JP2013136739A - Colored resin composition, color filter, liquid crystal display device, and organic el display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter whose contrast by time at a color filter production is prevented from decreasing when a metal halide phthalocyanine pigment and a yellow dye are used to improve high contrast and heat resistance of the pixel of the color filter, and to provide a liquid crystal display device and an organic EL display of high quality.SOLUTION: The colored resin composition includes: (A) a metal halide phthalocyanine pigment; (B) a yellow dye; (C) a binder resin; and (D) a solvent, wherein the colored resin composition further includes a specific compound in addition.

Description

  The present invention resides in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

In recent years, a liquid crystal panel display with high brightness is desired from the viewpoint of low power consumption, and color filters are required to have higher transmittance and higher contrast.
As a color material for a color filter, a pigment is conventionally used from the viewpoint of heat resistance and light resistance.
As a pigment type, for example, a green pigment has been put to practical use in combination with various yellow pigments since a halogenated phthalocyanine green pigment has been used for a long time.

In recent years, a new phthalocyanine green pigment having a specific hue has been proposed for increasing the brightness of green pixels, and differentiation from conventional halogenated copper phthalocyanine green pigments has been realized (Patent Document 1 or 2).
However, when the new green pigment is refined to increase the contrast, the dispersion stability is extremely lowered, and there is a problem that the contrast becomes insufficient due to light scattering by the secondary aggregate.

In order to solve such problems, for example, Patent Document 2 proposes a dispersant for adjusting a pigment dispersion. Patent Document 3 proposes a binder resin for high contrast and stability over time.
On the other hand, it has been conventionally proposed to use a dye as a coloring material for the purpose of further increasing brightness and contrast (Patent Document 4).

  Furthermore, for the purpose of improving the heat resistance of the dye, for example, Patent Documents 4 to 6 disclose that the dye structure is chemically modified.

JP 2004-70342 A JP 2004-70343 A JP 2009-53652 A JP 2006-124634 A JP 2010-275533 A JP 2011-95732 A

However, even with the dyes described in Patent Documents 4 to 6, the contrast and heat resistance of the obtained pixel were particularly insufficient.
That is, according to the present invention, when a metal halide phthalocyanine pigment and a yellow dye are used for the purpose of increasing the contrast of a pixel of the color filter and improving the heat resistance, a decrease in contrast over time during the production of the color filter is suppressed. Is to provide a color filter.

Another object of the present invention is to provide a high-quality liquid crystal display device and an organic EL display device.

When the present inventors form a pixel by using a colored resin composition containing (A) a halogenated metal phthalocyanine pigment and (B) a yellow dye, the above-mentioned fact that curing by ultraviolet irradiation is not sufficient It was speculated that this is one of the causes that the luminance and contrast of the obtained pixel are insufficient.
As a result of further intensive studies, the present inventors have found that the above-mentioned problems can be solved by further containing a specific monomer in a colored resin composition containing a halogenated metal phthalocyanine pigment and a yellow dye. Reached.

  That is, the present invention comprises (A) a halogenated metal phthalocyanine pigment, (B) a yellow dye, (C) a binder resin and (D) a solvent, and further a compound represented by the following formula (1) (hereinafter, The present invention resides in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device characterized by containing “sometimes referred to as compound (1)”.

(In the formula (1),
m represents an integer of 3 or 4.
n represents an integer of 1 to 3.
R ¹ represents a hydrocarbon group which may have a substituent,
R ² represents a hydrogen atom or a hydrocarbon group which may have a substituent.

X represents a direct bond, a 3 or quaternary carbon atom, a 3 or 4 valent heterocyclic group or a 3 or 4 valent aromatic ring group.
However, when X is a quaternary carbon atom, m is 3 and may have a hydroxyl group as a substituent.
In addition, a plurality of molecules contained in one molecule

May be the same or different. )

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the colored resin composition which can form the pixel which maintained or improved the contrast and improved heat resistance.
Furthermore, the color filter of the present invention has high contrast and heat resistance, and the liquid crystal display device and organic EL display device of the present invention are of high quality.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".

Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.
Moreover, terms such as “CI Pigment Green” mean a color index (CI).
In the present invention, “coloring material” is a general term for “pigment” and “dye”.

