TW201623461A - Colored curable composition, color filter, pattern formation method, method for producing color filter, solid-state imaging device, and image display device - Google Patents

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

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

The present invention relates to a coloring curable composition, a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and an image display device.

In recent years, demand for solid-state imaging elements such as charge coupled device (CCD) image sensors has increased significantly due to the spread of digital cameras, camera-equipped mobile phones, and the like. As a main device of such a display or an optical element, a color filter is used, and the demand for further high sensitivity and miniaturization is improved. Such a color filter usually has red (R), green (G), and blue (B). The color patterns of the three primary colors function to decompose the transmitted light into three primary colors.

As a coloring agent for forming a green coloring pattern (green pixel portion) in a color filter, the use of a zinc halide phthalocyanine pigment for a center metal has been proposed (Japanese Patent Literatures 1, 2).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-161827

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-244028

In Examples 3 and 7 of Patent Document 1, a composition containing a zinc halide phthalocyanine pigment in which one chlorine atom, 14 bromine atoms, and one hydrogen atom are bonded to one molecule of phthalocyanine is used is formed. A green colored pattern in a color filter.

However, the inventors of the present invention have formed a green coloring pattern using the zinc halide phthalocyanine pigment disclosed in Patent Document 1, and formed a coloring pattern of another color adjacent to the green coloring pattern, and it is understood that when heating at a high temperature, sometimes A needle-like crystal based on a color mixture of a color pattern of another adjacent color is produced on the green coloring pattern. Further, when the pigment concentration is increased, needle crystals are easily generated at a lower temperature.

Further, in Patent Document 2, C.I. Pigment Green 58 is used as the zinc halide phthalocyanine pigment. However, even when C.I. Pigment Green 58 is used, the needle crystals are likely to be generated.

In order to solve the above problems, Patent Document 2 contains an epoxy compound, but in recent years, it has been required to further suppress precipitation of needle crystals.

Accordingly, an object of the present invention is to provide a color hardening composition which suppresses generation of needle crystals when a cured film such as a color filter is produced. Further, an object of the invention is to provide a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and an image display device using the coloring curable composition.

As a result of detailed studies, the present inventors have found that the average number of halogen atoms in the molecule of phthalocyanine is 14 to 16, and the average number of bromine atoms is 12 or less. The cyanine pigment can achieve the above object, thereby completing the present invention. The present invention provides the following.

<1> A colored curable composition comprising a coloring agent containing a zinc halide phthalocyanine pigment, a resin, a curable compound, and a solvent, wherein the average number of halogen atoms in the phthalocyanine 1 molecule in the zinc halide phthalocyanine pigment is 14 to 16 and the average number of bromine atoms is 12 or less.

<2> The colored curable composition according to <1>, wherein the average number of bromine atoms in the phthalocyanine 1 molecule in the zinc halide phthalocyanine pigment is from 1 to 8.

<3> The colored curable composition according to <1>, wherein the average number of bromine atoms in the phthalocyanine 1 molecule in the zinc halide phthalocyanine pigment is from 1 to 7.

The colored hardening composition according to any one of <1> to <3> wherein the resin contains an acidic resin.

The colored hardening composition according to any one of <1> to <4> which further contains a pigment derivative.

The colored hardening composition according to any one of <1> to <5> wherein the pigment derivative is a compound represented by the following formula (P); [Chemical Formula 1] In the formula (P), A represents a structure selected from the following formulae (PA-1) to (PA-3), B represents a single bond or a (t+1)-valent linking group, and C represents a single bond, -NH-, -CONH-, -CO ₂ -, -SO ₂ NH-, -O-, -S- or -SO ₂ -, D represents a single bond, an alkyl group or an extended aryl 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 represent an alkyl group or an aryl group, and Rpa and Rpb may be bonded to each other to form a ring, and t represents 1 An integer of ～5; [Chemical Formula 2] Rp ₁ represents an alkyl group or an aryl group having 1 to 5 carbon atoms, Rp ₂ represents a halogen atom, an alkyl group or a hydroxyl group, and Rp ₃ represents a single bond, -NH-, -CONH-, -CO ₂ -, -SO ₂ NH -, -O-, -S- or -SO ₂ -, s represents an integer of 0 to 4, and when s is 2 or more, a plurality of Rp ₂ may be the same or different, and * represents a connection portion with B.

The colored hardening composition according to any one of <1> to <6>, further comprising a photopolymerization initiator, wherein the curable compound contains at least 3 to 15 functional (meth)acrylic acid Ester compound.

<8> A color filter comprising the color hardening composition according to any one of <1> to <7>.

<9> A pattern forming method, comprising: forming a colored curable composition layer on a support by using the colored curable composition according to any one of <1> to <7>; a process in which the composition layer is exposed to a pattern; and a process of developing the colored portion by developing and removing the unexposed portion.

<10> A pattern forming method, comprising: using the color hardening composition according to any one of <1> to <7>, forming a colored curable composition layer on a support, and hardening to form a color a process of forming a photoresist layer on a colored layer; a process of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask to perform the coloring layer The process of forming a colored pattern by dry etching.

<11> A method of producing a color filter, comprising the pattern forming method according to <9> or <10>.

<12> A solid-state imaging device having the color filter of <8> or a color filter obtained by the method for producing a color filter according to <11>.

<13> An image display device comprising the color filter of <8> or a 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 color hardening composition which suppresses generation of needle crystals when a cured film such as a color filter is produced. Further, it is possible to provide a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and an image display device using the coloring curable composition.

Hereinafter, the contents of the present invention will be described in detail.

In the label of the group (atomic group) in the present specification, the label which is not labeled and unsubstituted includes those having no substituent and having a substituent. For example, "alkyl" means not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, light means active light or radiation. Further, "active light" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like.

The "exposure" in the present specification refers to not only the exposure of the ultraviolet light, the X-ray, the EUV light, etc. represented by the mercury lamp or the excimer laser, but also the drawing of the particle beam based on the electron beam or the ion beam, unless otherwise specified. Also included in the exposure.

In the present specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, the total solid content refers to the total mass of the components after the solvent is removed from the overall composition of the colored curable composition.

In the present specification, "(meth) acrylate" means either or both of acrylate and methyl acrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(A) The "allyl" group means either or both of an allyl group and a methallyl group, and "(meth)acryloyl group" means either or both of an acryloyl group and a methacryl group.

In the present specification, the polymerizable compound means 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 the polymerization reaction.

In this specification, the term "process" includes not only independent processes, but also the term as long as it is capable of exerting the desired effect of the process, even if it is not clearly distinguishable from other processes.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values based on GPC measurement. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, TKKgel Super AWM-H (manufactured by Tosoh Corporation) 6.0 mm ID × 15.0 cm by using HLC-8220 (manufactured by Tosoh Corporation). As a column, a 10 mmol/L lithium bromide NMP (N-methylpyrrolidone) solution was used as an eluent.

The pigment used in the present invention means an insoluble pigment compound which is not easily dissolved in a solvent. Typically, it means a pigment compound which exists in a state in which particles are dispersed in a composition. Here, the solvent may be any solvent, and examples thereof include a solvent exemplified in the solvent column described later. The pigment used in the present invention is preferably, for example, a dissolved amount of 100 g of propylene glycol monomethyl ether acetate at 25 ° C and a dissolved amount of 100 g with respect to water at 25 ° C of 0.1 g or less.

<Coloring hardenable composition>

The colored curable composition of the present invention contains a coloring agent containing a zinc halide phthalocyanine pigment, a resin, a curable compound, and a solvent, and the average number of halogen atoms in the phthalocyanine 1 molecule in the zinc halide phthalocyanine pigment is 14 to 16 Moreover, the average number of bromine atoms is 12 or less.

When a colored pattern is formed using a colored curable composition containing a zinc halide phthalocyanine pigment, conventionally, needle-like crystals based on color mixing with adjacent colored patterns may be generated during high-temperature heating, but according to the present invention, The use of a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of the phthalocyanine group of 14 to 16 and an average number of bromine atoms of 12 or less suppresses generation of needle crystals. Further, it is also possible to produce a cured film such as a color filter having small luminance unevenness and excellent spectral characteristics.

Hereinafter, the present invention will be described in detail.

<<<Coloring agent>>

<<<Hallium halide phthalocyanine pigment>>>

The coloring-curable composition of the present invention uses 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 (also referred to as The zinc halide phthalocyanine pigment A) is used as a coloring agent.

The zinc halide phthalocyanine pigment has a zinc halide phthalocyanine pigment as a center metal, and is represented by the following general formula (A1), and the zinc as a central metal is located in a plane surrounded by four nitrogens of an isoindole ring. structure.

[Chemical Formula 3]

In the 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 a substituent, the description of paragraphs 0025 to 0027 of JP-A-2013-209623 can be referred to, and the contents are incorporated in the present specification.

The average number of halogen atoms in one molecule of the phthalocyanine pigment of the zinc halide phthalocyanine pigment A is from 14 to 16, and from 15 to 16 is preferred.

The average number of bromine atoms in one molecule of the phthalocyanine pigment of the zinc halide phthalocyanine pigment A is from 0 to 12, preferably from 1 to 8, more preferably from 1 to 7, and further preferably from 2 to 7.

When the average number of halogen atoms and the average number of bromine atoms are as described above, generation of needle crystals can be suppressed. Further, it is also possible to produce a cured film (color filter) having a small unevenness in brightness, a cured film (color filter) excellent in spectral characteristics, and the like.

In the zinc halide phthalocyanine pigment A, a halogen atom other than a bromine atom may be a chlorine atom, a fluorine atom or an iodine atom. From the viewpoint of suppressing generation of needle crystals or uneven brightness, the chlorine atom and the fluorine atom are Preferably, the chlorine atom is more preferred.

In addition, the average number of halogen atoms in the phthalocyanine 1 molecule and the average number of bromine atoms in the zinc halide phthalocyanine pigment A can be calculated based on mass analysis and halogen content analysis by a flask combustion ion chromatograph. .

In the colored curable composition of the present invention, the content of the above-mentioned zinc halide phthalocyanine pigment A with respect to the total solid content of the colored curable composition is preferably from 10 to 80% by mass. The lower limit is more preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is more preferably 70% by mass or less, and more preferably 60% by mass or less.

Further, the content of the above-mentioned zinc halide phthalocyanine pigment A in the total amount of the colorant is preferably from 30 to 100% by mass. The lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is more preferably 90% by mass or less, and more preferably 80% by mass or less.

The zinc halide phthalocyanine pigment A may be one type. Further, X ¹ to X ^{16 of the} above formula (A1) may be a compound containing two or more different combinations (in the present invention, the average number of halogen atoms and the average number of bromine atoms and X ¹ are specified in the present invention. ～X ¹⁶ different combinations of compounds). When two or more types are contained, the total amount becomes the above range.

<<<Other colorants>>

The colored curable composition of the present invention may contain a coloring agent other than the zinc halide phthalocyanine pigment, and it is preferred to contain other coloring agents. As other colorants, a yellow colorant is preferred. Other colorants may be any of a dye and a pigment, or both may be used in combination.

The other coloring agents may be used alone or in combination of two or more.

Examples of the pigment include various conventional inorganic pigments or organic pigments. Further, in the case of an inorganic pigment or an organic pigment, in consideration of a high transmittance, it is preferred to use a pigment having a small average particle diameter as much as possible, and in consideration of handleability, the average particle diameter of the pigment is It is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.

Examples of the inorganic pigment include a metal compound represented by a metal oxide, a metal salt or the like, and specific examples thereof include black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper, and titanium. a metal oxide such as magnesium, chromium, zinc or bismuth and a composite oxide of the above metals.

In the present invention, the following organic pigments can be preferably used. However, the present invention is not limited to these.

CI 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.

CI 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 Wait,

CI 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 singly or in combination with various pigments in order to improve color purity.

Among them, C.I. Pigment Yellow 129, 138, 150, 185 is preferred, and C.I. Pigment Yellow 150, 185 is more preferred.

For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, and JP-A No. 2592207 can be used. , U.S. Patent No. 4,808, 051, U.S. Patent No. 5, 568, 920, U.S. Patent No. 5, 560, 950, U.S. Patent No. 5, 595, 950, U.S. Patent No. 5,567, 920, Japanese Patent Application Laid-Open No. Hei No. Hei No. 5-333207, Japanese Patent Laid-Open No. Hei 6-35183, No. 6-51115 A pigment in the publication of Japanese Laid-Open Patent Publication No. Hei 6-194928. If it is distinguished as a chemical structure, a pyrazole azo compound, a pyrrolemethylene compound, an anilino azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxophthalocyanine compound, or a pyrazole can be used. A triazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, or the like. Further, a dye polymer can also be used as the dye. The compound described in JP-A-2011-213925, and JP-A-2013-041097 can be mentioned as a pigment.

When the coloring-curable composition of the present invention contains another coloring agent, the content of the other coloring agent is preferably 10 to 150 parts by mass, and 10 to 120 parts by mass per 100 parts by mass of the zinc halide phthalocyanine pigment A. More preferably, 20 to 60 parts by mass is further preferred.

Further, when CI Pigment Yellow 150 and/or CI Pigment Yellow 185 are contained as other colorants, the content of the zinc halide phthalocyanine pigment A is preferably 10 to 150 parts by mass, preferably 10 to 120 parts by mass per 100 parts by mass. The mass portion is more preferably 20 to 60 parts by mass. If it is the above range, the spectral characteristics which are preferable in color reproducibility can be obtained.

