WO2016072259A1

WO2016072259A1 - Colored curable composition, color filter, pattern formation method, method for producing color filter, solid-state imaging device, and image display device

Info

Publication number: WO2016072259A1
Application number: PCT/JP2015/079637
Authority: WO
Inventors: 陽祐村上; 貴規田口
Original assignee: 富士フイルム株式会社
Priority date: 2014-11-04
Filing date: 2015-10-21
Publication date: 2016-05-12
Also published as: TW201623461A; JP2017226709A

Abstract

A colored curable composition containing a resin, a curable compound, a solvent, and a colorant that includes a halogenated zinc phthalocyanine pigment, the halogenated zinc phthalocyanine pigment having an average of 14-16 halogen atoms and an average of 12 or fewer bromine atoms per phthalocyanine molecule.

Description

Colored curable composition, color filter, pattern forming method, color filter manufacturing method, solid-state imaging device, and image display device

In recent years, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased due to the spread of digital cameras and camera-equipped mobile phones. Color filters are used as key devices for these displays and optical elements, and there is an increasing demand for higher sensitivity and miniaturization. Such a color filter normally has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and plays a role of separating transmitted light into the three primary colors.

As a colorant for forming a green coloring pattern (green pixel portion) in a color filter, use of a halogenated phthalocyanine pigment using zinc as a central metal has been proposed (Patent Documents 1 and 2).

JP 2003-161827 A JP 2010-244028 A

Examples 3 and 7 of Patent Document 1 use a composition containing a zinc halide phthalocyanine pigment in which one chlorine atom, one bromine atom and one hydrogen atom are bonded to one phthalocyanine molecule, The formation of a green colored pattern is described.
However, when the present inventors formed a green coloring pattern using the halogenated zinc phthalocyanine pigment disclosed in Patent Document 1, and formed a coloring pattern of another color adjacent to the green coloring pattern, It has been found that needle-like crystals based on a color mixture with a colored pattern of an adjacent color may occur in the green colored pattern during high-temperature heating. Further, when the pigment concentration was increased, acicular crystals were likely to be generated at a lower temperature.

In Patent Document 2, C.I. as a zinc halide phthalocyanine pigment is used. I. Pigment Green 58 is used. I. Even when Pigment Green 58 was used, the above-mentioned needle-like crystals were likely to be generated.
In Patent Document 2, an epoxy compound is included in order to solve the above problem, but in recent years, further suppression of the precipitation of needle crystals has been demanded.

Therefore, an object of the present invention is to provide a colored curable composition in which the generation of needle crystals during the production of a cured film such as a color filter is suppressed. Another object of the present invention is to provide a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, and an image display device using the above-described colored curable composition.

As a result of detailed studies, the present inventors have used a halogenated zinc phthalocyanine pigment in which the average number of halogen atoms in one molecule of phthalocyanine is 14 to 16 and the average number of bromine atoms is 12 or less. The present inventors have found that the above object can be achieved, and have completed the present invention. The present invention provides the following.
<1> A colorant containing a halogenated zinc phthalocyanine pigment, a resin, a curable compound, and a solvent,
The zinc halide phthalocyanine pigment is a colored curable composition having an average number of halogen atoms in one molecule of phthalocyanine of 14 to 16 and an average number of bromine atoms of 12 or less.
<2> The colored curable composition according to <1>, wherein the halogenated zinc phthalocyanine pigment has an average number of bromine atoms in one molecule of phthalocyanine of 1 to 8.
<3> The colored curable composition according to <1>, wherein the zinc halide phthalocyanine pigment has an average number of bromine atoms in one molecule of phthalocyanine of 1 to 7.
<4> The colored curable composition according to any one of <1> to <3>, wherein the resin includes an acidic resin.
<5> The colored curable composition according to any one of <1> to <4>, further comprising a pigment derivative. <6> The colored curable composition according to any one of <1> to <5>, wherein the pigment derivative is a compound represented by the following general formula (P):

In the general formula (P), A represents a structure selected from the following general formulas (PA-1) to (PA-3):
B represents a single bond or a (t + 1) -valent linking group,
C represents a single bond, -NH -, - CONH -, - CO 2 -, - SO 2 NH -, - O -, - S-, or, -SO ₂ - represents,
D represents a single bond, an alkylene group, or an arylene group,
E represents —SO ₃ H or a salt thereof, —CO ₂ H or a salt thereof, or —N (Rpa) (Rpb);
Rpa and Rpb each independently represents an alkyl group or an aryl group, and Rpa and Rpb may be linked to each other to form a ring;
t represents an integer of 1 to 5;

Rp ₁ represents an alkyl group having 1 to 5 carbon atoms or an aryl group,
Rp ₂ represents a halogen atom, an alkyl group or a hydroxyl group,
Rp ₃ represents a single bond, -NH -, - CONH -, - CO 2 -, - SO 2 NH -, - O -, - S-, or, -SO ₂ - represents,
s represents an integer of 0 to 4, and when s is 2 or more, the plurality of Rp ₂ may be the same as or different from each other;
* Represents a connecting portion with B.
<7> The curable compound contains at least a 3 to 15 functional (meth) acrylate compound,
The colored curable composition according to any one of <1> to <6>, further comprising a photopolymerization initiator.
<8> A color filter formed using the colored curable composition according to any one of <1> to <7>.
<9> A step of forming a colored curable composition layer on a support using the colored curable composition according to any one of <1> to <7>, and the colored curable composition layer in a pattern A pattern forming method comprising a step of exposing and a step of developing and removing an unexposed portion to form a colored pattern.
<10> A step of forming a colored curable composition layer on a support using the colored curable composition according to any one of <1> to <7> and curing to form a colored layer; A step of forming a photoresist layer on the layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a dry pattern of the colored layer using the resist pattern as an etching mask to form a colored pattern A pattern forming method including a process.
<11> A method for producing a color filter, comprising the pattern forming method according to <9> or <10>.
<12> A solid-state imaging device having the color filter according to <8> or the color filter obtained by the method for producing a color filter according to <11>.
<13> An image display device having the color filter according to <8> or the color filter obtained by the method for producing a color filter according to <11>.

According to the present invention, it is possible to provide a colored curable composition in which the generation of needle crystals during the production of a cured film such as a color filter is suppressed. In addition, it is possible to provide a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, and an image display device using the above-described colored curable composition.

Hereinafter, the contents of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, light means actinic rays or radiation. “Actinic light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
In this specification, “exposure” means not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also drawing with electron beams, ion beams, etc. unless otherwise specified. Include in exposure.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored curable composition.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ") Allyl" represents both and / or allyl and methallyl, and "(meth) acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
The pigment used in the present invention means an insoluble coloring compound that is difficult to dissolve in a solvent. Typically, it means a dye compound that exists in a dispersed state as particles in the composition. Here, an arbitrary solvent is mentioned with a solvent, For example, the solvent illustrated in the column of the solvent mentioned later is mentioned. For example, the pigment used in the present invention preferably has a dissolution amount in 100 g of propylene glycol monomethyl ether acetate at 25 ° C. and a dissolution amount in 100 g of water at 25 ° C. of 0.1 g or less.

<Colored curable composition>
The colored curable composition of the present invention contains a colorant containing a halogenated zinc phthalocyanine pigment, a resin, a curable compound, and a solvent. The halogenated zinc phthalocyanine pigment contains halogen atoms in one molecule of phthalocyanine. The average number is 14 to 16, and the average number of bromine atoms is 12 or less.
When a colored pattern is formed using a colored curable composition containing a halogenated zinc phthalocyanine pigment, conventionally, acicular crystals based on a color mixture with an adjacent colored pattern may be generated during high-temperature heating. According to the above, by using a zinc halide phthalocyanine pigment having an average number of halogen atoms in one molecule of phthalocyanine of 14 to 16 and an average number of bromine atoms of 12 or less, generation of needle-like crystals Could be suppressed. Furthermore, a cured film such as a color filter having small luminance unevenness and excellent spectral characteristics can be manufactured.
Hereinafter, the present invention will be described in detail.

<< Colorant >>
<<< Zinc Halogenated Phthalocyanine Pigment >>>
The colored curable composition of the present invention is a halogenated zinc phthalocyanine pigment having, as a colorant, an average number of halogen atoms in one molecule of phthalocyanine of 14 to 16 and an average number of bromine atoms of 12 or less. Those containing (also referred to as zinc halide phthalocyanine pigment A) are used.
The halogenated zinc phthalocyanine pigment is a halogenated phthalocyanine pigment having zinc as a central metal, and as represented by the following general formula (A1), the central metal zinc is surrounded by four nitrogen atoms of an isoindole ring. It takes a planar structure located in the region.

In the general formula (A1), X ¹ to X ¹⁶ each independently represent a halogen atom, a hydrogen atom, or a substituent.

Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
As the substituent, the description in paragraph numbers 0025 to 0027 of JP2013-209623A can be referred to, and the contents thereof are incorporated in the present specification.