The colored resin composition of the present invention contains (A) a metal halide phthalocyanine pigment, (B) a yellow dye, (C) a binder resin and (D) a solvent, and further contains a compound (1).
First, the compound (1) in the present invention will be described in detail.
[Compound (1)]

(In the formula (1),
m represents an integer of 3 or 4.
n represents an integer of 1 to 3.
R ¹ represents a hydrocarbon group which may have a substituent,
R ² represents a hydrogen atom or a hydrocarbon group which may have a substituent.

X represents a direct bond, a 3 or quaternary carbon atom, a 3 or 4 valent heterocyclic group or a 3 or 4 valent aromatic ring group.
However, when X is a quaternary carbon atom, m is 3 and may have a hydroxyl group as a substituent.
In addition, a plurality of molecules contained in one molecule

May be the same or different. )
(About m)
m represents an integer of 3 or 4.
M is preferably 4 in that the double bond equivalent is reduced and the crosslink density of the obtained pixel is increased, whereby a reduction in contrast can be further suppressed.

(About n)
n represents an integer of 1 to 3.
It is preferable that n is 1 in that the reduction in contrast of the obtained pixel can be further suppressed.
(About R ¹ )
The hydrocarbon group for R ¹ usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.

Examples of the hydrocarbon group include methylene, ethylene, linear propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, cyclohexylene, and phenylene.
Examples of the substituent that the hydrocarbon group in R ¹ may have include those described in the following [Substituent Group W] section, but the present invention is not limited thereto.

In addition, as R ¹ , the double bond equivalent of the compound (1) does not become too large, the film curability is sufficient, and the effect of suppressing the decrease in contrast of the obtained pixel is easily obtained, A methylene group or an ethylene group is preferred.
[Substituent group W]
Methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl, cyclopentyl group, linear or branched hexyl group, cyclohexyl group.

(About R ² )
The hydrocarbon group for R ² usually has 0 to 6 carbon atoms, preferably 0 to 1 carbon atoms.
Examples of the hydrocarbon group include the divalent groups described in the above section (about R ¹ ).
(About X)
X represents a direct bond, a 3 or quaternary carbon atom, a 3 or 4 valent heterocyclic group or a 3 or 4 valent aromatic ring group.

However, when X is a quaternary carbon atom, m is 3 and may have a hydroxyl group as a substituent. Further, X being a tertiary carbon atom means a state in which the remaining one bond of the carbon atom is bonded to a hydrogen atom.
The heterocyclic group (that is, non-aromatic heterocyclic group) may be a single ring or a condensed ring.

The heterocyclic group is a non-aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom.
When the heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.
Specific examples include a pyridinyl group, a quinolinyl group, an isoquinolinyl group, a benzothiazolinyl group, a phthalimidoyl group, a piperidinyl group, and a pyrrolidinyl group.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 18, but for example, one free valence Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

  In addition, the aromatic heterocyclic group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, but for example, one free atom Having a valence, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole Ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, Synoline ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, groups such as azulene ring.

The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.
(About molecular weight)
The molecular weight of the compound (1) is usually 200 or more, preferably 250 or more, and usually 500 or less, preferably 400 or less.

When it is at least the lower limit, the unreacted compound (1) present after photocuring is preferable in that it is difficult to sublimate in the subsequent process. This is preferable in that the ratio of heavy bonds is relatively large and photocuring is sufficient.
[Concrete example]
Preferred specific examples of the compound (1) include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and glycerol (meth) acrylate. And (meth) acrylic acid esters.

(About content)
The content of the compound (1) in the present invention is usually 5% by weight or more, preferably 7% by weight or more, more preferably 10% by weight or more, and usually 65% by weight or less, preferably in the solid content of the colored resin composition. Is 60% by weight or less, more preferably 55% by weight or less.
If it is within the above lower limit, the curability of the film is good and the resulting pixel has sufficient contrast, and if it is within the above lower limit value, the content of the binder resin in the colored resin composition is sufficient. It is preferable because a coating film having a uniform film thickness and free from coating unevenness and defects can be produced.

<Reason for effect>
The reason why the effect is obtained by using the configuration of the present invention is estimated as follows.
Compound (1) has a small double bond equivalent (the number of double bond groups in one molecule is large). Further, since the molecular weight is small, the number of molecules is large in the binder resin containing the dye and the pigment in the same weight as the polymerizable monomer other than the compound (1). In addition, it has a similar chemical structure to the binder resin (particularly the resins (C-1) to (C-5) described in [(C) Binder resin] described later), has high compatibility, and exists homogeneously. sell. As a result, even when the photocuring is suppressed by the dye, a photocured film having a high crosslinking density can be obtained, and the movement of the pigment and the dye is limited in the film, and the contrast is maintained without aggregating with time.