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 from 10 to 90% by mass. The lower limit is more preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less.

Moreover, when the coloring 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 from 10 to 60% by mass. The lower limit is more preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 55% by mass or less. When the content of the colorant is the above-described range, the content of components other than the colorant can be increased, and the developability can be further improved.

Moreover, when the coloring 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 from 40 to 90% by mass. The lower limit is more preferably 45% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less. When the content of the colorant is the above-described range, it is easy to obtain a colored pattern having a uniform film thickness and excellent squareness.

<<Cure compound>>

The colored curable composition of the present invention contains a curable compound. As the curable compound, a known compound which can be crosslinked by a radical, an acid, and heat can be used. For example, a compound containing a group having an ethylenically unsaturated bond, a cyclic ether (epoxy group, oxetane) group, or a methylol group can be given. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group.

In the present invention, the curable compound is preferably a polymerizable compound and a compound having an epoxy group.

<<Polymerized compound>>

In the present invention, the polymerizable compound may be, for example, a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or a mixture thereof, and a chemical form such as the polymer. Any of them.

The polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.

Examples of the monomer and the prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines, and the like. Such polymers are preferably esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and such polymers. Further, an addition reaction product of an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, and a monofunctional or polyfunctional isocyanate or epoxy group may be suitably used, and A dehydration condensation reaction of a monofunctional or polyfunctional carboxylic acid or the like. Further, a reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or a guanamine and a monofunctional or polyfunctional alcohol, an amine or a thiol may be suitably used. And a reaction product of an unsaturated carboxylic acid ester or a guanamine having a destructive substituent such as a halogen group or a tosyloxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, a compound group in which the above unsaturated carboxylic acid is substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether or an allyl ether can also be used.

As the specific compound, the compound described in paragraphs 0095 to 0108 of JP-A-2009-288705 can be suitably used in the present invention.

In the present invention, a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C or higher at normal pressure is also preferable as the polymerizable compound. For example, the compound described in Paragraph No. 0227 of JP-A-2013-29760, and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to in the present specification.

The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU CO., LTD.) or dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; NIPPON KAYAKU CO.). , manufactured by LTD.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD) DPHA; manufactured by NIPPON KAYAKU CO., LTD., manufactured by A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., and structures of (meth)acryloyl sulfhydryl groups via ethylene glycol and propylene glycol residues (e.g., SR454, SR499, marketed by SARTOMER Company, Inc.). These types of oligomers can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), KAYARAD RP-1040 (manufactured by NIPPON KAYAKU CO., LTD.), or the like can be used.

The aspect of the preferred polymerizable compound is 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 preferred, and a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group polymerizability. More preferably, the compound is particularly preferred in the case where the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, ARONIX TO-2349, M-305, M-510, M-520, etc. by TOAGOSEI CO., LTD. are mentioned, for example.

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

A compound having a caprolactone structure in the polymerizable compound is also a preferred state.

The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate, which is ε-caprolactone. The modified polyfunctional (meth) acrylate can be obtained by using trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, three Polyols such as pentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferred.

[Chemical Formula 4]

In the general formula (Z-1), all of the six R's are represented by the following formula (Z-2), or one to five of the six R are represented by the following formula (Z-2) The group represented by the formula is the group represented by the following formula (Z-3).

[Chemical Formula 5]

In the formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

[Chemical Formula 6]

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

A polymerizable compound having a caprolactone structure is commercially available, for example, from NIPPON KAYAKU CO., LTD. as KAYARAD DPCA series, and DPCA-20 (in the above formulas (Z-1) to (Z-3), m= 1. The formula (Z-2) represents the number of groups of R in 6 R = 2, the compound in which all R ¹ are a hydrogen atom), DPCA-30 (the above formula (Z-1) to (Z- In 3), m = 1, the number of groups in which R in 6 R is represented by the formula (Z-2) = 3, and the compound in which all R ¹ are a hydrogen atom), DPCA-60 (the above formula (Z-) In 1) to (Z-3), m=1, the number of groups in which R in 6 R is represented by the formula (Z-2) = 6, and all compounds in which R ¹ is a hydrogen atom), DPCA-120 (In the above formulae (Z-1) to (Z-3), m = 2, the number of groups in which R in the six Rs is represented by the formula (Z-2) = 6, and R ^{1 is} all a hydrogen atom. Compound) and the like.

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

[Chemical Formula 7]

In the general formulae (Z-4) and (Z-5), E independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom or a carboxyl group.

In the general formula (Z-4), the total of (meth)acrylonyl groups is three or four, and m each independently represents an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40. In the case where the total of each of m is 0, one of X is a carboxyl group.

In the general formula (Z-5), the total of (meth)acrylonyl groups is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. In the case where the total of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), an integer of m of from 0 to 6 is preferred, and an integer of from 0 to 4 is more preferably.

Further, 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 the formula (Z-5), n is an integer of 0 to 6 and preferably an integer of 0 to 4 is more preferable.

Further, the total of 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.

Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (Z-4) or the formula (Z-5) is preferred. It is a form in which the end of the oxygen atom side is bonded to X.

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), it is preferred that all of the six X atoms are acrylonitrile groups.

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

The compound represented by the formula (Z-4) or the formula (Z-5) can be synthesized by a conventionally known process: a ring-opening skeleton of ethylene oxide or propylene oxide by a ring-opening addition reaction A process of bonding to pentaerythritol or dipentaerythritol; and, for example, a process of reacting (meth)acrylofluorene chloride with a terminal hydroxyl group of a ring-opening skeleton to introduce a (meth)acrylonitrile group. Each process is a well-known process, and those skilled in the art can easily synthesize a compound represented by the formula (Z-4) or (Z-5).

Among the compounds represented by the formula (Z-4) or the formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are also more preferable.

Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)"), wherein the compounds (a) and (b) are exemplified. ), (e), (f) are preferred.

[Chemical Formula 8]

[Chemical Formula 9]

As a commercial item of the polymerizable compound represented by the general formula (Z-4) or (Z-5), for example, SR of a tetrafunctional acrylate having four ethyleneoxy chains manufactured by SARTOMER Company, Inc. -494, DPCA-60 having 6 penteneoxy chain 6-functional acrylates, TPA-330 having 3 isobutyleneoxy chains, and TPA-330 having 3 isobutyleneoxy chains, manufactured by NIPPON KAYAKU CO., LTD.

The urethane described in Japanese Patent Publication No. Hei 2-16765, and Japanese Patent Publication No. Hei 2-26765 The acrylate-based structure having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 Amino acid compound is also preferred. In addition, the addition of an amine-based structure and a sulfide structure in the molecule is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A polymerizable compound can be obtained as a color-curable composition having an excellent photospeed.

Commercially available products include urethane oligomer UAS-10, UAB-140 (made by SANYO-KOKUSAKU PULP CO., LTD.), and UA-7200 (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 CO., LTD.).

<<<Compound with epoxy group>>>

In the present invention, a compound having an epoxy group can also be used as the curable compound.

In the case of forming a pattern by dry etching, a compound having an epoxy group can be preferably used as the curable compound.

As the compound having an epoxy group, it is preferred to have two or more epoxy groups in one molecule. By using a compound having two or more epoxy groups in one molecule, the effects of the present invention can be exhibited more effectively. The epoxy group is preferably 2 to 10 in one molecule, more preferably 2 to 5, and particularly preferably 3.

The compound having an epoxy group in the present invention can preferably be used as a structure having two benzene rings bonded by a hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.

Further, it is preferred that the epoxy group is connected via a linking group. The linking group may, for example, be an aryl group selected from an alkyl group, an extended aryl group, -O-, an alkyl group which may have a substituent, or an alkyl group which may have a substituent, represented by -NR'- (R' represents a hydrogen atom. The hydrogen atom is preferably a structure represented by at least one of -SO ₂ -, -CO-, -O-, and -S-.

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

The compound having an epoxy group may be a low molecular compound (for example, having a molecular weight of less than 2,000 and further having a molecular weight of less than 1,000), or may be a macromolecular compound (for example, a molecular weight of 1,000 or more, and in the case of a polymer, a weight average molecular weight). It is more than 1000). The weight average molecular weight of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000.

As the epoxy group-containing compound having a structure in which two benzene rings are bonded by a hydrocarbon group, a compound represented by the following formula (2a) can be preferably used.

[Chemical Formula 10]

In the formula (2a), R ¹ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.

The details of R ¹ to R ¹⁹ of the general formula (2a) can be referred to in paragraph 0036 of JP-A-2013-011869, and the contents are included in the present specification.

In particular, it is preferred that each of R ¹ to R ^{19 is} independently a hydrogen atom, a methyl group, an ethyl group or a methoxy group. Further, one or more selected from the group consisting of R ¹³ , R ¹⁸ and R ¹⁹ is more preferably a methyl group. R ¹³ , R ¹⁸ and R ¹⁹ are each a methyl group, and it is more preferable that R ¹ to R ¹² and R ¹⁴ to R ¹⁷ are a hydrogen atom.

The compound represented by the above formula (2a) can be synthesized by referring to paragraph 0036 of JP-A-2013-011869. As a commercial item, VG-3101L by Printec Corporation, NC-6000 by NIPPON KAYAKU CO., LTD., NC-6300, etc. are mentioned.

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

[Chemical Formula 11]

In the formula (EP1), R ^EP1 to R ^EP3 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group may have a cyclic structure or may have a substituent. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may also be bonded to each other to form a ring structure.

Q ^EP represents a single bond or an organic group of n ^EP valence. R ^EP1 to R ^EP3 may also bond with Q ^EP to form a ring structure.

n ^EP represents an integer of 2 or more, 2 to 10 is preferable, and 2 to 6 is further more preferable. However, when Q ^EP is a single bond, n ^EP is 2.

For details of R ^EP1 to R ^EP3 and Q ^EP , the descriptions of paragraphs 0087 to 088 of JP-A-2014-089408 can be referred to.

Specific examples of the compound having an epoxy group are exemplified below, but the present invention is not limited to these.

[Chemical Formula 12]

As the compound having an epoxy group, an oligomer or a polymer having an epoxy group in a side chain can also be preferably used. Examples of such a compound include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolac type epoxy resin, and an aliphatic epoxy resin.

These compounds can be used as a commercial product, and can also be obtained by introducing an epoxy group into a side chain of a polymer.

As a commercial item, for example, bisphenol A type epoxy resin system, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 860 EPICLON 1050, EPICLON 1051, EPICLON 1055 (manufactured by DIC Corporation), etc., as bisphenol F type epoxy resin system, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 830, EPICLON 835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (manufactured by NIPPON KAYAKU CO., LTD.), etc., as phenol novolak type epoxy resin system, JER152, JER154, JER157S70, JER157S65 (above) , manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc., as a cresol novolac epoxy resin system, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 Above, NIPPON KAYAKU CO., LTD., etc., as an aliphatic epoxy resin system, ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above, manufactured by ADEKA CORPORATION), CELLOXIDE2021P, CELLOXIDE2081 CELLOXIDE2083, CELLOXIDE2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above, manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, Nagase ChemteX Corporation) and the like. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN 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 Resins Co., Ltd.), and the like.

Further, 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), and EPICLON 840 (manufactured by DIC Corporation) can be preferably used. EPICLON N660 (manufactured by DIC Corporation), EPICLON HP7200 (manufactured by DIC Corporation), and the like.

In the colored curable composition of the present invention, the content of the curable compound to the total solid content of the colored curable composition is preferably from 0.1 to 40% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, more preferably 20% by mass or less. One type of the curable compound may be used alone or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably in the above range.

<<Multifunctional 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, a compound having a structure represented by the following formula (T1) is preferred.

General formula (T1)

[Chemical Formula 13]

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

In the above formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and an L-alkyl group having 2 to 12 carbon atoms is particularly preferable. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulae (T2) to (T4), and compounds represented by the formula (T2) are particularly preferred. These polyfunctional thiols can be used singly or in combination of plural kinds.

[Chemical Formula 14]

In the case where the colored curable composition of the present invention contains a polyfunctional thiol, the content of the polyfunctional thiol relative to the total solid content of the colored curable composition is preferably 0.3 to 8.9% by mass, and preferably 0.8 to 6.4% by mass. Better. Further, the polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

<<Solvent>>

The color hardening composition of the present invention contains a solvent.

The solvent is not particularly limited as long as the solubility of each component or the coating property of the coloring curable composition is satisfied, but it is selected in consideration of solubility, coating property, and safety of a coloring agent, a resin, and a curable compound. good.

As the solvent, preferred are as follows: esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, butyric acid Propyl ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg , methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate ( Examples: methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxopropionate (eg methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxygen) Propyl propyl propionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -ethyl ethoxypropionate)), methyl 2-oxy-2-methylpropanoate and 2-oxy-2-methylpropane Ethyl ester (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, and sodium pyruvate Ester, ethyl acetate, ethyl acetate, ethyl 2-butyrate, ethyl 2-butyrate, etc.; and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol Methyl 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 diethyl ether acetate, propylene glycol propyl ether acetate, etc.; and ketones: methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3 - heptanone or the like; and aromatic hydrocarbons such as toluene, xylene, and the like.