In the halogenated zinc phthalocyanine pigment A, the average number of halogen atoms in one molecule of phthalocyanine is 14 to 16, and preferably 15 to 16.
In the halogenated zinc phthalocyanine pigment A, the average number of bromine atoms in one molecule of phthalocyanine is 0 to 12, preferably 1 to 8, more preferably 1 to 7, and still more preferably 2 to 7.
If the average number of halogen atoms and the average number of bromine atoms are within the above ranges, the generation of needle crystals can be suppressed. Furthermore, a cured film (color filter) with small luminance unevenness, a cured film (color filter) excellent in spectral characteristics, and the like can be manufactured.
In the halogenated zinc phthalocyanine pigment A, examples of the halogen atom other than the bromine atom include a chlorine atom, a fluorine atom, and an iodine atom. From the viewpoint of suppressing the generation of needle-like crystals, or from the viewpoint of uneven brightness, a chlorine atom, A fluorine atom is preferable, and a chlorine atom is more preferable.
In the halogenated zinc phthalocyanine pigment A, the average number of halogen atoms and the average number of bromine atoms in one molecule of phthalocyanine can be calculated from mass analysis and halogen content analysis by flask combustion ion chromatography.

In the colored curable composition of the present invention, the content of the zinc halide phthalocyanine pigment A based on the total solid content of the colored curable composition is preferably 10 to 80% by mass. The lower limit is more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is more preferably 70% by mass or less, and still more preferably 60% by mass or less.
The content of the halogenated zinc phthalocyanine pigment A in the total amount of the colorant is preferably 30 to 100% by mass. The lower limit is more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is more preferably 90% by mass or less, and still more preferably 80% by mass or less.
One kind of the halogenated zinc phthalocyanine pigment A may be used. Further, X ¹ to X ^{16 in} the general formula (A1) are different combinations of compounds (which satisfy the average number of halogen atoms and the average number of bromine atoms as defined in the present invention, and X ¹ to X ¹⁶ are Two or more kinds of compounds in different combinations may be included. When 2 or more types are included, the total amount falls within the above range.

<<< Other colorants >>>
The colored curable composition of the present invention may contain a colorant other than the halogenated zinc phthalocyanine pigment, and preferably contains another colorant. As other colorants, yellow colorants are preferred. The other colorant may be either a dye or a pigment, or a combination of both.
1 type may be sufficient as another colorant, and 2 or more types may be sufficient as it.

Examples of the pigment include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling properties, the average particle size of the pigment is 0.01 to 0.1 μm is preferable, and 0.01 to 0.05 μm is more preferable.

Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper, Mention may be made of metal oxides such as titanium, magnesium, chromium, zinc and antimony, and composite oxides of the above metals.

Examples of the organic pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175 176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279
C. I. Pigment Green 7, 10, 36, 37, 58
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80
C. I. Pigment Black 1
These organic pigments can be used alone or in various combinations in order to increase color purity.
Especially, C.I. I. Pigment Yellow 129, 138, 150, and 185 are preferred, and C.I. I. Pigment Yellow 150 and 185 are more preferable.

Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. US Pat. No. 5,667,920, US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6- The pigment | dye currently disclosed by 194828 gazette etc. can be used. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

When the colored curable composition of the present invention contains another colorant, the content of the other colorant is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the zinc halide phthalocyanine pigment A. More preferred is 120 parts by mass, and still more preferred is 20-60 parts by mass.
Other colorants include C.I. I. Pigment yellow 150, and / or C.I. I. When pigment yellow 185 is contained, it is preferably 10 to 150 parts by weight, more preferably 10 to 120 parts by weight, and still more preferably 20 to 60 parts by weight with respect to 100 parts by weight of the zinc halide phthalocyanine pigment A. If it is the said range, the spectral characteristic preferable on color reproducibility will be acquired.

In the colored curable composition of the present invention, the content of the colorant with respect to the total solid content in the colored curable composition is preferably 10 to 90% by mass. The lower limit is more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is more preferably 80% by mass or less, and more preferably 70% by mass or less.
When the colored curable composition is used for photolithography, the content of the colorant with respect to the total solid content in the colored curable composition is preferably 10 to 60% by mass. The lower limit is more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is more preferably 55% by mass or less. If content of a colorant is the range mentioned above, content of components other than a colorant can be raised and developability can be improved more.
When the colored curable composition is used for dry etching, the content of the colorant with respect to the total solid content in the colored curable composition is preferably 40 to 90% by mass. The lower limit is more preferably 45% by mass or more, and further preferably 50% by mass or more. The upper limit is more preferably 80% by mass or less, and more preferably 70% by mass or less. If the content of the colorant is in the above-described range, a color pattern having a uniform film thickness and excellent rectangularity can be easily obtained.

<< Curable compound >>
The colored curable composition of the present invention contains a curable compound. As the curable compound, a known compound that can be crosslinked by a radical, an acid, and heat can be used. For example, a compound having a group having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group and the like can be mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
In the present invention, the curable compound is preferably a polymerizable compound and a compound having an epoxy group.

<<< polymerizable compound >>>
In the present invention, the polymerizable compound may be in a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can be preferably used in the present invention.

In the present invention, the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure. As examples thereof, for example, the compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, the contents of which are incorporated herein.

The polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.). Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, SR454, SR499, commercially available from Sartomer) preferable. These oligomer types can also be used. NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used.
Preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

The polymerizable compound is also preferably a compound having a caprolactone structure.
The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, Mention is made of an ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying (meth) acrylic acid and ε-caprolactone with a polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and the like. Can do. Of these, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.

In the general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six R are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2,
“*” Indicates a bond.

In general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. )

Polymerizable compounds having a caprolactone structure are commercially available from, for example, Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = 1 Among the six Rs, R is the number of groups represented by the formula (Z-2) = 2 and R ¹ is all hydrogen atoms), DPCA-30 (same formula, m = 1, six R In which R is the number of groups represented by the formula (Z-2) = 3 and R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, R out of 6 R Number of groups represented by formula (Z-2) = 6, a compound in which R ¹ is all hydrogen atoms, DPCA-120 (m = 2 in the formula, R is a group represented by formula (Z— The number of groups represented by 2) = 6, and compounds in which all R ¹ are hydrogen atoms).

As the polymerizable compound, a compound represented by the following general formula (Z-4) or (Z-5) can also be used.

In general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O). —, Each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40 . However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 . However, when the total of each n is 0, any one of X is a carboxyl group.

In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In the general formula (Z-4) or the general formula (Z-5), — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — represents oxygen A form in which the end on the atom side is bonded to X is preferred.

The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

The total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.

Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Thus, it is possible to obtain a colored curable composition having an excellent photosensitive speed.
Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

<<< Compound having epoxy group >>>
In the present invention, a compound having an epoxy group can also be used as the curable compound.
When a pattern is formed by a dry etching method, an epoxy group-containing compound is preferably used as the curable compound.
As the compound having an epoxy group, one having two or more epoxy groups in one molecule is preferable. By using a compound having two or more epoxy groups in one molecule, the effect of the present invention can be achieved more effectively. The number of epoxy groups is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 3 in one molecule.

In the present invention, the compound having an epoxy group preferably has a structure in which two benzene rings are connected by a hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.
Moreover, it is preferable that the epoxy group is connected via a connecting group. Examples of the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. And a group containing at least one selected from —SO ₂ —, —CO—, —O—, and —S—.

The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / eq or less, more preferably 100 to 400 g / eq, more preferably 100 to 300 g. More preferably, it is / eq.

The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.

As the compound having an epoxy group having a structure in which two benzene rings are linked by a hydrocarbon group, a compound represented by the following general formula (2a) is preferably used.

In the general formula (2a), R ¹ to R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
For details of R ¹ to R ^{19 in} the general formula (2a), paragraph number 0036 of JP2013-011869A can be referred to, and the contents thereof are included in this specification.
In particular, R ¹ to R ¹⁹ are preferably each independently a hydrogen atom, a methyl group, an ethyl group or a methoxy group. More preferably, at least one selected from R ¹³ , R ¹⁸ and R ¹⁹ is a methyl group. More preferably, R ¹³ , R ¹⁸ and R ¹⁹ are methyl groups, and R ¹ to R ¹² and R ¹⁴ to R ¹⁷ are hydrogen atoms.
The compound represented by the general formula (2a) can be synthesized in consideration of paragraph number 0036 of JP2013-011869A. Examples of commercially available products include VG-3101L manufactured by Printec Co., Ltd., NC-6000 and NC-6300 manufactured by Nippon Kayaku Co., Ltd.

As the compound having an epoxy group, for example, a compound represented by the following general formula (EP1) can be used.

In the formula (EP1), R ^EP1 to R ^EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and may have a substituent. Also good. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure.
^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 ~ R ^EP3 may be combined to form a ring structure Q ^EP.
^nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, n ^EP is 2 when Q ^EP is a single bond.
Details of R ^EP1 to R ^EP3 and Q ^EP can be referred to the descriptions in paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408, the contents of which are incorporated herein.

Specific examples of the compound having an epoxy group are illustrated below, but the present invention is not limited thereto.