[(A) Halogenated metal phthalocyanine pigment]
The colored resin composition of the present invention contains (A) a metal halide phthalocyanine.
Ordinary metal phthalocyanines have 16 hydrogen atoms in one molecule, and these hydrogen atoms are substituted with bromine atoms or chlorine atoms in halogenated metal phthalocyanines, which are preferably used in the present invention. Is a brominated metal phthalocyanine pigment.

  Of these, a brominated metal phthalocyanine having an average of 13 or more bromine atoms in one molecule is preferable because it exhibits extremely high transmittance and is suitable for forming a green pixel of a color filter. Furthermore, brominated zinc phthalocyanine having 13 to 16 bromine atoms in one molecule and not containing chlorine or having an average of 3 or less in one molecule is preferable, and in particular, an average of 14 bromine atoms in one molecule is 14 Brominated metal phthalocyanine having ˜16 and containing no chlorine atom in one molecule or having an average of 2 or less is preferred. Preferred brominated metal phthalocyanines include brominated copper phthalocyanine and brominated zinc phthalocyanine. The brominated copper phthalocyanine is preferably C.I. I. Pigment Green 36. The brominated zinc phthalocyanine is preferably C.I. I. Pigment Green 58.

  Among such halogenated metal phthalocyanines, for example, brominated zinc phthalocyanine pigments can be produced by a known production method disclosed in JP-A-50-130816. For example, a method of synthesizing a pigment using phthalic acid or phthalonitrile in which some or all of the hydrogen atoms of the aromatic ring are substituted with a halogen atom such as chlorine in addition to bromine as an appropriate starting material. In this case, a catalyst such as ammonium molybdate may be used as necessary.

  As another method, a method of brominating zinc phthalocyanine with bromine gas in a melt of about 110 to 170 ° C. composed of a mixture of aluminum chloride, sodium chloride, sodium bromide and the like can be mentioned. In this method, the ratio of various brominated zinc phthalocyanines with different bromine contents can be adjusted by adjusting the ratio of chloride and bromide in the molten salt, or by changing the amount of chlorine gas introduced and the reaction time. Can be controlled arbitrarily.

When the obtained mixture is put into an acidic aqueous solution such as hydrochloric acid after the reaction is completed, the produced brominated zinc phthalocyanine is precipitated. Thereafter, post-treatment such as filtration, washing and drying is performed to obtain brominated zinc phthalocyanine.
The brominated zinc phthalocyanine thus obtained may be used singly, but the brominated zinc phthalocyanine having a different bromination rate or chlorination rate and other metals as long as the effect of the present invention is not impaired. It can be used by mixing with brominated phthalocyanine or the like substituted. Changing the chlorination rate and bromination rate, or changing the central metal changes the color tone of the pigment and increases the number of hues that can be reproduced.

The average primary particle size of the green pigment containing a metal halide phthalocyanine is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, and further preferably 0.025 μm or less. 005 μm or more. The average primary particle size of other pigments is the same as described above.
By setting the average primary particle size to be equal to or less than the above upper limit value, it is difficult to generate foreign matters in the composition, the depolarization is low, and a pixel having sufficient contrast and light transmittance can be formed. By setting it as the above, the colored resin composition which has favorable dispersion stability and ensured sufficient heat resistance and light resistance can be obtained.

In addition, the average primary particle diameter of a pigment can be calculated | required with the following method. That is, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). The primary particle diameter is measured from this image, the number average value is calculated according to the following formula, and the average particle diameter is obtained.
In the case of an organic pigment, the particle diameter of each pigment particle was determined for each of a plurality of pigment particles, usually about 200 to 300, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area. Thereafter, the number average value is calculated according to the following formula, and the average particle diameter is obtained.