From the viewpoints of the solubility of the coloring agent, the resin, the curable compound, and the like, and the improvement of the coating surface, it is preferable to mix two or more of these solvents. For example, selected from 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, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether A mixed solution of two or more kinds of acid esters is preferred.

The content of the peroxide in the solvent is preferably 0.8 mm mpl/L or less, and more preferably a solvent containing no peroxide.

The content of the solvent is preferably from 5 to 80% by mass in terms of the total solid content concentration of the colored curable composition from the viewpoint of coatability. The lower limit is, for example, more preferably 5% by mass or more, and still more preferably 10% by mass or more. The upper limit is, for example, 60% by mass or less, more preferably 50% by mass or less.

The colored curable composition of the present invention may contain only one type of solvent, or may contain two or more types of solvents. When two or more types are contained, it is preferable that the total amount becomes the above range.

<<Resin>>

The color hardening 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 use of the binder. Further, a resin mainly used for dispersing a colorant such as a pigment is also referred to as a dispersant. However, such use of the resin is an example, and it may be used for the purpose other than the use.

In the colored curable composition of the present invention, the content of the resin relative to the total solid content of the colored curable composition is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. When the content of the resin is in 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 an alkaline dispersant (basic resin).

The dispersant preferably contains at least an acidic dispersant, and is preferably only an acidic dispersant. The dispersant can effectively suppress the generation of needle crystals by containing at least an acidic dispersant. Further, the dispersibility of the colorant is improved, and unevenness in brightness is less likely to occur. Further, since excellent developability can be obtained, a pattern can be appropriately formed by photolithography. In addition, the content of the acidic dispersant in the total mass of the dispersant is preferably 99% by mass or more, and may be 99.9% by mass or more.

Here, the acidic dispersant (acid resin) represents a resin having a larger amount of acid groups than the amount of the basic group. When the total amount of the acid group and the amount of the basic group is set to 100 mol%, the acidic dispersant (acid resin) is preferably a resin having an acid group content of 70 mol% or more, substantially only The resin composed of an acid group is more preferable. The acid group of the acidic dispersant (acid resin) is preferably a carboxyl group.

Further, the alkaline dispersant (basic resin) means a resin having a larger amount of a basic group than the acid group. When the total amount of the acid group and the amount of the basic group is set to 100 mol%, it is preferred that the basic dispersant (basic resin) is a resin having a basic group content of 50 mol% or more. It is preferred that the basic group of the basic dispersant is an amino group.

The acid dispersant (acid resin) preferably has an acid value of 40 to 105 mgKOH/g, more preferably 50 to 105 mgKOH/g, and further preferably 60 to 105 mgKOH/g.

In the present invention, the dispersant is preferably used in an amount of 10 to 100 parts by mass, more preferably 20 to 60 parts by mass, per 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 relative to the total solid content of the colored curable composition is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. As long as the content of the acidic resin is as described above, the developability is good.

In the colored curable composition of the present invention, the ratio of the acidic resin to the total mass of the resin is preferably from 50 to 100% by mass, more preferably from 75 to 100% by mass, still more preferably from 80 to 100% by mass, and further preferably 90. It is particularly preferable to be 100% by mass, and preferably 95 to 100% by mass.

The dispersing agent may, for example, be a polymer dispersing agent (for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester) And modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure. The polymer dispersant adsorbs on the surface of the pigment to prevent re-agglomeration. Therefore, as a preferable structure, the terminal modified type polymer, the graft type polymer, and the block type polymer which have an anchor part to the surface of a pigment are mentioned.

For example, JP-A-2002-273191 discloses a polymer having a phosphate group at a terminal, which is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2003-533455. The polymer having a sulfonic acid group at the terminal, and a polymer having a partial skeleton or a heterocyclic ring of an organic dye described in JP-A-9-77994, and the like. Further, a polymer which introduces two or more anchoring sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic rings, etc.) to the surface of the pigment at the end of the polymer described in JP-A-2007-277514 The dispersion stability is also excellent, so it is preferred.

The graft type polymer may, for example, be a polyester-based dispersant or the like. Specifically, poly(lower alkylene imine) and poly group described in JP-A-H05-370820, JP-A-H08-507960, JP-A-2009-258668, and the like. The reaction product of the polyallylamine and the polyester described in Japanese Laid-Open Patent Publication No. Hei 9-169821, and the like, and the publication of the International Publication No. 2004-37986 A copolymer of a macromonomer and a nitrogen atom monomer described in WO2010/110491, etc., as described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like. A graft-type polymer having a partial skeleton or a heterocyclic ring of an organic dye; a copolymer of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268, and the like; An inert resin having a basic group and an acid group.

As the macromonomer used in the production of the graft polymer by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 (end group A) manufactured by TOAGOSEI CO., LTD. can be used. Acryl fluorenyl polymethyl methacrylate), AS-6 (polystyrene based terminal group is methacryl fluorenyl), AN-6S (styrene and acrylonitrile whose terminal group is methacryl fluorenyl) Copolymer), AB-6 (polybutyl acrylate of methacryl fluorenyl group), PLACEL FM5 manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD. (ε-caprolactone of 2-hydroxyethyl methacrylate) 5 molar equivalents of the finished product), FA10L (2-hydroxyethyl acrylate ε-caprolactone 10 mil equivalents of the finished product), and the polyester-based macromonomer described in JP-A No. 2-272009.

As the block type polymer, a block type polymer described in, for example, JP-A-2003-49110, and JP-A-2009-52010 is preferable.

The resin used as the dispersing agent 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, the 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 acid group-derived monomer 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, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid. Dimer and the like. Further, it is also possible to use a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride or cyclohexane dicarboxylic anhydride. The reactant is ω-carboxy-polycaprolactone mono(meth)acrylate or the like. Further, as the precursor of the carboxyl group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride can be used. Among them, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a monomer such as maleic anhydride, phthalic anhydride, succinic anhydride, or cyclohexane, from the viewpoint of development removability of the unexposed portion. An addition reactant of a cyclic anhydride such as an alkanedicarboxylic acid anhydride is preferred.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid and the like.

Examples of the vinyl monomer having a phosphoric acid group include mono(2-propenyloxyethyl ester) phosphate and mono(1-methyl-2-propenyloxyethyl phosphate).

Further, as a repeating unit having an acid group, the description of paragraphs 0067 to 0069 of JP-A-2008-165059 can be referred to, and the content is included in the present specification.

Further, in the present invention, as the dispersing agent, a graft copolymer comprising a repeating unit represented by any one of the formula (A1) and the formula (A2) and a repeating unit having an acid group can be used. Acidic resin.

[Chemical Formula 15]

In the general formulae (A1) and (A2), R ¹ to R ⁶ each independently represent 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 phenylene, and L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and A ¹ and A ² each independently represent a monovalent organic group. The bases, m and n each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.

R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferred. 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.

As R ^1, R ^2, R ⁴ and R ^5, a hydrogen atom is preferred as R ³ and R ^6, from the viewpoint of adsorption efficiency on the pigment surface view, a hydrogen atom or a methyl group is also preferred.

X ¹ and X ² each independently represent -CO-, -C(=O)O-, -CONH-, -OC(=O)- or a phenylene group. Among them, from the viewpoint of the sorption property to the pigment, -C(=O)O-, -CONH-, and phenylene are preferred, and -C(=O)O- is preferred.

L ¹ and L ² each independently represent a single bond or a divalent organic linking group. As the divalent organic linking group, a substituted or unsubstituted alkylene group, a divalent organic linking group composed of an alkylene group and a hetero atom or an alkylene group and a partial structure containing a hetero atom are preferred.

As the alkylene group, an alkylene group having 1 to 12 carbon atoms is preferred, an alkylene group having 1 to 8 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is particularly preferred.

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 them, an oxygen atom or a nitrogen atom is preferred.

As the divalent organic linking group, from the viewpoint of the sorption property to the pigment, it is preferred to have a terminal group selected from -C(=O)-, -OC(=O)- at the terminal of the above alkylene group. a hetero atom of -NHC(=O)- or a partial structure containing a hetero atom, which is bonded to an adjacent oxygen atom via a hetero atom or a partial structure containing a hetero atom. Here, the adjacent oxygen atom means the general formula (A1) in the L ^1, and the formula (A2), the L ^2, an oxygen atom of the side chain end side key junction.

A ¹ and A ² each independently represent a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferred. The substituents described in Paragraph No. 0027 of JP-A-2009-256572, the contents of which are incorporated herein by reference.

A ¹ and A ^{2 are} a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and 5 carbon atoms from the viewpoint of dispersion stability and developability. A cyclic alkyl group of -20 is preferred, a linear 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 linear alkyl group having 6 to 10 carbon atoms or a branched alkyl group having 6 to 12 carbon atoms is further preferred.

m and n each independently represent an integer of 2-8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferred, and 5 is most preferred.

p and q each independently represent an integer of 1 to 100. It is also possible to mix two or more different types of p and different ones of q. From the viewpoint of dispersion stability and developability, p and q are preferably from 5 to 60, more preferably from 5 to 40, and further preferably from 5 to 20.

For details of the repeating unit represented by the general formula (A1) and the repeating unit represented by the general formula (A2), the contents of the paragraphs 0034 to 0044 of JP-A-2009-256572 can be referred to. Into this manual.

Examples of the repeating unit having an acid group include the above.

For the details of the above-mentioned acidic resin, the contents of paragraphs 0021 to 0,088 of JP-A-2009-256572 can be referred to, and the contents are incorporated in the present specification. Specific examples of the acidic resin include the following.

[Chemical Formula 16]

Further, in the present invention, an oligomeric imine (Oligoimine) resin containing a nitrogen atom in at least one of a main chain and a side chain can be used as the dispersant. The oligomeric imide resin is preferably a resin having a repeating unit and a side chain and having a basic nitrogen atom in at least one of a main chain and a side chain, wherein the repeating unit has _a functional group having a pKa 14 or less Part of the structure X, the side chain contains an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000.

Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The oligomeric imide resin preferably has a structure having a nitrogen atom having a salt strength of pK _b 14 or less, and more preferably has a structure having a nitrogen atom of pK _b 10 or less.

In the present invention, the salt refers to the strength pK _b pK _b at temperature 25 ℃, based index for quantitatively showing one salt intensity, the basicity constant based same meaning. The salt strength pK _b and the acid strength pK _a described later have _a relationship of pK _b =14-pK _a .

The oligomeric imine resin is particularly preferably having a repeating unit (i) selected from a poly(lower alkylene imine) repeating unit and a polyallylamine system, and a side chain (ii). a repeating unit, a polydiallylamine-based repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and a polyvinylamine-based repeating unit, and having a repeating unit of a basic nitrogen atom, and A partial structure X having a functional group bonded to a basic nitrogen atom and containing pK _a 14 or less, and the side chain (ii) contains an oligomer chain or a polymer chain Y having an atomic number of 40 to 10,000.

The poly(lower alkylene imide) may be in the form of a chain or a mesh. Here, in the present invention, the lower alkyleneimine means an alkyleneimine having an alkylene chain having 1 to 5 carbon atoms.

It is preferred that the repeating unit (i) forms a main chain portion in the oligomeric imide resin. The number average molecular weight of the main chain portion, that is, the number average molecular weight of the side chain (ii) portion removed from the oligomeric imide resin is preferably from 100 to 10,000, more preferably from 200 to 5,000, and further preferably from 300 to 2,000. For the best. The number average molecular weight of the main chain portion can be determined from the ratio of the hydrogen atom integrated value of the terminal group and the main chain portion measured by the nuclear magnetic resonance spectroscopy, or the oligomer or polymer containing the amine group as a raw material can be determined. The molecular weight of the main chain portion was determined by the molecular weight.

(First aspect of oligomeric imide resin)

In a preferred embodiment of the oligo-imine resin, a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2) can be mentioned.

[Chemical Formula 17]

In the general formulae (I-1) and (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group, and a each independently represents an integer of 1 to 5, and * represents a repeating unit. In the connection portion, X represents a group having _a functional group of pK _a 14 or less, and Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.

The oligomeric imide resin further preferably contains a repeating unit represented by the formula (I-3). In this state, the dispersibility of the coloring agent or the like is further improved.

[Chemical Formula 18]

In the formula (I-3), R ¹ , R ² and a have the same meanings as R ¹ , R ² and a in the formula (I-1). Y' represents an oligomer chain or a polymer chain having an anion group having an atomic number of 40 to 10,000. An oligomer or a polymer having a group which forms a salt by reacting with an amine in a resin having a primary or secondary amine group in the main chain portion can be reacted to form a general formula (I-3). ) indicates the repeating unit.

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

The oligomeric imide resin may contain a lower group having a primary or tertiary amine group in addition to the repeating unit represented by the general formula (I-1), the general formula (I-2), and the general formula (I-3). The alkylimine is used as a repeating unit. Further, the nitrogen atom in the lower alkylene imine repeating unit may be further bonded to a group represented by X, Y or Y'.

The repeating unit represented by the formula (I-1) is preferably contained in an amount of from 1 to 80 mol%, more preferably from 3 to 50 mol%, based on the total repeating unit contained in the oligomeric imide resin.

The repeating unit represented by the formula (I-2) is preferably 10 to 90 mol%, and preferably 30 to 70 mol%, based on the total repeating unit contained in the oligomeric imide resin.