As the compound having an epoxy group, an oligomer or polymer having an epoxy group in the side chain can also be preferably used. Examples of such compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic epoxy resins.
These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.
As a commercial product, for example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835. (Above, manufactured by DIC Corporation), LCE-21, RE-602S (above, Nippon Kayaku) As the phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 The cresol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690. EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and aliphatic epoxy resins include ADEKA RESIN EP-4080S, E -4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
In addition, JER1031S (manufactured by Mitsubishi Chemical Corporation), JER1032H60 (manufactured by Mitsubishi Chemical Corporation), EPICLON HP-4700 (manufactured by DIC Corporation), EPICLON N-695 (manufactured by DIC Corporation), EPICLON840 ( DIC Corporation), EPICLON N660 (DIC Corporation), EPICLON HP7200 (DIC Corporation), and the like can also be preferably used.

In the colored curable composition of the present invention, the content of the curable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the colored curable composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. One curable compound may be used alone, or two or more curable compounds may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<< Polyfunctional thiol compound >>
The colored curable composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
General formula (T1)

(In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

In the above general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiols can be used alone or in combination.

When the colored curable composition of the present invention contains a polyfunctional thiol, the content of the polyfunctional thiol is preferably 0.3 to 8.9% by mass with respect to the total solid content of the colored curable composition. More preferably, the content is from 8 to 6.4 mass%. Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.

<< Solvent >>
The colored curable composition of the present invention contains a solvent.
The solvent is basically not particularly limited as long as the solubility of each component and the applicability of the colored curable composition are satisfied, but the solubility, applicability, and safety of the colorant, resin, curable compound, etc. are improved. It is preferable to select in consideration.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) ) 2 Oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like and ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and 3-heptanone, and aromatic hydrocarbons such as , Preferable examples include toluene and xylene.

It is also preferable to mix two or more of these solvents from the viewpoints of solubility of the colorant, resin, curable compound, etc., and improvement of the coated surface. For example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl carbitol acetate A mixed solution composed of two or more selected from butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
The solvent preferably has a peroxide content of 0.8 mmmpl / L or less, and is preferably a solvent substantially free of peroxide.

The content of the solvent is preferably such that the total solid concentration of the colored curable composition is 5 to 80% by mass from the viewpoint of applicability. For example, the lower limit is more preferably 5% by mass or more, and still more preferably 10% by mass or more. For example, the upper limit is more preferably 60% by mass or less, and still more preferably 50% by mass or less.
The colored curable composition of the present invention may contain only one type of solvent or two or more types of solvents. When two or more types are included, the total amount is preferably within the above range.

<< Resin >>
The colored curable composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing the colorant in the composition or the purpose of the binder. A resin used mainly for dispersing a colorant such as a pigment is also referred to as a dispersant. However, such use of the resin is merely an example, and the resin can be used for other purposes.

In the colored curable composition of the present invention, the resin content is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, based on the total solid content of the colored curable composition. When the resin content is within the above range, the dispersibility of the colorant is good.

<<< Dispersant >>>
In the present invention, the resin preferably contains a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
The dispersant preferably includes at least an acidic dispersant, and more preferably only an acidic dispersant. When the dispersant contains at least an acidic dispersant, the generation of acicular crystals can be more effectively suppressed. In addition, the dispersibility of the colorant is improved and luminance unevenness is less likely to occur. Furthermore, since excellent developability can be obtained, pattern formation can be suitably performed by photolithography. In addition, it is preferable that content of an acidic dispersing agent is 99 mass% or more in the total mass of a dispersing agent, for example that a dispersing agent is only an acidic dispersing agent, and shall be 99.9 mass% or more. You can also.

Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
The basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups accounts for 50 mol% or more when the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.
The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
In the present invention, the content of the dispersant is preferably 10 to 100 parts by mass, more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the zinc halide phthalocyanine pigment.
In the colored curable composition of the present invention, the content of the acidic resin is preferably 10 to 50% by mass and more preferably 20 to 40% by mass with respect to the total solid content of the colored curable composition. If content of acidic resin is the said range, developability will be favorable.
In the colored curable composition of the present invention, the proportion of the acidic resin in the total mass of the resin is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, further preferably 80 to 100% by mass, and 90 to 100%. Mass% is particularly preferred, and 95 to 100 mass% is most preferred.

Examples of the dispersant include a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth). Acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.

Polymer dispersants can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures. The polymer dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.

Examples of the terminal-modified polymer include a polymer having a phosphate group at the end described in JP-A-3-112992 and JP-T-2003-533455, and JP-A-2002-273191. Examples thereof include a polymer having a sulfonic acid group at the terminal and a polymer having a partial skeleton of organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.

Examples of the graft polymer include a polyester-based dispersant. Specifically, reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, etc. Reaction products of polyallylamine and polyester described in JP-A-169821, etc., macromonomers described in JP-A-10-339949, JP-A-2004-37986, international publication pamphlet WO2010 / 110491, and the like, and nitrogen atom monomers A graft type polymer having a partial skeleton of organic dye or a heterocyclic ring described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc. Copolymers of macromonomer and acid group-containing monomer described in JP 2010-106268 A, etc. Such amphoteric resin having a basic group and an acid group described in 009-203462 JP thereof.

As the macromonomer used when the graft polymer is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 manufactured by Toa Gosei Co., Ltd. Acid-6), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polyester whose terminal group is a methacryloyl group) Butyl acrylate), Placel FM5 manufactured by Daicel Chemical Industries, Ltd. (2-hydroxyethyl methacrylate with 5 molar equivalents of ε-caprolactone), FA10L (2-hydroxyethyl acrylate with 10 molar equivalents of ε-caprolactone) And polyester described in JP-A-2-272009 And the like.

As the block polymer, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin contains a repeating unit having an acid group, when a colored pattern is formed by photolithography, a residue generated on the base of the colored pixel can be further reduced.
The repeating unit having an acid group can be constituted using a monomer having an acid group. Examples of the monomer derived from the acid group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, ω- Carboxy-polycaprolactone mono (meth) acrylate and the like can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Among these, from the viewpoint of developing removability of unexposed areas, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride and the like. An addition reaction product with a cyclic anhydride is preferred.
Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid.
Examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), and the like.
As the repeating unit having an acid group, the description in paragraph numbers 0067 to 0069 of JP-A-2008-165059 can be referred to, and the contents thereof are included in the present specification.

Moreover, in this invention, acidic resin which consists of a graft copolymer containing the repeating unit represented by either general formula (A1) and general formula (A2) and the repeating unit which has an acid group as a dispersing agent. Can be used.

In general formulas (A1) and (A2), R ¹ to R ⁶ each independently represents a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent —CO—, — C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, L ¹ and L ² each independently represents a single bond or a divalent organic linking group; A ¹ and A ² each independently represents a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents an integer of 1 to 100 Represents.

R ¹ to R ⁶ each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are most preferably a hydrogen atom or a methyl group from the viewpoint of adsorption efficiency on the pigment surface.

X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Among them, —C (═O) O—, —CONH—, and a phenylene group are preferable from the viewpoint of adsorptivity to the pigment, and —C (═O) O— is most preferable.

L ¹ and L ² each independently represents a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising an alkylene group and a hetero atom or a partial structure containing a hetero atom.
The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
Examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Among these, an oxygen atom and a nitrogen atom are preferred. And a partial structure containing a heteroatom or a heteroatom having a heteroatom or a heteroatom selected from —C (═O) —, —OC (═O) —, —NHC (═O) — In view of the adsorptivity to the pigment, those linked to the adjacent oxygen atom via are preferable. Here, the adjacent oxygen atom means an oxygen atom bonded on the side of the side chain to L ¹ in the general formula (A1) and L ² in the general formula (A2).

A ¹ and A ² each independently represents a monovalent organic group. The monovalent organic group is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the substituent include the substituent described in paragraph No. 0028 of JP-A-2009-256572, and the contents thereof are incorporated in the present specification.

A ¹ and A ² are, from the viewpoint of dispersion stability and developability, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. A straight-chain alkyl group having 4 to 15 carbon atoms, a branched alkyl group having 4 to 15 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms, more preferably a straight-chain group having 6 to 10 carbon atoms. More preferred are alkyl groups and branched alkyl groups having 6 to 12 carbon atoms.

M and n each independently represents an integer of 2 to 8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

P and q each independently represents an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

Details of the repeating unit represented by the general formula (A1) and the repeating unit represented by the general formula (A2) can be referred to the descriptions in paragraph Nos. 0034 to 0044 of JP-A-2009-256572. Are incorporated herein.

Examples of the repeating unit having an acid group include those described above.
Details of the acidic resin can be referred to the descriptions in paragraph numbers 0021 to 0088 of JP-A-2009-256572, and the contents thereof are incorporated in the present specification. Specific examples of the acidic resin include the following.

In the present invention, an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain can be used as the dispersant. The oligoimine resin has a repeating unit having a partial structure X having a functional group of pKa14 or less, a side chain containing an oligomer chain or a polymer chain Y having 40 to 10,000 atoms, and has a main chain and a side chain. A resin having a basic nitrogen atom in at least one of the chains is preferred.
Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The oligoimine resin preferably contains a structure having a nitrogen atom having a base strength of pK _{b of} 14 or less, and more preferably contains a structure having a nitrogen atom of pK _{b of} 10 or less.
The base strength pK _b in the present invention means a pK _b at a water temperature 25 ° C., is one of the index for quantitatively indicating the strength of the base, is synonymous with basicity constants. A base strength pK _b, the acid strength pK _a below, a relationship of pK _b = 14-pK _a.