  The metal halide phthalocyanine pigment thus obtained is dry-ground in a pulverizer such as an attritor, ball mill, vibration mill, vibration ball mill or the like as necessary, and then pigmented by a solvent salt milling method or a solvent boiling method. Thus, a brominated zinc phthalocyanine green pigment that develops a green color with high transmittance and contrast can be obtained. There is no particular limitation on the pigmentation method, but it is preferable to employ the solvent salt milling method in that pigment growth can be easily suppressed and pigment particles having a large specific surface area can be obtained.

  The solvent salt milling method means kneading and grinding a crude pigment immediately after synthesis, an inorganic salt, and an organic solvent. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein. The kneading machine at this time has, for example, a kneader, a mix muller, or a pulverizing space in which a gap portion of a rotating disk concentric with an annular fixed disk as described in JP-A-2006-77062 is formed. A continuous kneader or the like is preferably used.

As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Further, the particle diameter of these inorganic salts is more preferably 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.
The content of the (A) halogenated metal phthalocyanine contained in the colored resin composition of the present invention is usually 30 to 99.95% by weight, preferably 35 to 99.92% by weight, more preferably in all pigments. 38-99.9% by weight.

Within the above-mentioned range, it is preferable in terms of obtaining a good color filter with sufficient luminance, few missing pixels, excellent pattern linearity and few defects.
[(B) Yellow dye]
The colored resin composition of the present invention contains (B) a yellow dye.
(B) The yellow dye is not particularly limited as long as the effect of the present invention is not impaired, and a known dye can be used. For example, azo dyes, quinophthalone dyes, cyanine dyes, anthraquinone dyes, Examples include methine dyes and dipyrromethene dyes. Among them, azo dyes are preferable.

  Examples of yellow dyes other than azo dyes include JP 2005-170974 A, JP 2005-250420 A, JP 2005-263926 A, JP 2006-58787 A, and JP 2006-72135 A. JP, 2006-91768, JP, 2007-147784, JP, 2008-248123, JP, 2009-203430, JP, 2009-242757, JP, 2011-215537, JP JP 2011-219655 A, JP 2012-012492 A, JP 2012-082337 A, International Publication No. 2012/101946, International Publication No. 2010/110199, and the like.

Examples of the azo dyes include pyridone azo dyes, pyrazolone azo dyes, and barbituric acid azo dyes. In particular, pyridone azo dyes have pixels having a sharp absorption spectrum and high luminance. Is preferable in that it can be obtained.
Examples of azo dyes other than pyridone azo dyes include JP-A-2004-83903, JP-A-2004-339273, JP-A-2005-55585, JP-A-2005-97376, JP-A-2005-120132, JP, 2005-154478, JP, 2005-154544, JP, 2005-250224, JP, 2005-290351, JP, 2005-320423, JP, 2006-3873, JP JP-A-2006-47498, JP-A-2007-31616, JP-A-2007-39478, JP-A-2007-41050, JP-A-2007-41076, JP-A-2007-63520, JP-A-2007-. No. 139906, Japanese Patent Application Laid-Open No. 2007-191590, Japanese Unexamined Patent Application Publication No. 2008-7652, Japanese Unexamined Patent Application Publication No. 2008-7732, Japanese Unexamined Patent Application Publication No. 2008-88198, Japanese Unexamined Patent Application Publication No. 2008-88200, Japanese Unexamined Patent Application Publication No. 2008-239731, Japanese Unexamined Patent Application Publication No. 2009-190973, Japanese Unexamined Patent Application Publication No. 2010. Azo dyes described in JP-A-275532, JP-A 2011-145540, JP-A 2011-184493, JP-A 2007-191559, JP-A 2010-168531, JP-A 2011-164564 Is mentioned.

  The pyridone azo dye is not particularly limited, and a known substance can be used, but a compound represented by the following formula (I) (hereinafter referred to as “compound (I)”) is highly soluble in a solvent. It may be referred to).

(In the above formula (I), A represents an aromatic hydrocarbon ring group which may have a substituent or a heterocyclic group which may have a substituent.
R ^1a represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a carboxy group, or a trifluoromethyl group.
R ^2a represents a hydrogen atom, a cyano group, a carbamoyl group, an alkylcarbamoyl group which may have a substituent, an arylcarbamoyl group which may have a substituent, a carboxy group, a sulfamoyl group or a sulfo group.