The content ratio of the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2) from the viewpoint of the dispersion stability and the balance between the hydrophilicity and the hydrophobicity [(I) -1): (I-2)] is preferably in the range of 10:1 to 1:100 in terms of molar ratio, and more preferably in the range of 1:1 to 1:10.

Further, the repeating unit represented by the formula (I-3), which is used in combination as needed, contains an oligomer chain having an atomic number of 40 to 10,000 or a partial structure of the polymer chain Y' and a nitrogen atom ionic bond of the main chain. In the total repeating unit contained in the oligoenimine resin, it is preferably from 0.5 to 20 mol%, and preferably from 1 to 10 mol%, from the viewpoint of the effect. Further, it was confirmed by ion spectrometry or salt titration that the polymer chain Y' was ion-bonded.

(Second aspect of oligomeric imide resin)

Other preferred aspects of the oligo-imine-based resin include a repeating unit represented by the following formula (II-1) and a repeating unit represented by the formula (II-2).

[Chemical Formula 19]

In the general formulae (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 the general formulae (I-1) and (I-2).

The oligomeric imide resin further preferably contains a repeating unit represented by the formula (II-3). In this way, the dispersibility of the colorant or the like is further improved.

[Chemical Formula 20]

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

From the viewpoint of availability of raw materials, in the general formulae (II-1), (II-2) and (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom.

The general formula (II-1) is preferably contained in an amount of from 1 to 80 mol%, more preferably from 3 to 50 mol%, based on the total repeating unit contained in the oligomeric imide resin.

The general formula (II-2) is preferably contained in an amount of from 10 to 90 mol%, more preferably from 30 to 70 mol%, based on the total repeating unit contained in the oligomeric imide resin.

From the viewpoint of dispersion stability and the balance between hydrophilicity and hydrophobicity, the 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)] The range of 10:1 to 1:100 in terms of molar ratio is preferred, and the range of 1:1 to 1:10 is better.

The repeating unit represented by the formula (II-3), which is used in combination, is preferably contained in an amount of from 0.5 to 20 mol%, more preferably from 1 to 10 mol%, based on the total repeating unit of the oligoenimine resin.

From the viewpoint of dispersibility, the oligoimide-based resin is particularly the one containing both the repeating unit represented by the formula (I-1) and the repeating unit represented by the formula (I-2). good.

(Partial structure X having _a functional group of pK _a 14 or less)

X has the above-described partial structure at a water temperature of 25 deg.] C has _a pK _a of 14 or less functional groups. The "pK _a " system mentioned here is the definition described in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.).

"PK _a 14 or less-functional group" as long as the system physical properties satisfy the condition, which structure is not particularly limited, and conventionally known functional groups may include pK _a satisfies the above range Tong persons, but pK _a of 12 or less of functional groups Particularly preferred is _a functional group having _a pKa of 11 or less. Specific examples of the partial structure X include a carboxylic acid group (pK _a : about 3 to 5), a sulfonic acid (pK _a : about -3 to -2), and -COCH ₂ CO- (pK _a : 8). ～10 or so), -COCH ₂ CN (pK _a : about 8 to 11), -CONHCO-, phenolic hydroxyl group, -R _F CH ₂ OH or -(R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group. pK _a: about 9 to 11), sulfonylurea group (the pK _a: about 9 to 11) or the like, a carboxylic acid group (the pK _a: about 3 to 5), a sulfonic acid group (the pK _a: -3 to -2) -COCH ₂ CO-(pK _a : about 8 to 10) is particularly preferred.

Part of the structure X is preferably bonded directly to a basic nitrogen atom in a repeating unit having a basic nitrogen atom. The nitrogen atom having a repeating unit of a basic nitrogen atom and the partial structure X may be bonded in such a manner that not only covalent bonding but also ionic bonding forms a base.

As the partial structure X, it is particularly preferable to have a structure represented by the following general formula (V-1), general formula (V-2) or general formula (V-3).

[Chemical Formula 21]

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

The divalent linking group represented by U may, for example, be an alkyl group having an oxygen atom, an extended aryl group or an alkylene oxide group, and an alkyl group having 1 to 30 carbon atoms or a carbon atom. It is particularly preferably an extended aryl group of 6 to 20, and an alkylene group having 1 to 20 carbon atoms or an extended aryl group having 6 to 15 carbon atoms is most preferred. Further, from the viewpoint of productivity, d is 1 is preferable, and e is 0 is preferable.

Q represents a mercapto or alkoxycarbonyl group. As the mercapto group in Q, a mercapto group having 1 to 30 carbon atoms is preferred, and an anthracene group is particularly preferred. The alkoxycarbonyl group in Q is preferably an ethylene group from the viewpoint of easiness of production and availability of a raw material (precursor X' of X).

(oligomer chain or polymer chain Y having an atomic number of 40 to 10,000)

Examples of the oligomer chain or polymer chain Y having an atomic number of 40 to 10,000 include a polyester, a polyamide, a polyimine, and a poly(methyl) which can be bonded to the main chain portion of the oligomeric imide resin. A well-known polymer chain such as acrylate. The terminal portion of Y in which Y is bonded to the oligoi-imide resin is preferably Y.

Y is preferably bonded to the basic nitrogen atom of the above repeating unit (i). The bonding mode of the basic nitrogen atom of the repeating unit (i) to Y is a covalent bond, an ionic bond or a covalent bond, and a mixture of ionic bonds. The ratio of the basic nitrogen atom of the repeating unit (i) to the bonding mode of Y is a covalent bond: ion bond = 100:0 to 0:100 is preferred, 95:5 to 5:95 is more preferable, 90: 10 to 10:90 is the best. Y is preferably bonded to the basic nitrogen atom of the repeating unit (i) or ionicly bonded as a carboxylate.

From the viewpoint of dispersibility, dispersion stability, and developability, the number of atoms of the oligomer chain or polymer chain Y is preferably from 50 to 5,000, more preferably from 60 to 3,000.

The number average molecular weight of Y can be measured by conversion of polystyrene based on GPC method. The number average molecular weight of Y is particularly preferably from 1,000 to 50,000, and from 1,000 to 30,000 is preferable from the viewpoint of dispersibility, dispersion stability, and developability.

The side chain structure represented by Y is preferably two or more of the main chain of the resin, and it is preferable to connect five or more.

For the details of Y, the descriptions of paragraphs 0086 to 0098 of JP-A-2013-064979 can be referred to, and the contents are incorporated in the present specification.

The above oligomeric imide resin can be synthesized by the method described in paragraphs 0110 to 0117 of JP-A-2013-064979.

Specific examples of the above oligomeric imide resin include the following resins. Further, the resin described in paragraphs 0099 to 0109 and 0119 to 0124 of JP-A-2013-064979 is incorporated herein by reference.

[Chemical Formula 22]

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

A dispersant can be obtained as a commercial product, and as such a specific example, "DA-7301" manufactured by KUSUMOTO Chemicals, LTD.; "Disperbyk-101 (polyamide-amine phosphoric acid) manufactured by BYK-Chemie GmbH) Salt), 107 (carboxylate), 110 (copolymer containing acid group), 111 (phosphate dispersant), 130 (polyamine), 161, 162, 163, 164, 165, 166, 170 (high "Molecular Copolymers"", "BYK-P104, P105 (High Molecular Weight Unsaturated Polycarboxylic Acids)", "EFKA4047, 4050-4010-4165 (Polyurethane), EFKA 4330 to 4340, manufactured by EFKA) Segment copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment derivative)"; "AJISPER PB821, PB822, PB880, PB881" manufactured by AJINOMOTO FINE-TECHNO Co., Inc.; "FLOWLEN TG-710 (polyurethane) manufactured by KYOEISHA Chemical Co., Ltd. Oligomer)", "POLYFLOW No. 50E, No. 300 (acrylic copolymer)"; KUSUMOTO Chemica "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725" manufactured by ls, Ltd.; "DEMOL RN, N (formalin naphthalenesulfonate polycondensate), MS, C, SN-B (aromatic sulfonate fumarate polycondensate)", "HOMOGENOL L-18 (polymer polycarboxylic acid)" manufactured by KAO Corporation "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN86 (stearylamine acetate)"; "SOLSPERSE 5000 (phthalocyanine derivative) manufactured by LUBRIZOL JAPAN, LTD., 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional portion at the terminal portion), 24000, 28000, 32000, 38500 (graft-type polymer) "NIKKOR T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikko Chemicals Co., Ltd.; KAWAKEN FINE CHEMICALS CO., LTD . manufactured by HINOACT T-8000E, etc.; organic siloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.; YUSHO CO., LTD. "W001: Cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl benzene Nonionic surfactants such as ethyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester, and anionic surfactants such as "W004, W005, W017" "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450" manufactured by MORISHITA & CO., LTD., "DISPERSE AID" manufactured by SUN NOPCO LIMITED 6. DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100" and other polymer dispersants, ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87 "IONET (trade name) S-20" manufactured by SANYO CHEMICAL INDUSTRIES, LTD., P94, L101, P103, F108, L121, P-123", and the like. Further, ACRYBASE FFS-6752, ACRYBASE FFS-187, ACRYCURE-RD-F8, and CYCLOMER P can also be used.

Further, the resin described by the above dispersant may be used in applications other than the dispersant. For example, it can also be used as a binder.

<<<Alkali Soluble Resin>>

The colored curable composition of the present invention can contain an alkali-soluble resin as a resin. The developability and pattern formability are improved by containing an alkali-soluble resin. In addition, alkali-soluble resins can also be used as a dispersant and a binder.

The molecular weight of the alkali-soluble resin is not particularly limited, and the weight average molecular weight (Mw) is preferably 5,000 to 100,000. Further, the number average molecular weight (Mn) is preferably from 1,000 to 20,000.

The alkali-soluble resin may be a linear organic high molecular polymer, or may have at least one base which promotes alkali solubility in a molecule (a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The alkali-soluble resin of the group (hereinafter referred to as "acid group") is appropriately selected.

The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of controlling developability, an acrylic resin, an acrylamide resin, and an acrylic/acrylamide copolymer resin are preferable.

Examples of the group which promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are preferably dissolved in an organic solvent, and can be preferably developed by using a weak alkali aqueous solution, and are particularly preferred. (Meth)acrylic acid is mentioned. These acid groups may be used alone or in combination of two or more.

In the case of producing an alkali-soluble resin, for example, a known method using a radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be experimentally set.

As the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferred, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial ester. An alkali-soluble phenol resin such as a maleic acid copolymer or a novolak resin; and an acid anhydride derivative having a carboxyl group in a side chain and an acid anhydride added to a polymer having a hydroxyl group. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is suitable as the alkali-soluble resin. Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc., and examples of the vinyl compound include styrene, α-methylstyrene, and vinyltoluene. , glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, methacrylic tetrahydrofurfuryl ester, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., in Japan Examples of the N-substituted maleimide monomer described in JP-A-10-300922 include N-phenylmaleimide and N-cyclohexylmaleimide. Further, the other monomers copolymerizable with the (meth)acrylic acid may be used alone or in combination of two or more.

Moreover, in order to improve the crosslinking efficiency of the color hardening composition in the present invention, an alkali-soluble resin having a polymerizable group can be used. Examples of the polymerizable group include a (meth)allyl group and a (meth)acryl fluorenyl group. An alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin containing a polymerizable group in a side chain.

The alkali-soluble resin containing a polymerizable group is preferably a resin or the like which is obtained by reacting an isocyanate group with a hydroxyl group to leave an unreacted isocyanate group, and a polymerizable group such as a (meth)acryl fluorenyl group. An alkali-soluble resin modified with a urethane obtained by reacting a compound with a carboxyl group-containing acrylic resin; and an acrylic resin having a carboxyl group and a compound having an epoxy group and a polymerizable double bond in the molecule; An alkali-soluble resin obtained by the reaction; an acid pendant acrylic acrylate resin; an alkali-soluble resin obtained by reacting a hydroxyl group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond; An alkali-soluble resin obtained by reacting an acrylic resin with a compound having an isocyanate and a polymerizable group; and the following resin is subjected to alkaline treatment as described in JP-A-2002-229207 and JP-A-2003-335814 The alkali-soluble resin obtained has a halogen atom or a sulfonic acid group at the α-position or the β-position in the side chain. Group of the ester group.

Examples of the alkali-soluble resin containing a polymerizable group include DIANAL NR series (manufactured by MITSUBISHI RAYON SHARES CO., LTD.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), and VISCOAT R. -264, KS RESIST 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.), and Ebecryl 3800 (DAICEL UCB CO.) , manufactured by LTD., Akurikyua-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), and the like.

As the alkali-soluble resin, benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl copolymer may be preferably used. And a multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer. In addition, it is also possible to use 2-hydroxyethyl (meth) acrylate copolymerized, and 2-hydroxypropyl (meth) acrylate/polyphenyl group described in JP-A-7-140654 Ethylene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 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 macromonomer/A Benzyl acrylate / methacrylic acid copolymer and the like.

It is also preferred that the alkali-soluble resin comprises a polymer (a) which contains a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (below) Further, the monomer components of these compounds are sometimes referred to as "ether dimers".

[Chemical Formula 23]

In the 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.

[Chemical Formula 24]

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

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 a methyl group, an ethyl group, and a n-propyl group. a linear or branched alkyl group such as isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 2-ethylhexyl; an aryl group such as phenyl; An alicyclic group such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl or 2-methyl-2-adamantyl; An alkyl group substituted with an alkoxy group such as an oxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among them, in particular, from the viewpoint of heat resistance, a substituent such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group which is not easily desorbed from a primary or secondary carbon by acid or heat is preferred.