The oligoimine-based resin is at least selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. One type of repeating unit having a basic nitrogen atom, which is a repeating unit (i) having a partial structure X bonded to the basic nitrogen atom and having a functional group of pKa14 or less, and 40 to 10, And side chains (ii) containing 000 oligomer chains or polymer chains Y.

The poly (lower alkyleneimine) may be a chain or a network. Here, in the present invention, the lower alkylene imine means an alkylene imine containing an alkylene chain having 1 to 5 carbon atoms.
The repeating unit (i) preferably forms a main chain portion in the oligoimine resin. The number average molecular weight of the main chain portion, that is, the number average molecular weight of the portion excluding the side chain (ii) from the oligoimine resin is preferably from 100 to 10,000, more preferably from 200 to 5,000, and more preferably from 300 to 2,000 is most preferred. The number average molecular weight of the main chain part is obtained from the ratio of the hydrogen atom integral value of the terminal group and main chain part measured by nuclear magnetic resonance spectroscopy, or by measuring the molecular weight of an oligomer or polymer containing an amino group as a raw material. Can be sought.

(First embodiment of oligoimine resin)
One preferred embodiment of the oligoimine resin includes an embodiment including a repeating unit represented by the following general formula (I-1) and a repeating unit represented by the general formula (I-2).

In the general formulas (I-1) and (I-2), R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group, a represents each independently an integer of 1 to 5, * Represents a connecting portion between repeating units, X represents a group having a functional group of pKa14 or less, and Y represents an oligomer chain or polymer chain having 40 to 10,000 atoms.

The oligoimine resin preferably further contains a repeating unit represented by the general formula (I-3). According to this aspect, the dispersion performance of a colorant or the like is further improved.

In the general formula ^{(I-3), R 1} , R 2 and a have the same meanings as R ^1, R ^2, and a in the general formula (I-1). Y ′ represents an oligomer chain or polymer chain having an anion group and having 40 to 10,000 atoms. The repeating unit represented by formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed.

In general formula (I-1), general formula (I-2) and general formula (I-3), R ¹ and R ² are preferably hydrogen atoms. a is preferably 2 from the viewpoint of raw material availability.

The oligoimine resin includes a lower alkyleneimine containing a primary or tertiary amino group in addition to the repeating units represented by the general formula (I-1), the general formula (I-2) and the general formula (I-3). May be included as a repeating unit. In addition, the group shown by X, Y, or Y 'may couple | bond with the nitrogen atom in a lower alkyleneimine repeating unit.

The repeating unit represented by formula (I-1) is preferably contained in an amount of 1 to 80 mol%, and most preferably 3 to 50 mol%, based on all repeating units contained in the oligoimine resin.
The repeating unit represented by formula (I-2) is preferably contained in an amount of 10 to 90 mol%, and most preferably 30 to 70 mol%, based on all repeating units contained in the oligoimine resin. .
From the viewpoint of dispersion stability and the balance between hydrophilicity and hydrophobicity, the content ratio of the repeating unit represented by formula (I-1) and the repeating unit represented by formula (I-2) [(I-1) :( I-2)] is preferably in the range of 10: 1 to 1: 100, more preferably in the range of 1: 1 to 1:10 in terms of molar ratio.

The repeating unit represented by the general formula (I-3) used in combination optionally has a partial structure containing an oligomer chain or polymer chain Y ′ having 40 to 10,000 atoms in the main chain nitrogen atom. From the viewpoint of the effect, it is preferably contained in an amount of 0.5 to 20 mol%, and preferably 1 to 10 mol% in all repeating units contained in the oligoimine resin. Is most preferred. In addition, it can confirm that the polymer chain Y 'has ionically bonded by infrared spectroscopy or base titration.

(Second embodiment of oligoimine resin)
Another preferred embodiment of the oligoimine resin includes an embodiment including a repeating unit represented by the following general formula (II-1) and a repeating unit represented by the general formula (II-2).

In general formulas (II-1) and (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. *, X and Y have the same meanings as *, X and Y in formulas (I-1) and (I-2).

The oligoimine resin preferably further contains a repeating unit represented by the general formula (II-3). According to this aspect, the dispersion performance of a colorant or the like is further improved.

In the general formula ^{(II-3), R 3} , R 4, R 5 and R ⁶ have the same meanings as R ^3, R ^4, R ⁵ and R ⁶ in Formula (II-1). Y ′ has the same meaning as Y ′ in formula (I-3).

In the general formulas (II-1), (II-2) and (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of raw materials.

The general formula (II-1) is preferably contained in an amount of 1 to 80 mol%, and most preferably 3 to 50 mol%, in all repeating units contained in the oligoimine resin.
The general formula (II-2) is preferably contained in an amount of 10 to 90 mol%, and most preferably 30 to 70 mol% in all repeating units contained in the oligoimine resin.
From the viewpoint of dispersion stability and the balance between hydrophilicity and hydrophobicity, the content ratio of the repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-1) [(II-1) :( II-2)] is preferably in the range of 10: 1 to 1: 100, more preferably in the range of 1: 1 to 1:10 in terms of molar ratio.
The repeating unit represented by the general formula (II-3) used in combination is preferably contained in an amount of 0.5 to 20 mol%, preferably 1 to 10 mol%, based on all repeating units of the oligoimine resin. Most preferably.

In view of dispersibility, the oligoimine resin is most preferably an embodiment containing both the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2). .

(Partial structure X having a functional group of pKa14 or less)
The partial structure X has a functional group having a pKa of 14 or less at a water temperature of 25 ° C. Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
The “functional group of pKa14 or less” is not particularly limited as long as the physical properties satisfy this condition, and examples thereof include those having a pKa satisfying the above range with known functional groups. The following functional groups are preferred, and those having a pKa of 11 or less are most preferred. Specific examples of the partial structure X include, for example, a carboxylic acid group (pKa: about 3 to 5), a sulfonic acid (pKa: about −3 to −2), —COCH ₂ CO— (pKa: about 8 to 10), —COCH ₂ CN (pKa: about 8 to 11), —CONHCO—, phenolic hydroxyl group, —R _F CH ₂ OH or — (R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group. PKa: 9 to 11 Degree), sulfonamide groups (pKa: about 9 to 11) and the like, and in particular, carboxylic acid groups (pKa: about 3 to 5), sulfonic acid groups (pKa: about −3 to −2), —COCH ₂ CO- (pKa: about 8 to 10) is preferable.

The partial structure X is preferably directly bonded to the basic nitrogen atom in the repeating unit having a basic nitrogen atom. The nitrogen atom of the repeating unit having a basic nitrogen atom and the partial structure X may be linked in a form in which a salt is formed by ionic bond as well as a covalent bond.
As the partial structure X, those having a structure represented by the following general formula (V-1), general formula (V-2) or general formula (V-3) are particularly preferable.

In the general formulas (V-1) and (V-2), U represents a single bond or a divalent linking group. d and e each independently represents 0 or 1; In general formula (V-3), Q represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include an alkylene group which may have an oxygen atom, an arylene group, an alkyleneoxy group and the like, and in particular, an alkylene group having 1 to 30 carbon atoms or a carbon number of 6 An arylene group having 20 to 20 carbon atoms is preferable, and an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms is most preferable. Further, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents an acyl group or an alkoxycarbonyl group. As the acyl group in Q, an acyl group having 1 to 30 carbon atoms is preferable, and acetyl is particularly preferable. As the alkoxycarbonyl group in Q, Q is preferable from the viewpoint of ease of production of an acetyl group and availability of a raw material (precursor X ′ of X).

(Oligomer chain or polymer chain Y having 40 to 10,000 atoms)
Examples of the oligomer chain or polymer chain Y having 40 to 10,000 atoms include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylate that can be linked to the main chain portion of the oligoimine resin. The binding site with the oligoimine resin in Y is preferably the end of Y.
Y is preferably bonded to the basic nitrogen atom of the repeating unit (i) described above. The bonding mode between the basic nitrogen atom of the repeating unit (i) and Y is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the bonding mode between the basic nitrogen atom of the repeating unit (i) and Y is preferably covalent bond: ionic bond = 100: 0 to 0: 100, more preferably 95: 5 to 5:95, 90:10 to 10:90 is most preferred. Y is preferably ionically bonded to the basic nitrogen atom of the repeating unit (i) as an amide bond or carboxylate.

The number of atoms of the oligomer chain or polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoint of dispersibility, dispersion stability, and developability.
The number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. The number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability.
It is preferable that two or more side chain structures represented by Y are connected to the main chain in one molecule of the resin, and most preferably five or more are connected.
Regarding the details of Y, the description of paragraph numbers 0086 to 0098 of JP2013-064979A can be referred to, and these contents are incorporated in this specification.

The above-mentioned oligoimine resin can be synthesized by the method described in paragraph numbers 0110 to 0117 of JP2013-064979A.
Specific examples of the oligoimine-based resin described above include the following resins. In addition, resins described in paragraph numbers 0099 to 0109 and 0119 to 0124 of JP2013-064979A can be cited, and the contents thereof are incorporated in this specification.

