of substituents bonded to the aryl skeleton being 0.46 or more. Agents are preferred.

  The compound having the structure of triarylsulfonium salt is, for example, J. Amer. Chem. Soc. 112 (16), 1990; pp. 6004-6015, J. Org. Chem. 1988; pp. 5571- 5573, WO02 / 081439A1 pamphlet or European Patent (EP) No. 1,113,005, etc., can be easily synthesized.

  The triarylsulfonium salt in the present invention has one or more aryl skeletons having an electron withdrawing group as a substituent. Here, the electron withdrawing group means a substituent having a Hammett value (Hammett's substituent constant σ) larger than zero. In the present invention, from the viewpoint of increasing sensitivity, the sum of Hammett values of substituents bonded to the aryl skeleton of the triarylsulfonium salt is preferably 0.18 or more, more preferably 0.46 or more, and 60 or more is more preferable.

The Hammett value represents the degree of electron withdrawing property of a cation having a triarylsulfonium salt structure, and from the viewpoint of increasing sensitivity, there is no particular upper limit, but from the viewpoint of reactivity and stability. Is preferably 0.46 or more and 4.0 or less, more preferably 0.50 or more and 3.5 or less, and particularly preferably 0.60 or more and 3.0 or less.
In the present invention, the Hammett value uses the numerical value described in Naoki Inamoto, Chemistry Seminar 10 Hammett's Rule-Structure and Reactivity (published by Maruzen Co., Ltd. in 1983).

Examples of the electron withdrawing group introduced into the aryl skeleton include a trifluoromethyl group, a halogen atom, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxyl group, and a carbonyl group. The Hammett values of these substituents are shown below.
A trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), a halogen atom [eg, —F (m: 0.34, p: 0.06), —Cl (m: 0. 37, p: 0.23), - Br (m: 0.39, p: 0.23), - I (m: 0.35, p: 0.18) ], an ester group (e.g., _-CO 2 CH ₃ , o: 0.37, p: 0.45), a sulfoxide group (for example, —SOCH ₃ , m: 0.52, p: 0.45), a cyano group (—CN, m: 0.56, p: 0.66), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxy group (—COOH, m: 0.37, p: 0.45), a carbonyl group (—CO M: 0.36, p: 0.43). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value. For example, “m: 0.50” indicates that the Hammett value when the substituent is introduced at the meta position is 0.50. Indicates that there is.
Among the above-mentioned substituents, nonionic substituents such as halogen atoms and halogenated alkyl groups are preferred and soluble from the viewpoint of improving thermal stability or solubility in polymerizable compounds such as compounds having an oxetanyl group. from the viewpoint of the tendency, -F, -CF 3, -Cl, -Br are preferred, -Cl is preferable in view of inter alia reactivity.

  These substituents may be introduced into any one of the three aryl skeletons in the triarylsulfonium salt structure, or may be introduced into two or more aryl skeletons. When a substituent is introduced into each of the three aryl skeletons, one or more substituents may be introduced. The number of substituents to be introduced is arbitrary. For example, in the aryl skeleton having a triarylsulfonium salt structure, only one substituent having a particularly large Hammett value (for example, a Hammett value of 0.46 or more alone) may be introduced at one position. Further, for example, a plurality of substituents may be introduced and the sum of the Hammett values may be 0.46 or more.

As described above, since the Hammett value of the substituent varies depending on the position of introduction, the sum of Hammett values in the triarylsulfonium salt according to the present invention is determined by the type of substituent, the introduction position, and the number of introductions. Become.
The Hammett's rule is usually expressed by the m-position and the p-position, but in the present invention, the substituent effect at the o-position is calculated as the same value as the p-position as an index of electron withdrawing property. Preferred substitution positions are preferably the m-position and the p-position, and most preferably the p-position, from the viewpoint of synthesis.

  The “triarylsulfonium salt having at least one aryl skeleton having an electron-withdrawing group as a substituent” in the present invention is preferably a sulfonium salt having three or more substitutions by a halogen atom. More preferably, it is a sulfonium salt having an atom or a group containing a halogen atom as a substituent, more preferably a sulfonium salt in which each aryl skeleton is substituted by a halogen atom, and a sulfonium that is trisubstituted by a chloro group Most preferred is a salt. Specifically, those having a triarylsulfonium salt structure in which a halogen atom, most preferably —Cl is introduced into each of the three aryl skeletons are preferred, and those in which —Cl is substituted at the p-position are more preferred.