Specific examples of the ether dimer include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate and diethyl-2,2'-[oxygen Bis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isopropyl) -2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butyl)-2,2'-[oxy double (methylene Base]] bis-2-acrylate, bis(tert-amyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(stearyl)-2,2' -[oxybis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2- Ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxybis (methylene Bis-2-]acrylate, bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, Dibenzyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxybis(methylene)]bis-2-acrylic acid Ester, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butylcyclohexyl)-2,2'-[oxybis(methylene) )] bis-2-acrylate, bis(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tricyclodecyl)- 2,2'-[oxybis(methylene)]bis-2-acrylate, bis(isobornyl)-2,2'-[oxybis(methylene)]bis-2-acrylate , diamantyl-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxy Bis(methylene)] bis-2-acrylate. Wherein, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)]bis-2 - acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxybis(methylene)] double -2-acrylate is especially preferred. These ether dimers may be used alone or in combination of two or more. The structure derived from the compound represented by the general formula (ED) may also copolymerize other monomers.

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

[Chemical Formula 25]

In the 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 may have a benzene ring having 1 to 20 carbon atoms. alkyl. n represents an integer of 1 to 15.

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

The alkali-soluble resin can be referred to in the following paragraphs of JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding to [0685] to [0700] of the specification of the US Patent Application Publication No. 2012/0235099), and the contents are incorporated herein. In the manual.

In addition, the copolymer (B) described in paragraphs 0029 to 0063 described in JP-A-2012-32767, the alkali-soluble resin used in the examples, and the paragraph number of JP-A-2012-208474 can be used. The adhesive resin described in 0088 to 0098 and the adhesive resin used in the examples, the adhesive resin described in paragraphs 0022 to 0032 of JP-A-2012-137531, and the adhesive resin used in the examples, The adhesive resin described in paragraphs 0132 to 0143 of JP-A-2013-024934, and the adhesive resin used in the examples, and the adhesives described in paragraphs 0092 to 0098 of JP-A-2011-242752 The resin and the binder resin used in the examples, and the binder resin described in paragraphs 0030 to 0072 of JP-A-2012-032770. This content is incorporated into this specification.

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

When the coloring curable composition contains an alkali-soluble resin, the content of the alkali-soluble resin relative to the total solid content of the colored curable composition is preferably from 1 to 15% by mass, more preferably from 2 to 12% by mass, and more preferably 3 ～10% by mass is further preferred. The colored curable composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. In the case where two or more kinds of alkali-soluble resins are contained, the total amount thereof is preferably in 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 the organic pigment is substituted by an acidic group, a basic group or a phthalyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferred from the viewpoint of dispersibility and dispersion stability. Pigment derivatives having a basic group are particularly preferred. Further, in the combination of the above resin (dispersion resin) and the pigment derivative, it is preferred that the resin is an acidic resin having an acid group and the pigment derivative is a combination having a basic group.

Examples of the organic pigment constituting the pigment derivative include a diketopyrrolopyrrole pigment, an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, and a dioxazine pigment. A purple ring ketone pigment, an anthraquinone pigment, a thioindole pigment, an isoporphyrin pigment, an isoindolinone pigment, a quinophthalone pigment, a Shilin pigment, a metal complex pigment, and the like.

Further, as the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group and a salt thereof are preferred, and a carboxylic acid group and a sulfonic acid group are further preferred, and a sulfonic acid group is particularly preferred. As the basic group of the pigment derivative, an amine group is preferred, and a tertiary amine group is particularly preferred.

As the pigment derivative, a quinoline-based, a benzimidazolone-based or an isoporphyrin-based pigment derivative is particularly preferable, and a quinoline-based or benzimidazolone-based pigment derivative is further preferable. A pigment derivative having the following structure is particularly preferred.

[Chemical Formula 26]

In the general formula (P), A represents a structure selected from the following general formulae (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 -,

D represents a single bond, an alkyl group or an aryl 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 represent an alkyl group or an aryl group, and Rpa and Rpb may be bonded to each other to form a ring.

t represents an integer from 1 to 5;

[Chemical Formula 27]

In the general formulae (PA-1) to (PA-3), Rp ₁ represents an alkyl group or an 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 -,

s represents an integer of 0 to 4, and when s is 2 or more, a plurality of Rp ₂ may be the same or different.

* indicates the connection to B.

Rp ₁ is preferably a methyl group or a phenyl group, and a methyl group is most preferred.

Rp ₂ is preferably a halogen atom, and the chlorine atom is most preferred.

In the general formula (P), examples of the (t+1)-valent linking group represented by B include an alkylene group, an extended aryl group, and a heteroaryl group. Examples of the alkylene group include a linear chain, a branched chain, and a cyclic chain.

The linking group of the (t+1) valence is particularly preferably a linking group represented by the following structural formulae (PA-4) to (PA-9). * indicates the connection with A and C.

[Chemical Formula 28]

In the structural formulae (PA-4) to (PA-9), the pigment derivative having a linking group represented by the structural formula (PA-5) or (PA-8) is more excellent in dispersibility, and thus it is particularly preferable as B. good.

In the general formula (P), examples of the alkylene group and the extended aryl group represented by D include a methylene group, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, and a nonenyl group. Cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclodecenyl, phenylene, naphthylene, and the like. Among these, as D, a linear alkyl group is preferred, and a linear alkyl group having 1 to 5 carbon atoms is more preferred.

In the general formula (P), when E represents -N(Rpa)(Rpb), examples of the alkyl group and the aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, and an isopropyl group. , butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, Cyclodecyl, phenyl, naphthyl and the like. 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, an alkali metal or an ammonium atom such as a lithium atom, a sodium atom or a potassium atom is formed as an atom or a group of a salt. Tetraalkylammonium or the like is preferred.

It is preferred that t is 1 or 2.

Specific examples of the pigment derivative are shown below, but the present invention is not limited to these.

In addition, as a pigment derivative, the description of paragraphs 0162 to 0183 of JP-A-2011-252065 can be referred to, and the content is incorporated in the present specification. In the following formula, Me represents a methyl group, Et represents an ethyl group, and M represents a hydrogen atom or an atom or a group forming a salt.

[Chemical Formula 29]

[Chemical Formula 30]

[Chemical Formula 31]

[Chemical Formula 32]

The content of the pigment derivative in the colored curable composition of the present invention is preferably from 1 to 30% by mass, and more preferably from 3 to 20% by mass, based on the total mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

<<Photopolymerization initiator>>

The color hardening 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 the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Further, it may be an active agent which generates a living radical by some action with a photo-stimulated sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer.

Further, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, or a hexaarylbisimidazole or an anthracene. An anthracene compound such as a derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone.

Further, from the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, and a phosphine oxide compound. , metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron mismatch A compound of the group consisting of a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound is preferred.

a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzophenone compound, and an acetophenone compound are More preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound is particularly preferred.

In particular, when the colored curable composition of the present invention is used in the production of a color filter of a solid-state image sensor, it is necessary to form a fine pattern in a tapered shape, so that curing is performed and development is performed without residue on the unexposed portion. More important. From such a viewpoint, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, a stepper exposure apparatus (exposure machine) is used for curing exposure, but the exposure machine may be damaged by halogen, and a photopolymerization initiator is also required. In view of this, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator when forming a fine pattern such as a solid-state image sensor. Further, the transferability can be more optimized by using a ruthenium compound.

Specific examples of the photopolymerization initiator can be referred to, for example, in paragraphs 0265 to 0268 of JP-A-2013-29760.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and a mercaptophosphine-based initiator described in Patent No. 4,258,899 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF SE) can be used.

As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF SE) which are commercially available can be used. The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched with a long-wavelength light source such as 365 nm or 405 nm.

As the mercaptophosphine-based initiator, commercially available products IRGACURE-819 and DAROCUR-TPO (trade names: all manufactured by BASF SE) can be used.

As the photopolymerization initiator, a ruthenium compound can be more preferably mentioned.

As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used.

Examples of the ruthenium compound which can be suitably used in the present invention include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3- Propyl methoxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2one and 2-ethoxycarbonyloxy Amino-1-phenylpropan-1-one and the like.

Further, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, and Japanese specials are also cited. The compound described in each of the publications such as JP-A-2000-80068, JP-A-2000-80068, and JP-A-2006-342166, and the like.

IRGACURE-OXE01 (manufactured by BASF SE) and IRGACURE-OXE02 (manufactured by BASF SE) can also be suitably used in the commercial product. Further, TR-PBG-304 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation) can also be used.

In addition, as the ruthenium compound other than the above-mentioned description, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is attached to the N-position of carbazole, and a U.S. Patent No. 7,626,957 in which a hetero substituent is introduced at a benzophenone site can be used. The compound described in the Japanese Patent Laid-Open Publication No. 2010-15025, and the ketone oxime compound described in Japanese Laid-Open Patent Publication No. 2009-131189. The compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption of 405 nm, and has a good sensitivity to a g-line light source, as described in JP-A-2009-221114. Compounds, etc.

For example, it is preferable to refer to paragraphs 0274 to 0725 of JP-A-2013-29760, and the contents are incorporated in the present specification.

Specifically, as the hydrazine compound, a compound represented by the following formula (OX-1) is preferred. Further, the N-O bond of ruthenium may be an oxime compound of the (E) form, a ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical Formula 33]

In the 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), as the monovalent substituent represented by R, a monovalent non-metal atomic group is preferred.

The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above substituent may be further substituted with another substituent.

The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group.

In the formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.

In the general formula (OX-1), as the divalent organic group represented by A, an alkylene group having a carbon number of 1 to 12, a cycloalkylene group or an alkynylene group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.

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

[Chemical Formula 34]

The ruthenium compound is preferably one having a maximum absorption wavelength in a wavelength region of from 350 nm to 500 nm, more preferably having an absorption wavelength in a wavelength region of from 360 nm to 480 nm, and particularly preferably having a higher absorbance at 365 nm and 405 nm.

Among the ruthenium compounds, from the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000.

The molar absorption coefficient of the compound can be preferably measured by a known method, for example, by an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

The photopolymerization initiator to be used in the present invention may be used in combination of two or more kinds as needed.

In the case where the colored curable composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator relative to the total solid content of the colored curable composition is preferably from 0.1 to 50% by mass, preferably from 0.5 to 30. The mass % is more, and 1 to 20% by mass is further more preferable. Within this range, more excellent sensitivity and pattern formation can be obtained.

Moreover, when the colored curable composition of the present invention is used for dry etching, it can also be a composition which does not substantially contain a photopolymerization initiator. In the case where the photopolymerization initiator is not substantially contained, the content of the total amount of the total solid content of the photopolymerizable composition of the coloring curable composition of the present invention is preferably 1% by mass or less, more preferably 0.1% by mass or less. Good, 0% by mass is especially good.

The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. In the case where two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

<<Polymerization inhibitor>>

In the color hardening composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the colored curable composition, it is preferred to add a small amount of a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-sulfur. Di-bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first Salt and so on.

In the case where the colored curable composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the mass of the colored curable composition is preferably from about 0.01 to 5% by mass.

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 of polymerization inhibitors are contained, the total amount thereof is preferably in the above range.

<<Interfacial active agent>>

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

For example, when a coating liquid is prepared by containing a fluorine-based surfactant, liquid characteristics (especially fluidity) at the time of preparation of a coating liquid are further improved. In other words, when a film is formed using a color-curable composition containing a fluorine-based surfactant, the interface tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is moistened. The wettability is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to further appropriately form a film having a small thickness unevenness and a uniform thickness.

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

Examples of the fluorine-based surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, and MEGAFAC F479. , MEGAFAC F482, MEGAFAC F554, MEGAFAC F780, MEGAFAC F781, MEGAFAC F781F (above, manufactured by DIC Corporation); FLUORAD FC430, FLUORAD FC431, FLUORAD FC171 (above, manufactured by SUMITOMO 3M Limited); SURFLON S-382, SURFLON SC-101, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC1068, SURFLON SC-381, SURFLON SC-383, SURFLON S393, SURFLON KH-40 (above, manufactured by ASAHI GLASS CO., LTD.); PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), and the like.

As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and the like, and ethoxylates and propoxylates (for example, propoxylated glycerin, ethoxylate). Glycerol, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901 manufactured by BASF SE) , 904, 150R1), SOLSPERSE 20000 (LUBRIZOL JAPAN, LTD.), and the like. Further, PIONIN D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD. can also be used.

Specific examples of the cation-based surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), and an organic siloxane polymer KP341 (Shin-Etsu Chemical Co.). (manufactured by Ltd.), (meth)acrylic (co)polymers POLYFLOW No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), W001 (manufactured by YUSHOCO., LTD.), etc. .

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by YUSHOCO., LTD.).

Examples of the anthrone-based surfactants include "TORAY SILICONE DC3PA", "TORAY SILICONE SH7PA", "TORAY SILICONE DC11PA", "TORAY SILICONE SH21PA", and "TORAY SILICONE" manufactured by DOW CORNING TORAY CO., LTD. SH28PA", "TORAY SILICONE SH29PA", "TORAY SILICONE SH30PA", "TORAY SILICONE SH8400"; "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" manufactured by MOMENTIVE PERFORMANCE MATERIALS Inc. ""TSF-4452"; "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd.; "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie CO., LTD. "Wait.