In the present invention, as the acidic dispersant, a resin having an acid group and an unsaturated double bond described in JP-A-2008-165059, paragraphs 0020 to 0075 can be used.

The dispersant is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid). Ester), 110 (copolymer containing an acid group), 111 (phosphate dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”, "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), manufactured by EFKA""EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate)" , 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate) , 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) manufactured by Kyoeisha Chemical Co., Ltd. ”,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether) manufactured by Enomoto Kasei Co., Ltd. Ester), DA-703-50, DA-705, DA-725 ”,“ Demol RN, N (naphthalenesulfonic acid formalin polycondensate) ”, MS, C, SN-B (aromatic sulfonic acid formalin heavy) manufactured by Kao Corporation Condensate) ”,“ homogenol L-18 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative) ”manufactured by Nippon Lubrizol Co., Ltd., 22000 (azo) Pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ", manufactured by Nikko Chemical “Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)”, Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. Nosiloxane polymer KP341, “W001: cationic surfactant” manufactured by Yusho Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonyl Nonionic surfactants such as phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as “W004, W005, W017”, “EFKA-46, manufactured by Morishita Sangyo Co., Ltd.” EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by San Nopco" Disperse Aid 6 " , Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100, etc., "ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77 manufactured by ADEKA Corporation , P84, F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
In addition, resin demonstrated with the said dispersing agent can also be used for uses other than a dispersing agent. For example, it can be used as a binder.

<<< Alkali-soluble resin >>>
The colored curable composition of this invention can contain alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formation are improved. The alkali-soluble resin can also be used as a dispersant or a binder.

The molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5,000 to 100,000. The number average molecular weight (Mn) is preferably 1,000 to 20,000.
The alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a promoting group (hereinafter also referred to as “acid group”).

The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and those that are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution are preferable. Particularly preferred is meth) acrylic acid. These acid groups may be used alone or in combination of two or more.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

As the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used. Examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

Moreover, in order to improve the crosslinking efficiency of the colored curable composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing a polymerizable group in a side chain is useful.
The alkali-soluble resin containing a polymerizable group is prepared by reacting an isocyanate group and a hydroxyl group in advance, leaving one unreacted isocyanate group and containing a polymerizable group such as a (meth) acryloyl group, and a carboxyl group. Urethane-modified alkali-soluble resin obtained by reacting with an acrylic resin containing; an alkali-soluble resin obtained by reacting an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond in the molecule; acid Pendant-type epoxy acrylate resin; alkali-soluble resin obtained by reacting an acrylic resin containing a hydroxyl group with a dibasic acid anhydride having a polymerizable double bond; an acrylic resin containing a hydroxyl group, an isocyanate and a polymerizable group An alkali-soluble resin obtained by reacting a compound; Basic treatment of a resin having in the side chain an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2002-229207 and JP-A-2003-335814 Alkali-soluble resin obtained by 1 is preferable.
Examples of the alkali-soluble resin containing a polymerizable group include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264, KS resist). 106 (both manufactured by Osaka Organic Chemical Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB), Acryl-RD -F8 (manufactured by Nippon Shokubai Co., Ltd.)

Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

The alkali-soluble resin is a monomer containing a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer (a) obtained by polymerizing the components.

In general formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description in JP 2010-168539 A can be referred to.

In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n Linear or branched alkyl groups such as -propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene).
] Bis-2-propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2 -Propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (Tert-butyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (stearyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoe Di (2-ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate Di (1-ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[Oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di (tert-butylcyclohexyl) -2,2 '-[oxybis (methylene )] Bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-pro Noate, di (tricyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di And adamantyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate . Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the above formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. The alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

As for the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to <0685> to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. Incorporated herein.
Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 to 2020 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, The binder resin described in paragraph Nos. 0132 to 0143 of No. 024934 and the binder resin used in Examples, the binder resin used in paragraph Nos. 0092 to 0098 and Examples of JP 2011-242752 A, Paragraph No. of Kokai 2012-032770 030 can also be used a binder resin according to ~ 0072. These contents are incorporated herein.

The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.

When the colored curable composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1 to 15% by mass, more preferably 2 to 12% by mass with respect to the total solid content of the colored curable composition. Preferably, 3 to 10% by mass is more preferable. The colored curable composition of the present invention may contain only one type or two or more types of alkali-soluble resins. When two or more types are included, the total amount is preferably within the above range.

<< Pigment derivative >>
The colored curable composition of the present invention preferably contains a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferable from the viewpoint of dispersibility and dispersion stability. Particularly preferred are pigment derivatives having a basic group. Further, the combination of the above-described resin (dispersion resin) and the pigment derivative is preferably an acidic type resin in which the resin has an acid group and a combination in which the pigment derivative has a basic group.

Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.

As the pigment derivative, quinoline-based, benzimidazolone-based and isoindoline-based pigment derivatives are particularly preferable, and quinoline-based and benzimidazolone-based pigment derivatives are more preferable. In particular, a pigment derivative having the following structure is preferable.

In the general formulas (PA-1) to (PA-3), Rp ₁ represents an alkyl or aryl group having 1 to 5 carbon atoms,
Rp ₂ represents a halogen atom, an alkyl group or a hydroxyl group,
Rp ₃ represents a single bond, -NH -, - CONH -, - CO 2 -, - SO 2 NH -, - O -, - S-, or, -SO ₂ - represents,
s represents an integer of 0 to 4, and when s is 2 or more, the plurality of Rp ₂ may be the same as or different from each other;
* Represents a connecting portion with B.

Rp ₁ is preferably a methyl group or a phenyl group, and most preferably a methyl group.
Rp ₂ is preferably a halogen atom, and most preferably a chlorine atom.

In the general formula (P), examples of the (t + 1) -valent linking group represented by B include an alkylene group, an arylene group, and a heteroarylene group. Examples of the alkylene group include straight chain, branched, and cyclic.
The (t + 1) -valent linking group is particularly preferably a linking group represented by the following structural formulas (PA-4) to (PA-9). * Represents a connecting part with A and C.

Among structural formulas (PA-4) to (PA-9), pigment derivatives having a linking group represented by the structural formula (PA-5) or (PA-8), particularly as B, are more excellent in dispersibility. This is preferable.

In general formula (P), examples of the alkylene group and arylene group represented by D include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a decylene group, a cyclopropylene group, and a cyclobutylene group. , Cyclopentylene group, cyclohexylene group, cyclooctylene group, cyclodecylene group, phenylene group, naphthylene group and the like. Among these, as D, a linear alkylene group is preferable, and a linear alkylene group having 1 to 5 carbon atoms is more preferable.

In the general formula (P), when E represents —N (Rpa) (Rpb), examples of the alkyl group and aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, octyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, phenyl group And a naphthyl group. As Rpa and Rpb, a linear or branched alkyl group is particularly preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is most preferable.
In the general formula (P), when E represents a salt of —SO ₃ H or a salt of —CO ₂ H, the atom or atomic group forming the salt includes a lithium atom, a sodium atom, a potassium atom, etc. Alkali metals, ammonium, tetraalkylammonium and the like are preferable.
T is preferably 1 or 2.

Specific examples of the pigment derivative are shown below, but the present invention is not limited thereto.
In addition, as the pigment derivative, the description in paragraphs 0162 to 0183 of JP2011-252065A can be referred to, and the contents thereof are incorporated in the present specification. In the following formulae, Me represents a methyl group, Et represents an ethyl group, and M represents a hydrogen atom or an atom or atomic group forming a salt.

The content of the pigment derivative in the colored curable composition of the present invention is preferably 1 to 30% by mass, more preferably 3 to 20% by mass with respect to the total mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<< photopolymerization initiator >>
The colored curable composition of the present invention may further contain a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

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

In particular, when the colored curable composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that there is no development. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, a stepper exposure apparatus (exposure machine) is used for exposure for curing. In view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No. 7,556,910 contained therein, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

Specific examples of the compound represented by the general formula (OX-1) are shown below, but the present invention is not limited thereto.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

When the colored curable composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably based on the total solid content of the colored curable composition. Is 0.5 to 30% by mass, more preferably 1 to 20% by mass. Within this range, better sensitivity and pattern formability can be obtained.
Moreover, when the colored curable composition of this invention is an object for dry etching, it can also be set as the composition which does not contain a photoinitiator substantially. When the photopolymerization initiator is not substantially contained, the content of the photopolymerization initiator is preferably 1% by mass or less, and preferably 0.1% by mass or less, based on the total solid content of the colored curable composition of the present invention. More preferred is 0% by mass.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
In the colored curable composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored curable composition.
Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When the colored curable composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably about 0.01 to 5% by mass relative to the mass of the colored curable composition.
The colored curable composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Surfactant >>
Various surfactants may be added to the colored curable composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

For example, by containing a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. That is, when forming a film using a colored curable composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. As a result, the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored curable composition.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781, F781F (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Corporation), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like. Alternatively, Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd. can be used.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.