The counter anion of the triarylsulfonium salt is sulfonate anion, benzoylformate anion, carboxylate anion, sulfinate anion, sulfate anion, borate anion, halogen anion, polymer sulfonate anion, polymer carboxylic acid in terms of stability. An anion may be mentioned, but in view of reactivity and stability, a sulfonate anion or a polymer thereof, a benzoylformate anion or a polymer thereof is preferable, and most preferably, a sulfonate anion or a polymer thereof, B (C ₆ F ^{_{5) 4 -, PF 6 -}} , AsF 6 -, SbF 6 -, BF 4 - are preferable.

  Hereinafter, although the preferable specific example [Exemplary compound (OS-A1)-(OS-H7)] of the (B) triarylsulfonium salt in this invention is given, it is not limited to these.

(B-2: Diaryliodonium salt)
The diaryl iodonium salt in the present invention is a compound having at least one aryl skeleton having an electron donating group as a substituent, and a polymerization initiator having a sum of Hammett values of substituents bonded to the aryl skeleton of -0.2 or less. Is preferred.

The diaryl iodonium salt in the present invention is preferably an iodonium salt compound having a diaryl iodonium skeleton and having three or more electron donating groups on the aryl ring from the viewpoint of stability. The electron donating group of the diaryl iodonium salt may be introduced into any one of the two aryl skeletons of the diaryl iodonium salt structure, or may be introduced into both of the two aryl skeletons.
In addition, groups on the aryl ring of the iodonium salt 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, and these groups do not lose the electron donating property. In the range, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an alkoxy group, a thiol group, a thioalkoxy group, an amino group, a halogen atom and the like may be substituted. Further, these substituents may be further substituted with these substituents, and if possible, may be bonded to form a ring.

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 an alkyl group or an alkoxy group, and the most preferred substituent is an alkoxy group.
The number of substitution of the electron donating group is preferably 3 substitutions or more, more preferably 4 substitutions or more with an alkoxy group.
That is, the diaryl iodonium salt in the present invention is preferably one having three or more substitutions, more preferably one having three or more substitutions with an alkoxy group.

  In the diaryl iodonium salt having three or more electron donating groups on the aryl ring, the sum of the Hammett values of all substituents with respect to the iodonium group in the two aryl skeletons is preferably 0.33 or less, more preferably Is -0.2 or less, more preferably -0.3 or less. Here, the “total substituents for the iodonium group” refers 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.

The counter anion of the diaryl iodonium salt in the present invention 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.

  In addition, the diaryl iodonium salt in the present invention may be a low molecular weight compound as long as it has a diaryl iodonium salt structure and a substituent is introduced into the aryl skeleton under specific conditions. As described above, it may have a plurality of diaryliodonium salt structures.

  Hereinafter, preferred specific examples of the diaryliodonium salt in the present invention [Exemplary compounds (OI-1) to (OI-39)] are listed below, but are not limited thereto.

  Moreover, the compound which combined the cation in the compound of said (OI-1)-(OI-39) and the anion ((OI-A1)-(OI-A16)) shown below can also be illustrated preferably. Note that the above description is given priority for compounds overlapping with the above.

  A triarylsulfonium salt having at least one aryl skeleton having an electron withdrawing group as a substituent, or a diaryl iodonium salt having at least one aryl skeleton having an electron donating group as a substituent is a reaction between oxetanyl groups, And / or reaction of oxetanyl group and carboxyl group, and / or reaction of acidic group of acidic dye and oxetanyl group, and / or reaction of acidic group and / or alkali soluble group of pigment dispersion resin and oxetanyl group Any acid can be used as long as it generates an acid capable of accelerating the reaction. In the present invention, these triarylsulfonium salts and diaryliodonium salts decompose and function not only as an acid generator but also as an initiator for radical polymerization.

The content of the (B-1) triarylsulfonium salt and / or (B-2) diaryliodonium salt in the present invention in the curable composition is 0.1 to 50 mass with respect to the total mass of the composition. % Is preferable, More preferably, it is 0.5-30 mass%, More preferably, it is 1-20 mass%. It is preferable for the content to be in the above-mentioned range since sensitivity is high and stability over time is not impaired.
(B-1) Triarylsulfonium salt and (B-2) diaryliodonium salt may be used alone or in combination of two or more. Triarylsulfonium salts and diaryliodonium salts can generate radicals together with acids during decomposition, and can be used as radical polymerization initiators when used in combination with radically polymerizable compounds.

  In the present invention, the combination of (A) a compound having an oxetanyl group and (B) a triarylsulfonium salt and / or a diaryliodonium salt is (A) (OS-B4) and ( B) Combination with (OI-16), (A) (OS-A4) and (B) (OI-23), (A) (OS-B4) and (B) (OI-3) A combination of (F) and an oxime polymerization initiator is further more preferable.

-Sensitizer-
The curable composition for a color filter of the present invention may contain a sensitizer for the purpose of improving the generation efficiency of acid and radical of the (B) triarylsulfonium salt and diaryliodonium salt in the present invention.