R ^3a has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and a substituent. May be an aralkyl group having 7 to 20 carbon atoms, an optionally substituted heterocyclic group having 3 to 20 carbon atoms, a carbamoyl group, or an optionally substituted alkyl carbamoyl group having 2 to 20 carbon atoms. An arylcarbamoyl group having 7 to 30 carbon atoms which may have a substituent, a sulfamoyl group having 1 to 20 carbon atoms, an alkylsulfamoyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent. An optionally substituted arylsulfamoyl group having 6-30 carbon atoms, an optionally substituted alkyloxycarbonyl group having 2-20 carbon atoms, and an optionally substituted 7-30 carbon atoms. Aryloxycarbonyl group, substituent An optionally substituted acyl group having 2 to 30 carbon atoms, an optionally substituted alkylsulfonyl group having 1 to 30 carbon atoms or an optionally substituted aryl having 6 to 30 carbon atoms Represents a sulfonyl group. )
(About A)
A represents an aromatic hydrocarbon ring group which may have a substituent or a heterocyclic group which may have a substituent.

Examples of the aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence. Acenaphthene ring, fluoranthene ring, fluorene ring and the like.
The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.

  Examples of the heterocyclic group include pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, oxazolyl group, triazolyl group, thiadiazolyl group, pyridinyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, benzothiazolinyl group Phthalimidoyl group, benzimidazolonyl group, furyl group, thiophenyl group and the like. As the substituent that the aromatic hydrocarbon ring group or the heterocyclic group may have, the color tone as a hydrophilic group or a dye introduced to enhance the solubility of the compound (I) in the solvent is adjusted. In order to do so, a group having electron donating property or electron withdrawing property is preferable, specifically, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A monovalent heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an amino group, an alkylamino group which may have a substituent, or a substituent. Good arylamino group, optionally substituted acylamino group, carbamoyl group, optionally substituted alkylcarbamoyl group, optionally substituted arylcarbamoyl group, sulfamoyl group, substituted Even if you have a group An alkylsulfamoyl group, an arylsulfamoyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, Examples thereof include a nitro group, a carboxy group, a sulfo group, a hydroxyl group, a cyano group, and a halogen atom.

  The alkyl group which may have a substituent has usually 1 or more, usually 12 or less, preferably 10 or less. Examples of the group that may be substituted with the alkyl group include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2 -(2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like can be mentioned.

  The aryl group which may have a substituent usually has 6 or more carbon atoms, usually 14 or less, and preferably 12 or less. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted for the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, and A carboxy group etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a naphthyl group, and an anthracenyl group.

The monovalent heterocyclic group which may have a substituent usually has 2 or more carbon atoms and usually 14 or less, preferably 12 or less. Examples of the monovalent heterocyclic group include pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, triazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiazolinyl Group, phthalimidoyl group, benzimidazolonyl group, furyl group, thiophenyl group, pyranyl group, piperidinyl group, pyrrolidinyl group, imidazolidinyl group, pyrazolidinyl group, piperazinyl group, morpholinyl group, indolinyl group, isoindolinyl group and the like. Examples of the group that may be substituted on the monovalent heterocyclic group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, and a halogen atom. , Sulfo group and carboxy group. Specific examples of the monovalent heterocyclic group include a 2-pyrrolyl group, a 2-imidazolyl group, a 1-pyrazolyl group, a 2-thiazolyl group, a 2-oxazolyl group, a 1,2,4-triazol-1-yl group, 4-pyridinyl group, 2-pyrimidinyl group, 4,6-diamino-2-triazinyl group, 8-quinolinyl group, 8-isoquinolinyl group, 2-benzothiazolinyl group, 6-methyl-7-sulfo-2-benzo Thiazolinyl group, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl group, 1H-benzimidazol-2-yl group, 2-furyl group, 2-thiophenyl group, 1-piperidinyl Group, 1-pyrrolidinyl group, 1-imidazolidinyl group, 1-pyrazolidinyl group, 1-piperazinyl group, 1-morpholinyl group, 1-indolinyl group, 2-isoindolinyl group It is below.

  The alkoxy group which may have a substituent usually has 1 or more carbon atoms and usually 12 or less, preferably 10 or less. Examples of the group which may be substituted for the alkoxy group include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, hydroxyethoxy group, 1,2-dihydroxypropoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2- Examples include butoxyethoxy group, 2- (2-methoxyethoxy) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 2- (2-butoxyethoxy) ethoxy group, benzyloxy group, phenethyloxy group and the like.