When the colored curable composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total mass of the colored curable composition, The amount is preferably 0.005 to 1.0% by mass.
The colored curable composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<< Silane coupling agent >>
The colored curable composition of the present invention can contain a silane coupling agent.
As the silane coupling agent, silane compounds having at least two types of functional groups having different reactivity in one molecule are also preferable, and those having an amino group and an alkoxy group as functional groups are particularly preferable. Examples of such silane coupling agents include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-amino. Propyl-trimethoxysilane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name, KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.) ), Γ-aminopropyl-trimethoxysilane (trade name KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltri And methoxysilane (trade name KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.). For details of the silane coupling agent, the description of paragraph numbers 0155 to 0158 in JP2013-254047A can be referred to, and the contents thereof are incorporated in the present specification.

When the colored curable composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass with respect to the total solid content of the colored curable composition, It is more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass.
The colored curable composition of the present invention may contain only one type of silane coupling agent or two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Other additives >>
The colored curable composition of the present invention may contain various additives such as a filler, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like, if necessary. Examples of these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
The colored curable composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the same publication. .

<Preparation method of colored curable composition>
The colored curable composition of the present invention is prepared by mixing the aforementioned components.
In preparing the colored curable composition, the components constituting the colored curable composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored curable composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth colored curable composition in a post process.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

The colored curable composition of the present invention can be suitably used for forming a colored layer of a color filter because it can form a cured film having good light resistance, color transfer and flatness. Further, the colored curable composition of the present invention is used for solid-state imaging devices such as charge coupled devices (CCD) and complementary metal oxide semiconductors (CMOS), and color filters used in image display devices such as liquid crystal display devices. It can be suitably used for forming a colored pattern. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. Especially, it can use suitably for manufacture of the color filter for solid-state image sensors, such as CCD and CMOS.

<Color filter, pattern formation method, color filter manufacturing method>
Next, the color filter, pattern forming method and color filter of the present invention will be described in detail through the manufacturing method. A method for producing a color filter using the pattern forming method of the present invention will also be described.

The color filter of the present invention is formed using the colored curable composition of the present invention.
In the pattern forming method of the present invention, a colored curable composition layer is formed on a support using the colored curable composition of the present invention, and unnecessary portions are removed to form a colored pattern.
The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern of a color filter.
In the pattern forming method of the present invention, pattern formation may be performed by a so-called photolithography method, or pattern formation may be performed by a dry etching method.
That is, the first aspect of the method for producing a color filter of the present invention includes a step of forming a colored curable composition layer on a support using the colored curable composition of the present invention, and a colored curable composition layer. And a step of developing and removing unexposed portions to form a colored pattern. If necessary, a step of baking the colored curable composition layer (pre-baking step) and a step of baking the developed colored pattern (post-baking step) may be provided.
Moreover, the 2nd aspect of the manufacturing method of the color filter of this invention forms a colored curable composition layer on a support body using the colored curable composition of this invention, and forms a colored layer by hardening | curing. A step, a step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and coloring the colored layer by dry etching using the resist pattern as an etching mask Forming a pattern.
The color filter of the present invention can be suitably obtained by the above production method. These details are described below.

<< Step of forming a colored curable composition layer >>
In the step of forming the colored curable composition layer, the colored curable composition layer is formed on the support using the colored curable composition of the present invention.

As the support, for example, a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
The colored pattern in the present invention may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface).
If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

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

The colored curable composition layer applied on the support can be dried (prebaked) at a temperature of 50 to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like.

<< When pattern is formed by photolithography (first aspect) >>
<<< Exposure process >>>
Next, the colored curable composition layer formed on the support is exposed in a pattern (exposure step). For example, pattern exposure can be performed by exposing a colored curable composition layer formed on a support using a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 30 ~ 1500mJ / cm ^2, more preferably 50 ~ 1000mJ / cm ^2, and most preferably 80 ~ 500mJ / cm ^2.

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and further preferably 0.2 to 0.8 μm. By setting the film thickness to 1.0 μm or less, high resolution and high adhesion can be easily obtained.

<<< Pattern formation process >>>
Next, the unexposed portion is developed and removed to form a colored pattern (pattern forming step). The development removal of the unexposed portion can be performed using a developer. Thereby, the coloring curable composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. An alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.
Moreover, you may use an inorganic alkali for a developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

It is preferable to perform heat treatment (post-bake) after development and drying. If a multicolor coloring pattern is formed, a cured film can be produced by sequentially repeating the process for each color. Thereby, a color filter is obtained.
The post-baking is a heat treatment after development for complete curing, and the heating temperature is preferably, for example, 100 to 240 ° C, more preferably 200 to 240 ° C.
The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so that the film after development is in the above condition. it can.

<< When pattern is formed by dry etching method (second embodiment) >>
Pattern formation by dry etching is performed by curing a colored curable composition layer formed on a support to form a colored layer, and then etching the obtained colored layer using a patterned photoresist layer as a mask. It can be performed using gas.
Specifically, the colored curable composition layer is cured by, for example, heat or exposure to form a colored layer, and a positive or negative radiation-sensitive composition is applied on the colored layer and dried. To form a photoresist layer. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable.

As the photoresist layer, for example, a positive radiation sensitive composition sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), excimer lasers, far ultraviolet rays, electron beams, ion beams and X rays. Is preferably used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to produce a carboxyl group, resulting in alkali-solubility from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolving power, it is used for manufacturing integrated circuits such as IC (integrated circuit) and LSI (Large Scale Integration). Examples of the quinonediazide compound include a naphthoquinonediazide compound. Examples of commercially available products include FHi622BC (manufactured by FUJIFILM Electronics Materials).

The thickness of the photoresist layer is preferably from 0.1 to 3 μm, more preferably from 0.2 to 2.5 μm, still more preferably from 0.3 to 2 μm. In addition, the application method of a positive type radiation sensitive composition can be suitably performed using the application method in the above-mentioned colored layer.

Next, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with resist through-hole groups. The formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the colored layer.

The exposure of the photoresist layer is performed by exposing the positive-type or negative-type radiation-sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. Can do. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.

Any developer can be used as long as it does not affect the colored layer and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, a combination of various solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene. When an alkaline aqueous solution is used, a washing treatment with water is generally performed after development.

Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that a through hole group is formed in the colored layer. Thereby, a colored pattern is formed. The through-hole group is preferably provided in a checkered pattern, for example, in the colored layer. Therefore, the first colored pattern in which the through hole group is provided in the colored layer has a plurality of square-shaped first colored pixels in a checkered pattern.

The dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing the damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first-stage etching is performed according to the etching time calculated in (2) above.
(4) The second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) The overetching time is calculated with respect to the total time of (3) and (4) described above, and overetching is performed.

The mixed gas used in the first-stage etching process preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed. Further, in the second stage etching process and the over etching process, after the etching is performed up to the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first stage etching process, damage to the support is avoided. From the viewpoint, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.

Further, the etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

Next, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes a step of applying a stripping solution or a solvent on the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern using cleaning water.

Examples of the step of applying a stripping solution or solvent on the resist pattern so that the resist pattern can be removed include, for example, a step of applying a stripping solution or solvent on at least the resist pattern and stagnating for a predetermined time to perform paddle development Can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

Further, examples of the step of removing the resist pattern using the cleaning water include a step of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern is more effectively removed by moving the support pattern from the center of the support to the end of the support more than twice during the process of removing the resist pattern and spraying the cleaning water. be able to.

The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds. 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenol compounds, 10) nitrogen compounds, 11) sulfur compounds, and 12) fluorine compounds. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine. Preferred are monoethanolamine, diethanolamine, and triethanolamine, and more preferred is monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of cyclic nitrogen-containing compounds include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, and 2,6-lutidine. Are N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes monoethanolamine and N-methyl-2-pyrrolidone.

When removing with a stripping solution, it is sufficient that the resist pattern formed on the colored pattern has been removed, and even when the deposit is an etching product on the side wall of the colored pattern, the deposit is completely removed. It may not be removed. A deposit means an etching product deposited and deposited on the side wall of a colored layer.

As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

The method for producing a color filter of the present invention may have a step known as a method for producing a color filter for a solid-state imaging device as a step other than the above, if necessary. For example, after performing the above-described colored curable composition layer forming step, exposure step and pattern forming step, a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary. .

In addition, the colored curable composition of the present invention is used to efficiently clean the nozzles and pipes of the discharge unit of the coating device, and the contamination of the colored curable composition and pigment in the coating machine due to adhesion, settling, and drying. It is preferable to use a solvent relating to the composition as the cleaning liquid. Also, JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can be suitably used.
Of the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid with respect to contaminants, a surfactant related to the colored curable composition of the present invention described above may be added to the cleaning liquid.

The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution 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 or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration that includes the color filter of the present invention and functions as a solid-state imaging device.

The support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.). It has a light-shielding film made of tungsten or the like that is open only in the light-receiving part, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. In addition, the solid-state image sensor color filter of the present invention is included.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protection layer and under the color filter (on the side close to the support), a structure having the light condensing means on the color filter It may be.

<Image display device>
The color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device. It is particularly suitable for liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.

For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".

In addition to the color filter of the present invention, the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.