Examples of the sensitizer 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.

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

-(C) Alkali-soluble resin-
The curable composition for color filters of the present invention contains at least one alkali-soluble resin. As the alkali-soluble resin, a linear organic polymer (preferably having a carboxyl group) is preferably used.

"
As the “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 in accordance with not only a curing function by a crosslinking reaction with an oxetanyl group but also a use as a developer of water, weak alkaline water or an organic solvent. 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, or the like, that is, a resin obtained by homogenizing or copolymerizing a monomer having a carboxyl group Resins in which monomers having acid anhydrides are singly or copolymerized and the acid anhydride units are hydrolyzed, half-esterified or half-amidated, and epoxy resins in which epoxy resins are modified with unsaturated monocarboxylic acids and acid anhydrides An acrylate etc. are mentioned. 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 copolymerizing and using an alkali-soluble resin as a copolymer, monomers other than the above-described monomers can also be used as a compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).
(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters having an aliphatic hydroxyl group such as methacrylic esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;
(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.
(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. Examples thereof include compounds described in Japanese Patent Application Nos. 2001-115595 and 2001-115598.

Among these, (meth) acrylic resins having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and double in the side chain described in JP-A Nos. 2000-187322 and 2002-62698 are disclosed. 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. No. 271741 and Japanese Patent Application No. 10-116232, a urethane-based binder polymer containing an acid group, and a urethane having an acid group and a double bond in the side chain described in JP-A No. 2002-107918. Since the binder polymer is very excellent in strength, it 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 EP999666, EP1204000, JP-A-2001-318463, etc. is excellent in balance between film strength and developability, and is suitable. It is.
Furthermore, 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 are also useful.

The weight-average molecular weight of the alkali-soluble resin is preferably 5,000 or more, more preferably 1 in order to realize a viscosity range that is easy to use in the process such as coating a color resist, and to secure film strength. The number average molecular weight is preferably 1,000 or more, and more preferably 2,000 to 250,000.
The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.

  The alkali-soluble resin used in the present invention is preferably a polymer having a large acid value from the viewpoint of reactivity with the oxetanyl group of the compound (A) having an oxetanyl group. On the other hand, if the acid value is too large, the solubility in alkali becomes too large and the appropriate development range (development latitude) becomes narrow. Accordingly, the preferred polymer acid value is preferably in the range of 20 to 300 (mg KOH / g polymer), more preferably in the range of 30 to 150 (mg KOH / g polymer), and even more preferably 35 to 120 (mg KOH / g polymer). ).

The alkali-soluble resin may be a random polymer, a block polymer, a graft polymer, or the like.
The alkali-soluble resin can be synthesized by a conventionally known method. Solvents that can be 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- Examples include methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.
As the radical polymerization initiator that can be used when synthesizing the alkali-soluble resin, known compounds such as azo initiators and peroxide initiators can be used.

-(D) Colorant-
The curable composition for a color filter of the present invention contains at least one colorant. By using a colorant, a colored cured body made of a curable composition can be formed and applied to the formation of a colored pattern of an image forming material or a color filter.

  There is no restriction | limiting in particular in the coloring agent added by necessity to the curable composition of this invention, A conventionally well-known various dye and pigment can be used individually by 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of durability such as heat resistance and light resistance.

  Various conventionally known inorganic pigments or organic pigments can be used as the pigment. Further, considering that it is preferable to obtain a high transmittance in both inorganic pigments and organic pigments, it is preferable to use a finer one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 to 0. .1 μm is preferable, and 0.01 to 0.05 μm is more preferable.

  Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like. A metal oxide and the complex oxide of the said metal can be mentioned.

Examples of the organic pigment include:
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 letter 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;
And carbon black.

Examples of pigments that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
CI pigment yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CI pigment orange 36, 71,
CI pigment leads 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 combinations are shown below.
For example, as red pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments And the like 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. When it is 100: 5 or more, the light transmittance of 400 nm to 500 nm can be suppressed, and the color purity can be increased. When it is 100: 50 or less, deviation from the NTSC target hue is suppressed. In particular, the mass ratio is preferably in the range of 100: 10 to 100: 30. In addition, the combination of red pigments can be adjusted according to chromaticity.

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

  As the blue pigment, a phthalocyanine pigment alone or a mixture of this with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

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

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

  From the viewpoint of color unevenness and contrast, it is preferable to use a dye that dissolves uniformly in the composition. The dye that can be used as the colorant 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 described 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.