In the case where the colored curable composition of the present invention contains a surfactant, the content of the surfactant to the total mass of the colored curable composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. .

The colored curable composition of the present invention may contain only one type of surfactant, or may contain two or more types. In the case where two or more kinds of surfactants are contained, the total amount thereof is preferably in the above range.

<<decane coupling agent>>

The color hardening composition of the present invention may contain a decane coupling agent.

As the decane coupling agent, a decane compound having at least two functional groups having different reactivity in one molecule is also preferable, and an amine group and an alkoxy group are particularly preferable as the functional group. As such a decane coupling agent, for example, N-β-aminoethyl-γ-aminopropyl-methyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602) is available. N-β-aminoethyl-γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ -Aminopropyl-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyl-trimethoxydecane (Shin-Etsu Chemical Co., Ltd.) Manufactured, trade name KBM-903), γ-aminopropyl-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, KBE-903), 3-methacryloxyloxy group Propyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, KBM-503) and the like. For the details of the decane coupling agent, the descriptions of paragraphs 0155 to 0158 of JP-A-2013-254047 are incorporated herein by reference.

In the case where the colored curable composition of the present invention contains a decane coupling agent, the content of the decane coupling agent to the total solid content of the colored curable composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass. Preferably, 0.1% by mass to 5% by mass is particularly preferred.

The colored curable composition of the present invention may contain only one type of decane coupling agent, or may contain two or more types. In the case where two or more kinds of decane coupling agents are contained, the total amount thereof is preferably in the above range.

<<Other additives>>

In the color hardening composition of the present invention, various additives such as a filler, an antioxidant, an ultraviolet absorber, a coagulation inhibitor, and the like can be blended as needed. The above-mentioned additives are described in paragraphs 0155 to 0156 of JP-A-2004-295116, and the contents are incorporated in the present specification.

In the coloring-curable composition of the present invention, the sensitizer and the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the above publication can be contained. .

<Method for Preparing Colored Curable Composition>

The color hardening composition of the present invention is prepared by mixing the above components.

In the preparation of the colored curable composition, the components constituting the colored curable composition may be uniformly blended, or may be blended one by one after the components are dissolved and dispersed in a solvent. Moreover, the order of placement and the working conditions at the time of fitting are not particularly restricted. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions or dispersions, and when used (at the time of coating), These were mixed to prepare a composition.

The colored hardenable composition of the present invention is preferably filtered by a filter for the purpose of removing foreign matter and reducing defects. The filter can be used without particular limitation as long as it is used for filtration purposes or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6, 6, a polyolefin resin such as polyethylene or polypropylene (PP) (including high density and super) may be mentioned. A filter composed of a high molecular weight or the like. Among these raw materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting this range, it is possible to reliably remove fine foreign matter which hinders uniform and smooth preparation of the colored curable composition in the subsequent process.

When using a filter, it is also possible to combine different filters for use. In this case, the first filter may be used for filtration only once or twice or more.

Further, the first filter having a different pore diameter may be combined within the above range. The aperture here can be found in the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., ADVANTECH TOYO KAISHA, LTD., NIHON ENTEGRIS K.K. (Mykrolis Corporation), or KITZ MICROFILTER CORPORATION.

The second filter can be formed of the same material or the like as the first filter described above.

For example, the filtration by the first filter may be performed only by the dispersion, or the second filtration may be performed after mixing the other components.

Since the colored curable composition of the present invention can form a cured film excellent in light resistance, transfer property, and flatness, it can be suitably used for forming a coloring layer of a color filter. Further, the colored curable composition of the present invention can be suitably used for forming a solid-state imaging device such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), and a color filter used in an image display device such as a liquid crystal display device. The use of colored patterns such as light sheets. In addition, it is also suitable for use in printing inks, inkjet inks, and coatings. Among them, it is suitable for use in the manufacture of color filters for solid-state imaging devices such as CCDs and CMOSs.

<Color filter, pattern forming method, and method of manufacturing color filter>

Next, the color filter, the pattern forming method, and the method of manufacturing the color filter of the present invention will be described in detail. Further, a method of manufacturing a color filter using the pattern forming method of the present invention will also be described.

The color filter of the present invention is obtained by using the colored curable composition of the present invention.

In the pattern forming method of the present invention, the colored curable composition layer of the present invention is used to form a colored curable composition layer on a support, and an unnecessary portion is removed to form a colored pattern.

The pattern forming method of the present invention can be preferably applied to a colored pattern forming a color filter.

The pattern forming method of the present invention may be patterned by a so-called photolithography method, or may be patterned by a dry etching method.

That is, the first aspect of the method for producing a color filter of the present invention includes a process of forming a colored curable composition layer on a support by using the colored curable composition of the present invention; and a colored curable composition layer a process of exposing to a pattern; and a process of developing and removing the unexposed part to form a colored pattern. If necessary, a process of baking the colored curable composition layer (prebaking process) and a process of baking the developed coloring pattern (post-baking process) may be also set.

Moreover, the second aspect of the method for producing a color filter of the present invention includes a process of forming a colored layer of a colored curable composition on a support by using the colored curable composition of the present invention, and curing to form a colored layer; a process of forming a photoresist layer on the colored layer; patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask, dry etching the colored layer to form The process of coloring patterns.

The color filter of the present invention can be preferably obtained by the above-described production method. Hereinafter, the details will be described.

<<Process for forming a color hardening composition layer>>

In the process of forming the colored curable composition layer, the colored curable composition layer of the present invention is used to form a colored curable composition layer on the support.

As the support, for example, a substrate for a solid-state imaging device in which a solid-state imaging device (light-receiving element) such as a CCD or a CMOS is provided on a substrate (for example, a germanium substrate) can be used.

The colored pattern in the present invention may be formed on the solid-state imaging device forming surface side (surface) of the solid-state imaging device substrate, or may be formed on the solid-state imaging device non-forming surface side (back surface).

If necessary, in order to improve the adhesion to the upper layer, prevent the scattering of the substance, or achieve flattening of the surface of the substrate, an undercoat layer may be provided on the support.

As a method of applying the color hardening composition of the present invention to a support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used.

The drying (prebaking) of the colored hardening composition layer applied to the support can be carried out at a temperature of 50 to 140 ° C for 10 to 300 seconds using a hot plate, an oven or the like.

<<The case of forming a pattern by photolithography (first aspect)>>

<<<Exposure Process>>>

Next, the colored curable composition layer formed on the support is exposed in a pattern (exposure process). For example, the coloring-curable composition layer formed on the support can be exposed by exposure using a mask having a predetermined mask pattern by using an exposure apparatus such as a stepper. Thereby, the exposed portion can be hardened.

As the radiation (light) which can be used for exposure, it is preferable to use ultraviolet rays such as g-line or i-line (i-line is particularly preferable). The irradiation amount (exposure amount) is preferably, for example, 30 to 1,500 mJ/cm ² , more preferably 50 to 1000 mJ/cm ² , and most preferably 80 to 500 mJ/cm ² .

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and still more preferably 0.2 to 0.8 μm. By setting the film thickness to 1.0 μm or less, it is easy to obtain high resolution and high adhesion.

<<<pattern forming process>>>

Next, the unexposed portion is developed and removed to form a colored pattern (pattern forming process). The development removal of the unexposed portion can be performed using a developer. Thereby, the colored curable composition layer of the unexposed portion in the exposure process is dissolved in the developer, and only the portion where the light is hardened remains.

An organic alkaline developing solution in which the developer does not damage the solid image sensor, the circuit, or the like of the substrate is preferable.

The temperature of the developer is preferably, for example, 20 to 30 °C. The development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the developer may be oscillated every 60 seconds, and the process of re-supplying the 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, and hydroxide. An organic basic compound such as tetrabutylammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo[5.4.0]-7-undecene. The alkaline aqueous solution obtained by diluting the alkali chemicals with pure water as a developing solution is preferably used in an amount of 0.001 to 10% by mass (preferably 0.01 to 1% by mass).

Further, an inorganic base may be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate or the like is preferable.

Further, in the case of using a developer composed of such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

After the development, it is preferred to carry out heat treatment (post-baking) after drying. When a multicolor coloring pattern is formed, a process can be repeated for each color to produce a cured film. Thereby, a color filter can be obtained.

The post-baking is used for heat treatment after development in which hardening is performed, and the heating temperature is preferably 100 to 240 ° C, more preferably 200 to 240 ° C.

The film after development can be post-baked in a continuous or batch manner by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high frequency heater.

<<The case of forming a pattern by dry etching method (second aspect)>>

The colored curable composition layer formed on the support is cured to form a colored layer, and then the patterned photoresist layer is used as a mask, and the obtained colored layer is patterned by dry etching using an etching gas. .

Specifically, for example, a colored layer is formed by curing the colored curable composition layer by heat or exposure, and a positive or negative radiation sensitive composition is applied onto the colored layer and dried, thereby forming Photoresist layer. When the photoresist layer is formed, it is preferred to further perform a prebaking treatment. In particular, as a forming procedure of the photoresist layer, it is preferable to perform a heat treatment after exposure and a heat treatment (post-baking treatment) after development.

As the photoresist layer, for example, a positive feeling of radiation induced by ultraviolet rays (g line, h line, i line), far ultraviolet rays including an excimer laser, an electron beam, an ion beam, and X-rays can be preferably used. Radiation linear composition. In the radiation, the g line, the h line, and the i line are preferable, and the i line is preferable.

Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin, which is decomposed by light irradiation of a wavelength of 500 nm or less to form a carboxyl group, and is changed from a non-alkali state. The result of alkali solubility. Since this positive type resist is excellent in resolution, it can be used for the production of integrated circuits such as IC (integrated circuit) or LSI (Large Scale Integration). As the quinonediazide compound, a naphthoquinonediazide compound can be mentioned. As a commercial item, "FHi622BC" (made by FUJIFILM Electronic Materials Co., Ltd.), etc. are mentioned, for example.

The thickness of the photoresist layer is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, and still more preferably 0.3 to 2 μm. Further, the method of applying the positive type radiation sensitive composition can be preferably carried out by a coating method in the coloring layer already described.

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

Exposure of the photoresist layer can be performed by exposing the positive or negative radiation sensitive composition to a predetermined mask pattern by using a g-line, an h-line, an i-line or the like, preferably by using an i-line. After the exposure, development processing is performed using a developing solution, thereby aligning the regions where the colored pattern is to be formed to remove the photoresist.

As the developer, any one of the exposed portions of the positive resist layer and the uncured portion of the negative resist layer can be used without affecting the colored layer. For example, a combination of various solvents or an aqueous alkaline solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving a basic compound in a concentration of 0.001 to 10% by mass, preferably dissolved at a concentration of 0.01 to 5% by mass, is preferable. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide. Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and the like. Further, when an alkaline aqueous solution is used, the cleaning treatment is usually carried out with water after development.

Next, the resist pattern is used as an etch mask, and patterned by dry etching so that a through hole group is formed in the colored layer. Thereby, a colored pattern is formed. It is preferable that the through hole group is provided in a black-and-white square shape, 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 black and white checkered shape.

As the dry etching, from the viewpoint of forming a pattern cross section closer to a rectangular shape or further reducing damage to the support, it is preferable to carry out the following aspects.

It is preferable to include an etching method in which etching is performed to a first step of a region (depth) in which a support is not exposed by a mixed gas of a fluorine-based gas and oxygen (O ₂ ); etching in the first step Thereafter, using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ), etching is preferably performed to the etching of the second step near the region (depth) where the support is exposed; and after the support is exposed Etching. Hereinafter, a specific method of dry etching, etching of the first step, etching of the second step, and overetching will be described.

The dry etching is performed by previously obtaining etching conditions by the following method.

(1) The etching rate (nm/min) in the etching of the first step and the etching rate (nm/min) in the etching of the second step were respectively calculated.

(2) The time for etching the desired thickness in the etching of the first step and the time for etching the desired thickness in the etching of the second step are respectively calculated.

(3) The etching of the first step is performed in accordance with the etching time calculated in the above (2).

(4) The second-stage etching is performed in accordance with the etching time calculated in the above (2). Alternatively, the end point detection may be used to determine the etching time, and the etching of the second stage may be performed according to the determined etching time.

(5) The overetching time is calculated for the total time of the above (3) and (4), and over etching is performed.

As the mixed gas used in the etching process of the first step, it is preferable to contain a fluorine-based gas and oxygen (O ₂ ) from the viewpoint of processing the organic material as the film to be etched into a rectangular shape. Further, the etching process in the first step can be avoided by damaging the region in which the support is not exposed. Further, in the etching process of the second step, the etching process in the first step is etched by a mixed gas of a fluorine-based gas and oxygen gas to a region where the support is not exposed, from the viewpoint of avoiding damage to the support. It is preferred to carry out etching treatment using a mixed gas of nitrogen and oxygen.

It is important to determine the ratio of the etching amount in the etching process in the first-stage etching process to the etching amount in the etching process in the second-stage etching process without impairing the squareness formed by the etching process in the etching process of the first-stage etching process. . Further, the ratio of the latter in the total etching amount (the total of the etching amount in the etching process in the first-stage etching process and the etching amount in the etching process in the second-stage etching process) is preferably greater than 0% and 50% or less. ~20% is better. The etching amount is an amount calculated from the difference between the film thickness of the film to be etched and the film thickness before etching.