When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue light emitting diode (LED) light sources are used. By using a backlight, a liquid crystal display device having high luminance and high color purity and excellent color reproducibility can be provided.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

(Synthesis Example) Synthesis of zinc halide phthalocyanine pigment Following the method described in paragraph Nos. 0098 to 0101 of JP-A No. 2003-161827, the average number of each atom bonded to one molecule of phthalocyanine has the composition shown in the following table. As described above, synthesis was carried out by appropriately changing the addition amount.
The composition of the halogenated zinc phthalocyanine pigment was calculated from mass analysis and halogen content analysis by flask combustion ion chromatography. The number of atoms in the following table is the number represented by X ¹ to X ¹⁶ of the zinc halide phthalocyanine pigment represented by the general formula (A1).

<Preparation of Green pigment dispersion>
The zinc halide phthalocyanine pigment of Table 1 obtained in the synthesis example, a yellow pigment, a pigment derivative, a dispersant, and a solvent were mixed so as to have a mass part shown in the following table, and the mixed solution was mixed by a bead mill. Each green pigment dispersion was prepared by mixing and dispersing for 15 hours.

<Preparation of Green Pigment-Containing Colored Curable Composition (Coating Liquid)>
Using the above green pigment dispersion, mixing and stirring were carried out so as to be the mass parts shown in the following table to prepare a green pigment-containing colored curable composition.

The raw materials shown in Tables 2 and 3 are as follows.
(Halogenated zinc phthalocyanine pigment)
Pigments A to M: Zinc halide phthalocyanine pigments A to M shown in Table 1
(Yellow pigment)
-PY185: C.I. I. Pigment Yellow 185
-PY150: C.I. I. Pigment Yellow 150
-PY139: C.I. I. Pigment Yellow 139
(Dispersant)
Dispersant A: The following structure (acid dispersant, weight average molecular weight = 24000, acid value = 52 mg KOH / g, ratio in repeating units is molar ratio)

Dispersant B: The following structure (acid dispersant, weight average molecular weight = 21000, acid value = 30 mgKOH / g, ratio in repeating units is molar ratio)

Dispersant C: The following structure (basic dispersant, weight average molecular weight = 5000, acid value = 0 mgKOH / g, ratio in repeating units is molar ratio)

(Pigment derivative)
Derivative A: the following structure

Derivative B: the following structure (wherein M is H)

Derivative C: the following structure

Derivative D: the following structure

Derivative E: the following structure

(Curable compound)
Compound A: polymerizable compound (dipentaerythritol hexaacrylate, KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
Compound B: Epoxy compound (EHPE 3150, manufactured by Daicel Chemical Industries, Ltd.)
Compound C: polymerizable compound (Aronix TO-2349, manufactured by Toagosei Co., Ltd., the following structure)

Compound D: polymerizable compound (NK ester A-DPH-12E (ethyleneoxy-modified dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.))
Compound E: polymerizable compound (NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.))
Compound F: Epoxy compound (EPICLON N-695 (epoxy resin with novolak skeleton), manufactured by DIC Corporation)
Compound G: polymerizable compound (M-305 (a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd.)
(Photopolymerization initiator)
Initiator A: IRGACURE OXE01 (manufactured by BASF)
Initiator B: IRGACURE OXE02 (manufactured by BASF)
Initiator C: the following structure

Initiator D: IRGACURE-369 (manufactured by BASF)
(Surfactant)
Activator A: Megafac F-781F (Fluorosurfactant, manufactured by DIC Corporation)
Activator B: KF6001 (silicon-based surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.)
(resin)
Resin A: The following structure (ratio in repeating unit is molar ratio)

Resin B: The following structure (ratio in repeating units is molar ratio, Me is a methyl group)

Resin C: 50:50 (molar ratio) copolymer of methacrylic acid / benzyl methacrylate (solvent)
・ PGMEA: Propylene glycol monomethyl ether acetate

<Preparation of Blue Pigment Dispersion>
9.5 parts of Pigment Blue 15: 6 as a pigment, 2.4 parts of Pigment Violet 23, 5.6 parts of BYK-161 (manufactured by BYK) as a resin (dispersant), and propylene glycol monomethyl ether as a solvent A mixed solution obtained by mixing 82.5 parts of acetate (PGMEA) was mixed and dispersed by a bead mill for 15 hours to prepare a Blue pigment dispersion.

<Preparation of Blue Pigment-Containing Colored Curable Composition (Coating Liquid)>
A blue pigment-containing colored curable composition (Blue colored radiation-sensitive composition) was prepared by using the above-mentioned Blue pigment dispersion and mixing and stirring so as to have the following composition.
<Composition>
Pigment dispersion: 51.2 parts of blue pigment dispersion Photopolymerization initiator: IRGACURE OXE01 (manufactured by BASF Corp.) 0.87 parts Polymerizable compound: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) 4.7 parts, resin (binder): ACA230AA (manufactured by Daicel Chemical Industries, Ltd.) 7.4 parts, polymerization inhibitor: p-methoxyphenol 0.002 parts, nonionic surfactant: Pionein D-6112-W 0.19 parts (manufactured by Takemoto Oil & Fat Co., Ltd.), 10.8 parts of cyclohexanone 0.9% solution of silane coupling agent: KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), organic solvent: 14.3 parts of PGMEA Organic solvent: 6.4 parts of cyclohexanone. Fluorosurfactant: Cyclohexanone 0.2% solution of F-781F (manufactured by DIC Corporation) 4.2 parts

[Production Example 1] (Manufacture of color filter including pattern formation process by photolithography)
<Formation of first colored layer (green layer)>
Using the spin coater, the green pigment-containing colored curable compositions of Examples 1 to 12, 15 to 33 and Comparative Examples 1 to 3 obtained above were applied so that the film thickness after application was 0.8 μm. Then, it was coated on a silicon wafer with an undercoat layer and subjected to heat treatment (pre-baking) for 120 seconds using a 100 ° C. hot plate to form a coated film.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), adjusting the exposure amount so that the pattern size becomes 1.4 μm square through a 1.4 μm square Bayer pattern mask, and coating The film was exposed by irradiating with i-line having a wavelength of 365 nm.
Thereafter, the silicon wafer on which the exposed coating film was formed was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with the spin shower and further washed with pure water. Next, heat treatment (post-baking) was performed for 300 seconds using a 200 ° C. hot plate to obtain a first colored layer (green layer) on which a 1.4 μm square Bayer pattern was formed.
<Formation of second colored layer (blue layer)>
The above-described Blue pigment-containing colored curable composition is applied to the first colored layer (green layer) obtained above so that the film thickness after application is 0.8 μm, dried, and then dried. A laminated color filter in which a second colored layer (blue layer) was formed on the colored layer (green layer) was obtained.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), adjusting the exposure amount so that the pattern size becomes 1.4 μm square through a 1.4 μm square island pattern mask, The color filter was exposed by irradiating with i-line having a wavelength of 365 nm.
Thereafter, paddle development was performed on the silicon wafer on which the laminated color filter had been formed, using a TMAH 0.3% aqueous solution at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water. Next, heat treatment (post-baking) was performed for 300 seconds using a 200 ° C. hot plate to obtain a color filter on which a laminated pattern of 1.4 μm square was formed.

[Production Example 2] (Manufacture of color filter including pattern formation process by dry etching)
<Formation of first colored layer>
After applying the green pigment-containing colored curable compositions of Examples 13 and 14 on a silicon wafer substrate having a diameter of 200 mm (8 inches) with a spin coater so that the film thickness after application was 0.8 μm, The first colored layer (green layer) was formed by heating the coating film at 200 ° C. for 5 minutes using a plate. The film thickness of this first colored layer (green layer) was 0.8 μm.
(Application of mask resist)
Next, a positive photoresist “FHi622BC” (manufactured by Fujifilm Electronics Materials) was applied on the first colored layer and prebaked to form a 0.8 μm-thick photoresist layer.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), adjusting the exposure amount so that the pattern size becomes 1.4 μm square through a 1.4 μm square Bayer pattern mask, The resist layer was exposed by irradiating it with i-line having a wavelength of 365 nm.
Next, heat treatment was performed for 1 minute at a temperature at which the temperature of the photoresist layer or the ambient temperature was 90 ° C. Thereafter, development processing was performed for 1 minute with a developer “FHD-5” (manufactured by Fujifilm Electronics Materials), and further post-baking processing was performed at 110 ° C. for 1 minute.
(Dry etching)
Next, dry etching was performed according to the following procedure.
RF (Radio Frequency) power: 800 W, antenna bias: 400 W, wafer bias: 200 W, chamber internal pressure: 4.0 Pa, substrate temperature: 50 ° C. using a dry etching apparatus (U-621, manufactured by Hitachi High-Technologies Corporation) The first stage etching process was performed for 80 seconds with the gas type and flow rate of the mixed gas being CF ₄ : 80 mL / min, O ₂ : 40 mL / min, and Ar: 800 mL / min.
Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas mixture type and flow rate of N ₂ : 500 mL / min, O ₂ : 50 mL / min, Ar: 500 mL / min (N ₂ / O ₂ / Ar = 10/1/10), overetching process, which is the second stage etching process, was performed for 28 seconds did.
After performing dry etching under the above conditions, a resist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is used for 120 seconds to remove the resist, and further cleaning with pure water. Spin drying was performed. Thereafter, a dehydration baking process was performed at 100 ° C. for 2 minutes. Thus, a first colored layer (green layer) after dry etching was obtained.
<Formation of second colored layer>
The above-mentioned Blue pigment-containing colored curable composition is applied to the first colored layer (green layer) after dry etching obtained above so that the film thickness after application is 0.8 μm, and dried. Thus, a laminated color filter in which the second colored layer (blue layer) was formed on the first colored layer (green layer) after dry etching was obtained.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), adjusting the exposure amount so that the pattern size becomes 1.4 μm square through a 1.4 μm square island pattern mask, The color filter was exposed by irradiating with i-line having a wavelength of 365 nm.
Thereafter, paddle development was performed on the silicon wafer on which the laminated color filter had been formed, using a TMAH 0.3% aqueous solution at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water. Next, heat treatment (post-baking) was performed for 300 seconds using a 200 ° C. hot plate to obtain a color filter on which a laminated pattern of 1.4 μm square was formed.