When configured to be a curable composition containing a dye, an acid is generated upon exposure, and the oxetanyl group and the acidic functional group contained in the dye are cross-linked by the acid, thereby curing the film more efficiently. In addition, since a pattern having excellent developability and a good pattern shape can be formed, an acid dye and / or a derivative thereof can be preferably used. In the case of a resist system developed with water or alkali, an acidic dye and / or a derivative thereof can be preferably used from the viewpoint of completely removing the resin component and / or dye in the unirradiated part by development.
As the dye, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof are also useful.

  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 acid dyes are given below. However, the present invention is not limited to these. For example, acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the above acid dyes,
acid black 24;
acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
acid orange 8, 51, 56, 74, 63;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
acid green 25;
Dyes such as these and derivatives of these dyes are preferred.

  As the acid dye derivative, an inorganic salt of an acid dye having a sulfo group or a carboxy group, a salt with a nitrogen-containing compound, and / or an amide compound can be used, and the acid dye derivative can be dissolved in the composition of the present invention. If it does not specifically limit. Derivatives of acid dyes are selected in consideration of all the required performance such as solubility in organic solvents and developer, absorbance, interaction with other components in the composition of the present invention, light resistance, heat resistance, etc. Is done.

  Other acid dyes and derivatives thereof are described in JP-A Nos. 2006-126649, 2006-126651, 2006-133508, JP-A 2006-330717, and JP-A-2006-330718. Acid dyes and acid dye derivatives can be preferably used.

As content in the curable composition of a coloring agent, 5-80 mass% is preferable with respect to the total solid of a composition, 10-70 mass% is more preferable, 20-70 mass% is still more preferable.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the colorant is preferably 40% by mass or more, more preferably within the range of the content. , 50% by mass or more. 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 using 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 tends to decrease, or the development latitude during alkali development tends to be narrow.

-(E) Radical polymerizable compound-
In the curable composition for color filters of this invention, it is preferable to comprise using (E) radically polymerizable compound.
In the present invention, since (B) triarylsulfonium salt and / or diaryliodonium salt which is an onium salt type initiator having not only an acid generating function but also a radical generating function is used, (E) a radical polymerizable compound is further used. It can be used in combination. Thus, the film strength when the film is cured can be further improved.

  (E) As the radically polymerizable compound, a compound widely known as a compound having an ethylenically unsaturated double bond in the color filter-related industrial field can be used without particular limitation. For example, the compound which has chemical forms, such as a monomer, a prepolymer, ie, a dimer, a trimer, an oligomer, or mixtures thereof, and those copolymers is mentioned.

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

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

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexane Diol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2 -Hydroxypropo ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

  As itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, There is 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-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

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

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

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (E)
(However, R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group.)

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

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

  In the present invention, when (E) a radical polymerizable compound is added, it preferably contains two or more ethylenically unsaturated bonds, and more preferably contains three or more, from the viewpoint of curing sensitivity. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product and the like are preferable, and as a commercial product, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) ), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) are preferred.

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

  (E) The radically polymerizable compound can be arbitrarily selected from an appropriate structure, blending, and addition amount from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface tackiness, and the like.

-Radical polymerization initiator-
The curable composition for a color filter of the present invention may contain a radical polymerization initiator. The radical polymerization initiator is a compound that is decomposed by light and starts and accelerates the polymerization of the compound having at least the (A) oxetanyl group, and preferably has absorption in a wavelength region of 300 to 500 nm. Moreover, a radical polymerization initiator can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the radical polymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peracid compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryes. Examples thereof include a rubiimidazole compound, an organic borate compound, a disulfone compound, an oxime compound, and an acylphosphine (oxide) compound.

In the present invention, an oxime polymerization initiator is preferred in terms of increasing sensitivity and forming a good pattern shape.
Examples of the oxime compounds include compounds described in JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP 2000-66385 A. And compounds described in JP-A No. 2000-80068 and JP-T No. 2004-534797.
As the oxime-based photopolymerization initiator, in terms of high storage stability and high sensitivity, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is most preferred. Examples of such commercially available oxime photopolymerization initiators include CGI-124 and CGI-242 (manufactured by Ciba Specialty Chemicals).

  The curable composition for a color filter of the present invention has high sensitivity, is cured well at a low exposure amount, and has good storage stability. Moreover, when it is applied (for example, applied) to the surface of a hard material such as a substrate, it exhibits high adhesion with the substrate or the like, and a fine and well-shaped pattern can be formed. Therefore, the curable composition for a color filter of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, and inks, paints, adhesives, and coating agents.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is configured by providing a color pattern formed using the curable composition for a color filter of the present invention described above (preferably on a support).
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention includes a step of applying a curable composition for a color filter on a support to form a curable layer (hereinafter sometimes referred to as “curable layer forming step”), and A step of exposing the coated curable layer through a mask (hereinafter, also referred to as “exposure step”), and a step of developing the curable layer after exposure to form a pattern (hereinafter, “development step”) If necessary, other processes such as a curing process for curing the formed pattern by heating and / or exposure and a post-baking process for heat treatment at a high temperature are further provided. Can be configured.