Further, the etching includes an overetching treatment preferably. It is preferable to set the overetching ratio and perform the overetching treatment. Further, it is preferable to calculate the overetch ratio based on the etching treatment time which is initially performed. The overetching ratio can be arbitrarily set. However, from the viewpoint of the etching resistance of the photoresist and the squareness of the etched pattern, 30% or less of the etching treatment time in the etching process is preferable, and 5 to 25% is more preferable. ~15% is especially good.

Next, the resist pattern remaining after the etching (that is, the etching mask) is removed. The removal of the resist pattern includes a process of applying a stripping liquid or a solvent to the resist pattern, a process of removing the resist pattern, and a process of removing the resist pattern by the cleaning water.

The process of applying a peeling liquid or a solvent to the resist pattern in a state in which the resist pattern can be removed, for example, at least a peeling liquid or a solvent is applied to the resist pattern, and the stirring is performed for a predetermined period of time (paddle) ) Development process. The time for stopping the stripping solution or solvent is not particularly limited, but it is preferably from several tens of seconds to several minutes.

Moreover, as a process of removing the resist pattern by the washing water, for example, a process of ejecting the washing water from the spray type or the spray type jet nozzle to the resist pattern to remove the resist pattern can be mentioned. As the washing water, pure water can be preferably used. Further, the injection nozzle may be an injection nozzle or a movable injection nozzle in which the entire support body is included in the injection range, that is, an injection nozzle whose movable body includes the entire support. In the case where the ejection nozzle is movable, in the process of removing the resist pattern, the cleaning water is sprayed two or more times between the center of the support body and the end of the support body, whereby the resist pattern can be removed more effectively. .

The stripper usually contains an organic solvent, but may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon compound, 2) a halogenated hydrocarbon compound, 3) an alcohol compound, 4) an ether or an acetal compound, 5) a ketone or an aldehyde compound, and 6) an ester system. a compound, 7) a polyol compound, 8) a carboxylic acid or an anhydride thereof, 9) a phenol compound, 10) a nitrogen-containing compound, 11) a sulfur-containing compound, and 12) a fluorine-containing compound. As the stripping liquid, a nitrogen-containing compound is preferable, and a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound are more preferable.

As the acyclic nitrogen-containing compound, an acyclic nitrogen-containing compound having a hydroxyl group is preferred. Specific examples thereof include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, and the like. Diethanolamine, triethanolamine, etc., monoethanolamine, diethanolamine, triethanolamine are preferred, and monoethanolamine (H ₂ NCH ₂ CH ₂ OH) is more preferred. Further, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α. -picolin, β-picoline, γ-picoline, Pipecoline, 3-piperonoline, 4-piperonphyrin, piperazine, piperidine, pyrazine, pyridine, pyrrole Alkane, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine, etc., N-methyl-2-pyrrolidone, N-ethylmorpholine Preferably, N-methyl-2-pyrrolidone (NMP) is more preferred.

The stripping liquid preferably comprises an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, but contains at least one acyclic nitrogen-containing compound selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine, and is selected from N-methyl groups. More preferably, at least one cyclic nitrogen-containing compound of 2-pyrrolidone and N-ethylmorpholine is further preferred, and monoethanolamine and N-methyl-2-pyrrolidone are further preferred.

When the removal is performed by the stripping solution, the resist pattern formed on the colored pattern may be removed, and even if a deposit as an etching product adheres to the side wall of the colored pattern, the deposit may not be completely removed. The deposit means that the etching product adheres to and deposits on the side wall of the colored layer.

The content of the acyclic nitrogen-containing compound is preferably 9 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the peeling liquid, and the content of the cyclic nitrogen-containing compound relative to 100 parts by mass of the peeling liquid is 65 parts by mass. More than 70 parts by mass or less. Further, the stripping liquid is preferably a mixture of a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound diluted with pure water.

In addition to the above-described processes, the method for producing a color filter of the present invention may have a process known as a method of producing a color filter for a solid-state image sensor, as needed. For example, the hardening process of hardening the formed colored pattern by heating and/or exposure may be performed after performing the above-described coloring hardening composition layer forming process, exposure process, and pattern forming process.

Further, in order to effectively clean the nozzle or the piping portion of the coating device discharge portion, and the contamination due to adhesion, precipitation, and drying of the colored curable composition or pigment in the coater, the coloring of the present invention is hardened. It is preferred that the solvent involved in the composition be used as a cleaning liquid. In addition, Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A cleaning liquid described in, for example, Japanese Laid-Open Patent Publication No. 2007-281523, and the Japanese Patent Publication No. 2007-281523, and the like.

Among the above, an alkylene glycol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether are preferred.

These solvents may be used singly or in combination of two or more. When two or more kinds are mixed, a solvent having a hydroxyl group and a solvent having no hydroxyl group are preferably mixed. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and further preferably from 20/80 to 80/20. A ratio of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) is particularly preferably 60/40. Further, in order to increase the permeability of the cleaning liquid to the contaminants, the surfactant related to the coloring curable composition of the present invention may be added to the cleaning liquid.

The color filter of the present invention can be preferably applied to a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for use in a high-resolution CCD, CMOS or the like of more than one million pixels.

The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion constituting each pixel of a CCD or CMOS and a microlens for collecting light.

The coloring pattern (coloring pixel) in the color filter of the present invention has a film thickness of 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 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, or 0.2 μm or more.

<Solid image sensor>

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 has a color filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

The structure is as follows: a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode composed of polysilicon or the like are provided on the support, The photodiode and the transfer electrode have a light-shielding film made of tungsten or the like that opens only the light-receiving portion of the photodiode, and the light-shielding film is formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. A device protective film made of tantalum nitride or the like has a color filter for a solid-state imaging device of the present invention on a device protective film.

Further, it may be configured to have a light collecting means (for example, a microlens or the like, the same below) on the protective layer of the device and on the lower side of the color filter (the side close to the support), or may have a color filter. The composition of the concentrating mechanism, and the like.

<Image display device>

The color filter of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device. It is especially suitable for the use of liquid crystal display devices. The liquid crystal display device including the color filter of the present invention can display a high-quality image in which the hue of the displayed image is good and the display characteristics are excellent.

The definition of the display device and the details of each display device are described, for example, in "Electronic display device (Kogyo Chosakai Publishing Co., Ltd., issued in 1990)", "Display device (Ibuki Shun, "Sangyo Tosho" Co., Ltd., issued in the first year of Heisei)" and so on. Further, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Edited by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable 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 can also be used in a liquid crystal display device of a color TFT (Thin Film Transistor) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD., issued in 1996)". In addition, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a horizontal electric field pulsation method such as IPS (In Plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment) is expanded, or STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend).

Moreover, the color filter of the present invention can also be provided in a bright and high-resolution COA (Color-filter On Array) method. In the liquid crystal display device of the COA type, in addition to the usual required characteristics as described above, in addition to the usual required characteristics, the required characteristics of the interlayer insulating film, that is, the low dielectric constant and the peeling liquid resistance may be required. . Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin coating may be provided on the color filter layer.

These image display methods are described, for example, in "EL, PDP, LCD Display - Technology and Market Trends - (Toray Research Center, Inc. Research and Research Department, issued in 2001)", page 43 and the like.

In the liquid crystal display device including the color filter of the present invention, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle assurance film, and the like are used. It is composed of various components. The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. These components are described, for example, in "The Market of Materials and Chemical Products for Liquid Crystal Display (Island Kent Co., Ltd., CMC Co., Ltd., 1994)", "The Status and Future of the 2003 Liquid Crystal Related Markets (Vol. 2)" "FUJI CHIMERA RESEARCH INSTITUTE, INC., issued in 2003)".

The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et. al), monthly publication December 2005, pages 18 to 24 (Island Kangyu), monthly publication 25 to 30 pages (Yamamu Takamori), and the like.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and by using red, green, and blue light-emitting diodes As a backlight, a body (LED) light source can provide a liquid crystal display device having high brightness and high color reproducibility.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are mass standards.

(Synthesis example) Synthesis of zinc halide phthalocyanine pigment

In the method described in paragraphs 0098 to 0101 of JP-A-2003-161827, the average number of atoms bonded to one molecule of phthalocyanine is appropriately changed as shown in the following table. The amount is used for synthesis.

Further, the composition of the zinc halide phthalocyanine pigment was calculated based on mass analysis and halogen content analysis by a flask combustion ion chromatograph. The number of atoms in the following table is represented by X ¹ to X ^{16 of the} zinc halide phthalocyanine pigment represented by the above formula (A1).

[Table 1]

<Preparation of Green Pigment Dispersion>

The zinc halide phthalocyanine pigment, the yellow pigment, the pigment derivative, the dispersant, and the solvent of Table 1 obtained in the synthesis example were mixed so as to have a mass part shown in the following table, and the bead mill was used. The mixed solution was mixed and dispersed for 15 hours to prepare respective Green pigment dispersions.

[Table 2]

<Preparation of color-curable composition (coating liquid) containing Green pigment>

The green pigment dispersion liquid described above was mixed and stirred so as to have a mass part shown in the following table to prepare a color-curable composition containing a Green pigment.

[table 3]

The raw materials shown in Tables 2 and 3 are as follows.

(halide zinc phthalocyanine pigment)

・Pigments A to M: The zinc halide phthalocyanine pigments A to M shown in Table 1

(yellow pigment)

・PY185: C.I. Pigment Yellow 185

・PY150: C.I. Pigment Yellow 150

・PY139: C.I. Pigment Yellow 139

(Dispersant)

・Dispersant A: The following structure (acidic dispersant, weight average molecular weight = 24000, acid value = 52 mgKOH/g, ratio in repeating unit is molar ratio)

[Chemical Formula 35]

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

[Chemical Formula 36]

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

[Chemical Formula 37]

(pigment derivative)

・Derivative A: The following structure

[Chemical Formula 38]

・Derivative B: The following structure (where M is H)

[Chemical Formula 39]

・Derivative C: The following structure

[Chemical Formula 40]

・Derivative D: The following structure

[Chemical Formula 41]

・Derivative E: The following structure

[Chemical Formula 42]

(hardening compound)

・Compound A: a polymerizable compound (dipentaerythritol hexaacrylate, KAYARAD DPHA, manufactured by NIPPON KAYAKU CO., LTD.)

・Compound B: Epoxy compound (EHPE 3150, manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.)

- Compound C: Polymeric compound (ARONIX TO-2349, manufactured by TOAGOSEI CO., LTD., the following structure)

[Chemical Formula 43]

- Compound D: a polymerizable compound (NK ester A-DPH-12E (ethylene oxide modified dipentaerythritol hexaacrylate, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

- Compound E: a polymerizable compound (NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

・Compound F: Epoxy compound (EPICLON N-695 (epoxy resin of phenolic skeleton), manufactured by DIC Corporation)

- Compound G: a polymerizable compound (M-305 (a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate, manufactured by TOAGOSEI CO., LTD.)

(photopolymerization initiator)

・Starter A: IRGACURE OXE01 (manufactured by BASF SE)

・Starter B: IRGACURE OXE02 (manufactured by BASF SE)

・Starter C: The following structure

[Chemical Formula 44]

・Initiator D: IRGACURE-369 (manufactured by BASF SE)

(surfactant)

Active agent A: MEGAFAC F-781F (fluorine-based surfactant, manufactured by DIC Corporation)

Active agent B: KF6001 (lanthanide surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.)

(resin)

Resin A: the following structure (the ratio in the repeating unit is the molar ratio)

[Chemical Formula 45]

Resin B: the following structure (the ratio in the repeating unit is the molar ratio, and Me is a methyl group).

[Chemical Formula 46]

Resin C: 50:50 (mole 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 and 2.4 parts of Pigment Violet 23 as a pigment, 5.6 parts of BYK-161 (manufactured by BYK SE) as a resin (dispersant), and 82.5 parts of propylene glycol monomethyl ether acetate as a solvent were mixed ( PGMEA) The mixed solution was mixed and dispersed by a bead mill for 15 hours to prepare a Blue pigment dispersion.

<Preparation of color-curable composition (coating liquid) containing Blue pigment>

The coloring curable composition (Blue coloring radiation composition) containing a blue pigment was prepared by mixing and stirring so as to have the following composition.

<composition>

・Pigment dispersion: Blue pigment dispersion 51.2 parts

・Photopolymerization initiator: IRGACURE OXE01 (manufactured by BASF SE) 0.87 parts

・Polymerizing compound: KAYARAD RP-1040 (manufactured by NIPPON KAYAKU CO., LTD.) 4.7 parts

・Resin (adhesive): ACA230AA (manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.) 7.4 parts

・Polymerization inhibitor: p-methoxyphenol 0.002 parts

・Non-ionic surfactant: 0.19 parts of PIONIN D-6112-W (manufactured by TAKEMOTO OIL & FAT CO., LTD.)