<Evaluation>
<< Evaluation of acicular crystal generation >>
Using a scanning electron microscope (S-9260 scanning electron microscope manufactured by Hitachi, Ltd.), the substrate after post-baking of the second colored layer and the silicon wafer additionally baked at 240 to 260 ° C. for 5 minutes are used. Observation was performed at a magnification of 20000 times, and the degree of occurrence of needle-like crystals was evaluated based on the following criteria. In the following evaluation, 3 to 5 is practical.
5: After post-baking (200 ° C./5 minutes) and after additional baking at 260 ° C./10 minutes, no needle crystals are generated 4: After post-baking (200 ° C./5 minutes) and 250 ° C./10 minutes No acicular crystals are generated even after additional baking at, but acicular crystals are generated after additional baking at 260 ° C./5 minutes.
3: Needle-like crystals are not generated even after post-baking (200 ° C / 5 minutes) and after additional baking at 240 ° C / 10 minutes, but needle-like crystals are generated after additional baking at 250 ° C / 5 minutes. .
2: After post-baking (200 ° C./5 minutes), acicular crystals are not generated, but after additional baking at 240 ° C./10 minutes, acicular crystals are generated.
1: Needle-like crystals are generated after post-baking (200 ° C./10 minutes).

<< Luminance unevenness >>
The green pigment-containing colored curable compositions of Examples 1 to 33 and Comparative Examples 1 to 3 were applied onto a glass substrate using a spin coater so that the film thickness after drying was 0.8 μm, and the coating was performed at 100 ° C. Pre-baked for 120 seconds to obtain a colored coating film.
The obtained colored coating film is placed between the observation lens and the light source of the optical microscope, irradiates the light toward the observation lens, and the transmitted light state is an optical microscope equipped with a digital camera with a magnification of 1000 times. Observed by. The digital camera provided in the optical microscope is equipped with a CCD with 1.28 million pixels, and the surface of the coating film in a transmitted light state was photographed with the digital camera. The captured image was stored as digitally converted data (digital image) in an 8-bit bitmap format.
In addition, imaging | photography of the coating film surface of a colored coating film was performed with respect to 20 area | regions selected arbitrarily. Further, the digitally converted data was stored by digitizing the captured image as a density distribution of 256 gradations from 0 to 255 for each of the three primary colors of red, green, and blue.
Next, the stored digital image was divided into a grid shape so that one grid size corresponds to 0.5 μm square on the actual substrate, and the luminance in one section was averaged.
In this example, since a 1.times.820,000 pixel digital camera took an image with a magnification of 1000 times, 0.5 μm on the actual substrate was 0.5 mm on the photographed image, and the image size on the display was 452 mm × 352 mm. Therefore, the total number of sections in one area was 636416.
For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. One section having an average luminance difference of 5% or more between one section and an adjacent section was recognized as a significant difference section, the average total number of significant difference sections in all regions was calculated, and luminance unevenness was evaluated based on the following criteria. The smaller the numerical value, the smaller the density difference between adjacent sections, the less the luminance unevenness, and the better the characteristics as a color filter.
5: The number of significant difference sections is 2000 or less.
4: The number of significant difference compartments is 2001 to 3000.
3: The number of significant difference compartments is 3001 to 5000.
2: The number of significant difference compartments is 5001 to 10,000.
1: The number of significant difference sections is 10001 or more.

<< Development residue >>
The green pigment-containing colored curable compositions of Examples 1 to 12, 15 to 33, and Comparative Examples 1 to 3 were applied on a silicon wafer with an undercoat layer using a spin coater so that the film thickness after application was 0.8 μm. And a heat treatment (prebake) for 120 seconds using a hot plate at 100 ° C. to form a coating film.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), adjusting the exposure amount so that the pattern size becomes 1.4 μm square through a 1.4 μm square Bayer pattern mask, and coating The film was exposed by irradiating with i-line having a wavelength of 365 nm.
Thereafter, paddle development was performed on the silicon wafer on which the exposed coating film was formed using a TMAH 0.3% aqueous solution at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water. Next, heat treatment (post-baking) was performed for 300 seconds using a 200 ° C. hot plate to obtain a monochromatic color filter on which a 1.4 μm square Bayer pattern was formed.
Development residue was evaluated based on the following criteria by observing the residue around the pattern using a length measuring SEM (S-4800, manufactured by Hitachi) on the obtained 1.4 μm square Bayer pattern. .
3: No residue is observed.
2: Although a residue is observed, it is a level which is satisfactory practically.
1: Residue is observed and it is the level which cannot be used practically.

As is clear from the above results, the Examples were able to efficiently suppress the generation of needle crystals. In Examples 1 to 12 and 15 to 33, a colored curable composition was prepared by changing the halogenated zinc phthalocyanine pigment A to the same amount of the halogenated phthalocyanine pigment F, I or M in Example 1. As compared with the case where a color filter was produced based on Production Example 1, the generation of needle crystals could be suppressed well.
Further, in the examples, the luminance unevenness was good.
On the other hand, in the comparative example, acicular crystals were easily generated.

Claims

A colorant containing a zinc halide phthalocyanine pigment, a resin, a curable compound, and a solvent;
The zinc halide phthalocyanine pigment is a colored curable composition having an average number of halogen atoms in one molecule of phthalocyanine of 14 to 16 and an average number of bromine atoms of 12 or less.
The colored curable composition according to claim 1, wherein the halogenated zinc phthalocyanine pigment has an average number of bromine atoms in one molecule of phthalocyanine of 1 to 8.
The colored curable composition according to claim 1, wherein the halogenated zinc phthalocyanine pigment has an average number of bromine atoms in one molecule of phthalocyanine of 1 to 7.
The colored curable composition according to any one of claims 1 to 3, comprising an acidic dispersant as the resin.
The colored curable composition according to any one of claims 1 to 4, further comprising a pigment derivative.
The colored curable composition according to any one of claims 1 to 5, wherein the pigment derivative is a compound represented by the following general formula (P):

In the general formula (P), A represents a structure selected from the following general formulas (PA-1) to (PA-3):
B represents a single bond or a (t + 1) -valent linking group,
C represents a single bond, -NH -, - CONH -, - CO 2 -, - SO 2 NH -, - O -, - S-, or, -SO 2 - represents,
D represents a single bond, an alkylene group, or an arylene group,
E represents —SO 3 H or a salt thereof, —CO 2 H or a salt thereof, or —N (Rpa) (Rpb);
Rpa and Rpb each independently represents an alkyl group or an aryl group, and Rpa and Rpb may be linked to each other to form a ring;
t represents an integer of 1 to 5;

Rp 1 represents an alkyl group having 1 to 5 carbon atoms or an aryl group,
Rp 2 represents a hydrogen atom, a halogen atom, an alkyl group or a hydroxyl group,
Rp 3 represents a single bond, -NH -, - CONH -, - CO 2 -, - SO 2 NH -, - O -, - S-, or, -SO 2 - represents,
s represents an integer of 1 to 4, and when s is 2 or more, the plurality of Rp 2 may be the same as or different from each other;
* Represents a connecting portion with B.
The curable compound contains at least a tri- to 15-functional (meth) acrylate compound,
The colored curable composition according to any one of claims 1 to 6, further comprising a photopolymerization initiator.
A color filter formed using the colored curable composition according to any one of claims 1 to 7.
A step of forming a colored curable composition layer on a support using the colored curable composition according to any one of claims 1 to 7, and exposing the colored curable composition layer in a pattern A pattern forming method including a step and a step of developing and removing an unexposed portion to form a colored pattern.
A step of forming a colored curable composition layer on a support using the colored curable composition according to any one of claims 1 to 7 and curing to form a colored layer; Forming a photoresist layer, patterning the photoresist layer by exposure and development to obtain a resist pattern, and dry-etching the colored layer using the resist pattern as an etching mask to form a colored pattern And a pattern forming method.
A method for producing a color filter, comprising the pattern forming method according to claim 9.
A solid-state imaging device having the color filter according to claim 8 or the color filter obtained by the method for producing a color filter according to claim 11.
An image display device comprising the color filter according to claim 8 or the color filter obtained by the method for producing a color filter according to claim 11.