Hereafter, each process in the manufacturing method of this invention is demonstrated.
(Curable layer forming step)
In the curable layer forming step, the curable composition for a color filter of the present invention is applied on a support to form a curable layer.

As the support, for example, soda glass used for liquid crystal display elements, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, photoelectric conversion element substrates used for imaging elements, For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These substrates may have black stripes that separate pixels.
If necessary, an undercoat layer may be provided on the support for improving adhesion between the formed layers, preventing diffusion of substances, or flattening the substrate surface.

  As the coating method, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.

  The coating thickness of the color filter curable composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and still more preferably 0.2 to 3 μm.

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

(Exposure process)
In the exposure step, the curable layer formed in the curable layer forming step is exposed in a pattern manner through a mask.
In the exposure, light irradiation W is performed through a predetermined mask pattern, and only the irradiated portion is cured. A colored film composed of colored pixels (preferably having three colors or four colors or more) remains in a pattern shape after being cured by development processing described later.

  As radiation used for exposure, ultraviolet rays such as g-line and i-line are preferable, 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)
In the development step, the exposed curable layer is developed to elute the unexposed portion (uncured portion) into the developer (for example, an alkaline aqueous solution), leaving only the exposed portion (cured portion).
As the developer, an organic alkali developer that does not cause damage to a circuit or the like provided on the support 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 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 suitably used. When a developer composed of an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  After the development, the excess developer is washed away and dried, followed by further heat treatment (post-bake).

  By repeating the above-described curable layer forming step, exposing step, and developing step (further, if necessary, a curing step and a post-bake step), a color filter having a desired hue can be produced.

Since the color filter of the present invention uses the above-described curable composition for a color filter of the present invention, the formed colored pattern exhibits high adhesion with the support, and the cured composition portion is Since the development resistance is excellent, it is possible to form a high-resolution pattern having high exposure sensitivity and giving a desired cross-sectional shape.
Accordingly, the color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD, and is particularly suitable for a high-resolution CCD device, CMOS, or the like exceeding 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, the present invention 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 thereof. Unless otherwise specified, “part” is based on mass.

<Synthesis of a compound having an oxetanyl group>
As shown in the following synthesis example, a “compound having an oxetanyl group” as a curable compound was synthesized.

(Synthesis Example 1)
To a 500 ml three-necked flask, 3-ethyloxetanemethanol (66 mmol, 3.3 eq) and tetrahydrofuran (THF) (100 ml) were added and stirred on an ice bath. Triethylamine (66 mmol, 3.3 eq) / THF (20 ml) was added thereto, and after the addition was completed, the mixture was stirred for 15 minutes on an ice bath, to which was added trimesyl chloride (20 mmol, 1.0 eq) for 1 hour at room temperature. Stir with. Then, when it put into ice water, solid precipitated, it filtered, and also the following compound 1 was obtained by recrystallizing (ethyl acetate / hexane) (yield 90%).

(Synthesis Example 2)
Pentaerythritol tetra (mercaptoacetate) (20 mmol, 1.0 eq) and N-methylpyrrolidinone (NMP) (100 ml) were added to a 500 ml three-necked flask and stirred. Sodium hydroxide (84 mmol, 4.2 eq) was added thereto, and after completion of the addition, the mixture was stirred for 15 minutes, and oxetane 3-ethyl-3-methanesulfonyloxymethyl oxetane (84 mmol, 4.2 eq) was added thereto. Heated to reflux for hours. Thereafter, the mixture was poured into water, the mixture was extracted with ethyl acetate, the organic layer was concentrated, and column purification (ethyl acetate / hexane) was performed to obtain the following compound 2 (yield 50%).

(Synthesis Example 3)
Dipentaerythritol hexakis (mercaptopropionate) (20 mmol, 1.0 eq) and N-methylpyrrolidinone (NMP) (100 ml) were added to a 500 ml three-necked flask and stirred. Sodium hydroxide (168 mmol, 8.4 eq) was added thereto, and after completion of the addition, the mixture was stirred for 15 minutes, and oxetane 3-ethyl-3-methanesulfonyloxymethyl oxetane (168 mmol, 8.4 eq) was added thereto. Heated to reflux for hours. Thereafter, the mixture was poured into water, the mixture was extracted with ethyl acetate, the organic layer was concentrated, and column purification (ethyl acetate / hexane) was performed to obtain the following compound 3 (yield 20%).

  First, an example using a curable composition containing a pigment (colorant) will be described as a color filter forming composition for use in a solid-state imaging device.