・Chane coupling agent: KBM-602 (Shin-Etsu Chemical Co., Ltd.) cyclohexanone 0.9% solution 10.8 parts

・Organic solvent: PGMEA 14.3 parts

・Organic solvent: cyclohexanone 6.4 parts

・Fluorine surfactant: cyclohexanone 0.2% solution of F-781F (manufactured by DIC Corporation) 4.2 parts

[Manufacturing Example 1] (Manufacture of color filter including pattern forming process by photolithography)

<Formation of the first colored layer (green layer)>

The green pigment-containing coloring curable composition of Examples 1 to 12, 15 to 33, and Comparative Examples 1 to 3 obtained in the above manner was applied to the film thickness after coating to a thickness of 0.8 μm using a spin coater. It was coated on a ruthenium wafer with an undercoat layer, and subjected to heat treatment (prebaking) for 120 seconds using a hot plate at 100 ° C to form a coating film.

Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), the exposure amount was adjusted so that the pattern size became 1.4 μm via a 1.4 μm square Bayer pattern mask, and the coating film was irradiated with 365 nm. The i-line of the wavelength is exposed.

Thereafter, the ruthenium wafer on which the exposed coating film was formed was subjected to agitated development at 23 ° C for 30 seconds using a tetramethylammonium hydroxide (TMAH) 0.3% aqueous solution. Thereafter, the mixture was washed by a rotary spray method, and further washed with pure water. Subsequently, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 ° C to obtain a first colored layer (green layer) in which a Bayer pattern of 1.4 μm square was formed.

<Formation of the second colored layer (blue layer)>

The coloring curable composition containing the blue pigment was applied to the first colored layer (green layer) obtained as described above so as to have a film thickness of 0.8 μm after coating, and dried. A laminated color filter in which a second colored layer (blue layer) is formed on a colored layer (green layer).

Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), the exposure amount was adjusted so that the pattern size became 1.4 μm via a 1.4 μm square island mask, and the color was adjusted to the laminated color. The filter is irradiated with an i-line of a wavelength of 365 nm and exposed.

Thereafter, the tantalum wafer on which the exposed laminated color filters were formed was subjected to agitated development at 23 ° C for 30 seconds using a TMAH 0.3% aqueous solution. Thereafter, the mixture was washed by a rotary spray method, and further washed with pure water. Subsequently, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 ° C to obtain a color filter in which a laminated pattern of 1.4 μm square was formed.

[Manufacturing Example 2] (Manufacturing of a color filter including a pattern forming process by a dry etching method)

<Formation of the first colored layer>

The coloring curability of the green pigments of Examples 13 and 14 was applied to a tantalum wafer having a diameter of 200 mm (8 inches) by a spin coater so that the film thickness after coating was 0.8 μm. After the composition, heating was performed at 200 ° C for 5 minutes using a hot plate, and the coating film was cured to form a first colored layer (green layer). The film thickness of the first colored layer (green layer) was 0.8 μm.

(Coating of mask resist)

Next, a positive photoresist "FHi622BC" (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied onto the first colored layer, and prebaking was performed to form a photoresist layer having a film thickness of 0.8 μm.

Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), the exposure amount was adjusted so that the pattern size became 1.4 μm via a 1.4 μm square Bayer pattern mask, and the photoresist layer was irradiated with a wavelength of 365 nm. The i line is exposed.

Next, heat treatment was performed for 1 minute at a temperature at which the temperature of the photoresist layer or the ambient temperature became 90 °C. Thereafter, development treatment was carried out for 1 minute using a developing solution "FHD-5" (manufactured by FUJIFILM Electronic Materials Co., Ltd.), and further post-baking treatment was performed at 110 ° C for 1 minute.

(dry etching)

Next, dry etching is performed in the following order.

Using a dry etching apparatus (manufactured by Hitachi High-Technologies Corporation, U-621), RF (Radio Frequency) power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the chamber: 4.0 Pa, The substrate temperature was 50° C., and the gas type and flow rate of the mixed gas were set to CF ₄ : 80 mL/min, O ₂ : 40 mL/min, and Ar: 800 mL/min, and the first-stage etching treatment was performed for 80 seconds.

Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, internal pressure of the chamber: 2.0 Pa, substrate temperature: 50 ° C, and the gas type of the mixed gas And the flow rate was set to N ₂ :500 mL/min, O ₂ :50 mL/min, Ar:500 mL/min (N ₂ /O ₂ /Ar=10/1/10), and 28 seconds was performed as the second-stage etching. The over-etching process is processed.

After dry etching under the above conditions, a photoresist stripping liquid "MS230C" (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used, and a stripping treatment was performed for 120 seconds to remove the resist, and further washed and rotated with pure water. dry. Thereafter, a dehydration baking treatment was performed at 100 ° C for 2 minutes. From the above, the first colored layer (green layer) after dry etching was obtained.

<Formation of the second colored layer>

The coloring curable composition containing the above-described blue pigment is applied to the first colored layer (green layer) after dry etching obtained as described above, and the film thickness after coating is 0.8 μm. After drying, a laminated color filter in which a 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.), the exposure amount was adjusted so that the pattern size became 1.4 μm via a 1.4 μm square island pattern mask, and the laminated color filter was applied. An i-line of a wavelength of 365 nm was irradiated and exposed.

Thereafter, the tantalum wafer on which the exposed laminated color filters were formed was subjected to agitated development at 23 ° C for 60 seconds using a TMAH 0.3% aqueous solution. Thereafter, the mixture was washed by a rotary spray method, and further washed with pure water. Subsequently, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 ° C to obtain a color filter in which a laminated pattern of 1.4 μm square was formed.

<evaluation>

<<Evaluation of needle crystal production rate>>

Using a scanning electron microscope (S-9260 scanning electron micromirror manufactured by Hitachi, Ltd.), the substrate after post-baking of the second colored layer and the further wafer baked at 240 to 260 ° C for 5 minutes were enlarged by 20,000. The degree of occurrence of needle crystals was evaluated based on the following criteria. In the following evaluations, practical use is 3 to 5.

5: No needle crystals are formed even after post-baking (200 ° C / 5 minutes) and additional baking at 260 ° C / 10 minutes

4: No needle crystals were formed even after post-baking (200 ° C / 5 minutes) and additional baking at 250 ° C / 10 minutes, but after additional baking at 260 ° C / 5 minutes , produces needle crystals.

3: No needle crystals were formed even after post-baking (200 ° C / 5 minutes) and additional baking at 240 ° C / 10 minutes, but after additional baking at 250 ° C / 5 minutes Produces needle crystals.

2: Although needle crystals were not produced after post-baking (200 ° C / 5 minutes), needle crystals were generated after additional baking at 240 ° C / 10 minutes.

1: Needle crystals were produced after post-baking (200 ° C / 10 min).

<<Brightness uneven>>

The green pigment-containing coloring curable composition of Examples 1 to 33 and Comparative Examples 1 to 3 was applied onto a glass substrate at 100 ° C by using a spin coater so that the film thickness after drying was 0.8 μm. The prebaking was carried out for 120 seconds to obtain a colored coating film.

The obtained colored coating film was placed between the spectacle lens of the optical micromirror and the light source, and the light was irradiated onto the spectacle lens, and the transmitted light state was observed by an optical micromirror having a digital camera with a magnification of 1000. The digital camera equipped with the optical micromirror is equipped with a CCD of 1.28 million pixels, and the digital camera is used to photograph the surface of the film in a transmitted light state. The photographic image is saved as data (digital image) digitally converted in the form of an 8-bit bitmap.

Further, the photographing of the surface of the coating film of the colored coating film was carried out on an arbitrarily selected region of 20. In addition, for the data of the digital conversion, the luminance of each of the three primary colors of red, green, and blue of the photographic image is set to a density distribution of 256 gradations from 0 to 255, and is quantized and stored.

Next, the stored digital image is divided into a grid shape so that one crystal lattice size corresponds to 0.5 μm square on the solid substrate, and the luminance in one segment is averaged.

In the present embodiment, since an image of 1000 times optical is photographed by a digital camera of 1.28 million pixels, 0.5 μm on the solid substrate becomes 0.5 mm on the photographic image, and the image size on the display is 452 mm × 352 mm. Therefore, the total number of segments in a region is 636,416.

For the total segment of each region, the average luminance of any one segment and all adjacent segments adjacent thereto is measured. A segment having a difference between the average brightness of one segment and an adjacent segment of 5% or more is regarded as a intentional difference segment, and the average total number of intentional difference regions of the total region is calculated, and the brightness is not based on the following reference. All were evaluated. The smaller the number, the smaller the difference in density from the adjacent segments, and the less the unevenness in brightness, indicating that the characteristics as the color filter are excellent.

5: The number of intentional difference segments is 2000 or less.

4: The number of intentional difference segments is 2001 to 3000.

3: The number of intentional difference segments is 3001 to 5000.

2: The number of intentional difference segments is 5001 to 10000.

1: The number of intentional difference segments is 10001 or more.

<<Development residue>>

The green pigment-containing coloring curable composition of Examples 1 to 12, 15 to 33, and Comparative Examples 1 to 3 was coated with a spin coater so that the film thickness after coating was 0.8 μm. On the ruthenium wafer of the undercoat layer, a 100 ° C hot plate was used for heat treatment (prebaking) for 120 seconds to form a coating film.

Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), the exposure amount was adjusted so that the pattern size became 1.4 μm via a 1.4 μm square Bayer pattern mask, and the coating film was irradiated with 365 nm. The i-line of the wavelength is exposed.

Thereafter, the ruthenium wafer on which the exposed coating film was formed was subjected to agitated development at 23 ° C for 60 seconds using a TMAH 0.3% aqueous solution. Thereafter, the mixture was washed by a rotary spray method, and further washed with pure water. Next, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 ° C to obtain a monochromatic color filter in which a Bayer pattern of 1.4 μm square was formed.

The residue of the pattern was observed on a 1.4 μm square Bayer pattern obtained by using a length measuring SEM (S-4800, manufactured by Hitachi, Ltd.), whereby the development residue was evaluated in accordance with the following criteria.

3: No residue was observed.

2: Although the residue is observed, it is not a problem level in practical use.

1: The residue was observed, which was a level that could not be practical.

[Table 4]

From the above results, it is understood that the examples can effectively suppress the generation of needle crystals. Further, compared with the first embodiment, the zinc halide phthalocyanine pigment A was changed to the same amount of the halogenated phthalocyanine pigment F, I or M to prepare a colored curable composition, and a color filter was produced according to Production Example 1. In the case of Examples 1 to 12 and 15 to 33, generation of needle crystals was more suppressed.

Further, in the examples, the brightness unevenness was good.

On the other hand, in the comparative example, needle crystals were easily generated.

no

no

no

Claims (15)

A coloring curable composition comprising a coloring agent containing a zinc halide phthalocyanine pigment, a resin, a curable compound, and a solvent, wherein the average number of halogen atoms in the phthalocyanine 1 molecule in the zinc halide phthalocyanine pigment is 14 There are 16 and the average number of bromine atoms is 12 or less. The colored hardening composition according to claim 1, wherein the average number of bromine atoms in the phthalocyanine 1 molecule in the zinc halide phthalocyanine pigment is from 1 to 8. The colored hardening composition according to claim 1, wherein the average number of bromine atoms in the phthalocyanine 1 molecule in the zinc halide phthalocyanine pigment is from 1 to 7. The color hardening composition according to claim 1, which comprises an acidic dispersant as the resin. The color hardening composition according to claim 1, which further comprises a pigment derivative. The colored hardening composition according to claim 1, wherein the pigment derivative is a compound represented by the following formula (P): [Chemical Formula 1] In the formula (P), A represents a structure selected from the following formulae (PA-1) to (PA-3), B represents a single bond or a (t+1)-valent linking group, and C represents a single bond, -NH-, -CONH-, -CO ₂ -, -SO ₂ NH-, -O-, -S- or -SO ₂ -, D represents a single bond, an alkyl group or an extended aryl 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 represent an alkyl group or an aryl group, and Rpa and Rpb may be bonded to each other to form a ring, and t represents 1 An integer of ～5; [Chemical Formula 2] Rp ₁ represents an alkyl group or an aryl group having 1 to 5 carbon atoms, Rp ₂ represents a hydrogen atom, a halogen atom, an alkyl group or a hydroxyl group, and Rp ₃ represents a single bond, -NH-, -CONH-, -CO ₂ -, - _{SO 2 NH -, - O -} , - S- or -SO ₂ -, s represents an integer of 1 to 4, s is 2 or more, a plurality of Rp of ₂ may be the same or different, * represents a linking portion and B . The color hardening composition according to any one of claims 1 to 6, further comprising a photopolymerization initiator, wherein the curable compound contains at least a 3-15 functional (meth) acrylate Compound. A color filter obtained by using the color hardening composition according to any one of claims 1 to 7. A pattern forming method comprising: a process for forming a colored curable composition layer on a support by using the colored curable composition according to any one of claims 1 to 7; and the coloring hardenability composition The process of exposing the layer to a pattern; and forming a colored pattern by developing and removing the unexposed portion. A pattern forming method, comprising: using the color hardening composition according to any one of claims 1 to 7 to form a colored curable composition layer on a support and hardening to form a colored layer; a process of forming a photoresist layer on the colored layer; patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask to color the foregoing The layer is dry etched to form a colored pattern process. A method of manufacturing a color filter, comprising the pattern forming method according to claim 9 or 10. A solid-state imaging device having the color filter of claim 8 of the patent application. A solid-state imaging device having a color filter obtained by the method for producing a color filter according to claim 11 of the patent application. An image display device having the color filter of claim 8 of the patent application. An image display device having a color filter obtained by the method for producing a color filter according to claim 11 of the patent application.