(Examples 1-12, Comparative Examples 1-4)
[1-1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
<composition>
Propylene glycol monomethyl ether acetate ... 19.20 parts (PGMEA: solvent)
-Ethyl lactate ... 36.67 parts-Binder polymer ... 30.51 parts [40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)]
-KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., photopolymerizable compound) ... 12.20 parts-Polymerization inhibitor (p-methoxyphenol)-0.0061 parts-Fluorosurfactant ... 0.83 parts (F -475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator: 0.586 parts (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)

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

[1-3. Preparation of curable composition solution]
First, the following components were kneaded and dispersed with two rolls to obtain a dispersion.
<composition>
・ C. I. Pigment Red 254… 22 parts ・ C.I. I. Pigment Yellow 139 ... 8 parts Resin solution ... 40 parts (Benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer (molar ratio = 80/10/10), weight average molecular weight Mw: 10,000, solvent: propylene glycol methyl ether acetate (60%, resin solid content concentration: 40%)
・ Solvent: Propylene glycol methyl ether acetate 20 parts ・ Dispersant: (Product name: Disperbyk-161, BYK chemie) 2 parts

  Subsequently, 200 parts of propylene glycol methyl ether acetate (PGMEA; solvent) was added to the obtained dispersion, and fine dispersion treatment was performed with a sand mill all day and night.

Next, the following components were further added to the dispersion after the fine dispersion treatment and stirred to prepare a curable composition solution.
<composition>
-Curable compounds listed in Table 1 below-12 parts-Polymerization initiators listed in Table 1 below-0.5 parts-9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd .; sensitizer) ... 0.2 Parts Alkali soluble resin 8.0 parts (copolymer of benzyl methacrylate and methacrylic acid (= 7: 3 [molar ratio]), weight average molecular weight Mw: 10,000, solvent: 60% propylene glycol methyl ether acetate, resin (Solid content concentration: 40%)
・ Propylene glycol methyl ether acetate (PGMEA; solvent): 100 parts

[1-4. (Production of color filter)
Using the curable composition solution obtained above as a resist solution, after applying slits to a glass substrate of 550 mm × 650 mm under the following conditions, waiting for 10 minutes as it is, and then applying the silicon with undercoat layer prepared in 1-2 above It apply | coated on the undercoat layer of the wafer, and vacuum-dried and prebaked (prebake; 100 degreeC, 80 second), and formed the curable composition layer.
<Slit application conditions>
・ Gap of the opening at the tip of the coating head: 50 μm
Application speed: 100 mm / sec Clearance between substrate and application head: 150 μm
-Application thickness (dry thickness): 2 μm
・ Application temperature: 23 ℃

  Thereafter, the curable composition layer was exposed in a pattern using a test photomask with a 2.5 kw ultra-high pressure mercury lamp. After the exposure, the entire surface of the curable composition layer was exposed to an organic developer (trade name: CD, The film was covered with a 10% aqueous solution of FUJIFILM Electronics Materials Co., Ltd., and developed after standing still for 60 seconds. After stationary, pure water was sprayed in a shower to wash away the developer, and the curable composition layer that had been exposed and developed was heated in an oven at 220 ° C. for 1 hour (post-baking). This produced the color filter.

[1-5. (Performance evaluation)
The storage stability of the curable composition solution obtained above, the exposure sensitivity of the curable composition layer (colored layer), the substrate adhesion, the developability, and the shape of the color filter pattern cross section are as follows. evaluated. The evaluation results are shown in Table 1 below.

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

-2. Exposure sensitivity
The curable composition solution was applied onto the undercoat layer of the silicon wafer with the undercoat layer prepared in 1-2 above to form a curable composition layer (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, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon, Inc.), exposure was performed at various exposure doses of 100 to 1600 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm. Thereafter, the silicon wafer on which the coating film after exposure is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (FUJIFILM Electronics). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd. to form a colored pattern on the silicon wafer.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is supplied from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device. A rinsing process was performed by supplying a shower from a jet nozzle, followed by spray drying. Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure dose at which the pattern line width was 2 μm was evaluated as the exposure sensitivity. The exposure sensitivity indicates that the smaller the exposure value, the higher the sensitivity.

-3. Developability
The color filter obtained above was observed for the presence or absence of residues in unexposed areas (unexposed areas) using an optical microscope and a scanning electron microscope (SEM) photograph, and developed according to the following evaluation criteria. evaluated.
<Evaluation criteria>
○: No residue was observed in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but there was no practical problem.
X: Residue was remarkably confirmed in the unexposed part.

-4. Substrate adhesion
Using the optical filter and scanning electron microscope (SEM) photograph of the color filter obtained above, the presence or absence of pattern chipping (pattern defect) was observed, and the substrate adhesion was evaluated according to the following evaluation criteria. .
<Evaluation criteria>
○: 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.

-5. Pattern shape
The color filter obtained above was observed using an optical microscope and a scanning electron microscope (SEM) photograph, and substrate adhesion was evaluated according to the following evaluation criteria.
<Evaluation criteria>
(Double-circle): It was a rectangle with a uniform shape or a forward taper.
○: The shape was a slightly broken rectangle or a forward taper.
(Triangle | delta): It was the rectangle or forward taper which the shape collapsed.
X: It was reverse taper.

Details of each component in Table 1 are as follows.
-O-4: (A) the above-mentioned exemplified compounds having a oxetanyl group-O-16: (A) the above-mentioned exemplified compounds having a oxetanyl group-O-6: (A) the above-mentioned examples of compounds having an oxetanyl group Compound · O-8: (A) the exemplified compound of a compound having an oxetanyl group · OS-B1: the exemplified compound of (B-1) triarylsulfonium salt · OS-B4: (B-1) triarylsulfonium salt The exemplified compound of OI-1: (B-2) the exemplified compound of diaryliodonium salt, OI-2: the exemplified compound of (B-2) diaryliodonium salt, KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd. Irgacure OXE01: manufactured by Ciba Specialty Chemicals, comparative compound 1: triglycidyl isocyanurate, comparative compound 2 2,4,6-tris (trichloromethyl) -s-triazine

  Next, an example of using a curable composition containing a dye (colorant) as a composition for forming a color filter for use in a solid-state imaging device will be described.

(Examples 13-17, Comparative Examples 5-7)
[2-1. Preparation of colored photosensitive composition (dye system)]
Components of the following composition were mixed and dissolved to prepare a colored photosensitive composition.
<composition>
・ Valifast Yellow 1101 (dye): 5.0 parts ・ Acid Red 57 (dye): 5.0 parts ・ Curable compounds listed in Table 2 below: 10.0 parts ・ Polymerization initiators listed in Table 2 below: 2.5 parts ・ 9,10-Dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd .; sensitizer)… 0.2
Cyclohexanone (solvent) 80 parts Alkali-soluble resin 20 parts copolymer (benzyl methacrylate and methacrylic acid (= 7: 3 [molar ratio]), weight average molecular weight Mw: 10,000, solvent: propylene glycol methyl ether (Acetate 60%, resin solid concentration: 40%)

[2-2. (Production and evaluation of color filter)
-Evaluation of pattern formation and sensitivity-
The colored photosensitive composition prepared in 2-1 is slit-coated on the undercoat layer of the silicon wafer with an undercoat layer prepared in 1-2 under the same conditions as described above to form a curable composition layer (coating film). Formed. Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.9 μm. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the formed curable composition layer was passed through an Island pattern mask having a pattern of 2 μm square with a wavelength of 365 nm, and 100 to 1600 mJ / It exposed with various exposure amount of cm ^2. Thereafter, the silicon wafer on which the curable composition layer after exposure was formed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 ( Paddle development was performed at 23 ° C. for 60 seconds using FUJIFILM Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is supplied from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device. A rinsing process was performed by supplying a shower from a jet nozzle, followed by spray drying. Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure dose at which the pattern line width was 2 μm was evaluated as the exposure sensitivity. The exposure sensitivity indicates that the smaller the exposure value, the higher the sensitivity.

The storage stability of the colored photosensitive composition obtained above, the substrate adhesion of the curable composition layer (colored layer), the developability, and the shape of the pattern cross section of the color filter are described in [1-5. Evaluation was performed in the same manner as in [Performance evaluation]. The evaluation results are shown in Table 2 below.
In addition, the detail of each component in following Table 2 is as above-mentioned.

  Next, an example of using a curable composition containing a pigment (colorant) as a composition for forming a color filter for liquid crystal display elements will be described.

(Examples 18-22, Comparative Examples 8-11)
[3-1. Preparation of curable composition solution]
First, the following components were kneaded and dispersed with two rolls to obtain a dispersion.
<composition>
・ C. I. Pigment Red 254… 22 parts ・ C.I. I. Pigment Yellow 139 ... 8 parts Resin solution ... 40 parts (Benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer (molar ratio = 80/10/10), methacrylic acid / hydroxyethyl methacrylate copolymer (molar ratio = 80) / 10/10), weight average molecular weight Mw: 10,000, solvent: propylene glycol methyl ether acetate 60%, resin solid content concentration: 40%)
・ Solvent: Propylene glycol methyl ether acetate: 20 parts ・ Dispersant: (trade name: BY-161, BYK) ... 2 parts

  Subsequently, 200 parts of propylene glycol methyl ether acetate (PGMEA; solvent) was added to the obtained dispersion, and fine dispersion treatment was performed with a sand mill all day and night.

Next, the following components were further added to the dispersion after the fine dispersion treatment and stirred to prepare a curable composition solution.
<composition>
-Curable compounds listed in Table 3 below-12 parts-Polymerization initiators listed in Table 3 below-0.5 parts-9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd .; sensitizer) ... 0.2 Part alkali-soluble resin: 20 parts (benzyl methacrylate and methacrylic acid (= 7: 3 [molar ratio]) copolymer, weight average molecular weight Mw: 10,000, solvent: propylene glycol methyl ether acetate 60%, resin solid content Concentration: 40%)
・ Solvent: PGMEA ... 100 parts

[3-2. (Production of color filter)
Using the obtained curable composition solution as a resist solution, slit coating is performed on a glass substrate of 550 mm × 650 mm under the following conditions, and after waiting for 10 minutes as it is, a silicon wafer with an undercoat layer prepared in 1-2 above The curable composition layer was formed by coating on the undercoat layer and vacuum drying and pre-baking (prebake; 100 ° C., 80 seconds).
<Slit application conditions>
・ Gap of the opening at the tip of the coating head: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
-Application thickness (dry thickness): 2 μm
・ Application temperature: 23 ℃

  Then, the curable composition layer is exposed in a pattern using a test photomask having a line width of 20 μm using a 2.5 kw ultra-high pressure mercury lamp, and the entire surface of the curable composition layer after the exposure is organically developed. The sample was covered with a 10% aqueous solution of a liquid (trade name: CD, manufactured by Fuji Film Electronics Materials Co., Ltd.) and developed by resting for 60 seconds. After stationary, pure water was sprayed in a shower to wash away the developer, and the curable composition layer that had been exposed and developed was heated in an oven at 220 ° C. for 1 hour (post-baking). This produced the color filter.

[3-3. (Performance evaluation)
The storage stability of the curable composition solution obtained above, the exposure sensitivity of the curable composition layer (colored layer), the substrate adhesion, the developability, and the shape of the pattern cross section of the color filter are described in [1- 5. Performance evaluation] was performed by the same method. The evaluation results are shown in Table 3 below.
In addition, about evaluation of exposure sensitivity, it exposed by changing various exposure amounts in the range of 10-100 mJ / cm < ² >, and evaluated the exposure amount from which the pattern line width after post-baking will be 20 micrometers as exposure sensitivity. The exposure sensitivity indicates that the sensitivity is higher as the exposure value is smaller.

Details of each component in Table 3 are as follows. The details of the same components as described above are as described above.
Comparative compound 3: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole + 2-mercaptobenzimidazole

  As shown in Tables 1 to 3 above, in the examples, the storage stability after preparation of the composition is high, and high sensitivity is obtained while the polymerization component is small even in the presence of air, and the developability is also good. there were. Further, the formed pattern was highly adhered to the substrate, the generation of chip defects was suppressed, and a good shape pattern having a tapered or rectangular cross-sectional shape could be obtained.

  In the above-mentioned examples, among (A) the compound having an oxetanyl group and (B) the triarylsulfonium salt and the diaryliodonium salt in the present invention described above, the former is a compound 1 to 3, and the latter is an initiator in the table. However, (A) the compound having an oxetanyl group in the present invention, and (B) the other compounds described above included in the triarylsulfonium salt and diaryliodonium salt were used. Even in this case, the same effect as described above can be obtained.

Claims (8)

  (A) a compound having an oxetanyl group, (B) a triarylsulfonium salt having at least one aryl skeleton having an electron withdrawing group as a substituent, and / or an aryl skeleton having an electron donating group as a substituent. A curable composition for a color filter, comprising at least one diaryl iodonium salt, (C) an alkali-soluble resin, and (D) a colorant.   2. The curable composition for a color filter according to claim 1, wherein the triarylsulfonium salt (B) has a sum of Hammett values of substituents bonded to an aryl skeleton of 0.46 or more.   2. The curable composition for a color filter according to claim 1, wherein the diaryl iodonium salt (B) has a sum of Hammett values of substituents bonded to the aryl skeleton of −0.2 or less.   (E) The curable composition for color filters of any one of Claims 1-3 which further contains a radically polymerizable compound.   The curability for a color filter according to any one of claims 1 to 4, further comprising (F) a radical polymerization initiator other than the (B) triarylsulfonium salt and the diaryliodonium salt. Composition.   6. The curable composition for a color filter according to claim 5, wherein the radical polymerization initiator (F) is an oxime polymerization initiator.   The color filter formed using the curable composition for color filters of any one of Claims 1-6.   The curable composition for a color filter according to any one of claims 1 to 6 is applied onto a support, the formed curable layer is exposed through a mask, and developed to form a pattern. A method for producing a color filter.