The alkylamino group which may have a substituent is represented by —NR ⁴¹ R ⁴² , R ⁴¹ represents an alkyl group which may have a substituent, and R ⁴² represents a hydrogen atom or a substituent. It represents an alkyl group that may have. The alkyl group usually has 1 or more carbon atoms and usually 12 or less, preferably 10 or less. Examples of the group that may be substituted with the alkyl group include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group. 2-butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like. Specific examples of the alkylamino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, and a cyclohexylethyl group.

The arylamino group which may have a substituent is represented by —NR ⁴³ R ⁴⁴ , R ⁴³ represents an aryl group which may have a substituent, and R ⁴⁴ represents a hydrogen atom or a substituent. The alkyl group which may have and the aryl group which may have a substituent are represented. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . The aryl group usually has 6 or more carbon atoms and usually 14 or less, preferably 12 or less, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, A sulfo group, a carboxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a naphthyl group,
Anthracenyl group etc. are mentioned. Specific examples of the arylamino group include a phenylamino group, a diphenylamino group, a di (p-tolyl) amino group, a di (p-methoxyphenyl) amino group, an ethylphenylamino group, and an n-butylphenylamino group. Can be mentioned.

The acylamino group which may have a substituent is represented by -NH-COR ⁴⁵ , and R ⁴⁵ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. . Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the acylamino group include acetylamino group, benzoylamino group, 2-ethylhexylcarbonylamino group and the like.

The optionally substituted alkylcarbamoyl group is represented by —CO—NR ⁴⁶ R ⁴⁷ , and each of R ⁴⁶ and R ⁴⁷ independently represents a hydrogen atom or an optionally substituted alkyl group. Represents. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a phenethylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a 2-ethoxyethylcarbamoyl group, a 2- (2-ethoxyethoxy) ethylcarbamoyl group, and the like. .

The arylcarbamoyl group which may have a substituent is represented by —CO—NR ⁴⁸ R ⁴⁹ , and R ⁴⁸ represents an aryl group which may have a substituent. R ⁴⁹ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the arylcarbamoyl group include phenylcarbamoyl group, naphthylcarbamoyl group, p-tolylcarbamoyl group, p-methoxyphenylcarbamoyl group and the like.

The alkylsulfamoyl group which may have a substituent is represented by —SO ₂ —NR ⁵⁰ R ⁵¹ , and R ⁵⁰ and R ⁵¹ may each independently have a hydrogen atom or a substituent. Represents a good alkyl group. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Specific examples of the alkylsulfamoyl group include methylsulfamoyl group, ethylsulfamoyl group, phenethylsulfamoyl group, 2-ethylhexylsulfamoyl group, 2-ethoxyethylsulfamoyl group, 2- ( And 2-ethoxyethoxy) ethylsulfamoyl group.

The arylsulfamoyl group which may have a substituent is represented by —SO ₂ —NR ⁵² R ⁵³ , and R ⁵² represents an aryl group which may have a substituent. R ⁵³ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the arylsulfamoyl group include a phenylsulfamoyl group, a naphthylsulfamoyl group, a p-tolylsulfamoyl group, and a p-methoxyphenylsulfamoyl group.

The alkyloxycarbonyl group which may have a substituent is represented by —CO—OR ⁵⁴ , and R ⁵⁴ represents an alkyl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Specific examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a phenethyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a 2-ethoxyethoxycarbonyl group, and a 2- (2-ethoxyethoxy) ethoxycarbonyl group. Is mentioned.

Which may have a substituent aryloxycarbonyl group is represented by ^{-CO-OR 55,} R ⁵⁵ represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the aryloxycarbonyl group include phenoxycarbonyl group, naphthoxycarbonyl group, p-tolyloxycarbonyl group, p-methoxyphenoxycarbonyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom and a chlorine atom having high electronegativity are preferable.
(About R ^1a )
R ^1a represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a carboxy group, or a trifluoromethyl group.

  The alkyl group which may have a substituent has usually 1 or more, usually 10 or less, preferably 5 or less. Examples of the group that may be substituted on the alkyl group include an alkoxy group having 1 to 8 carbon atoms and a hydroxyl group. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyethyl group, methoxymethyl group and the like.

(About R ^2a )
R ^2a represents a hydrogen atom, a cyano group, a carbamoyl group, an alkylcarbamoyl group which may have a substituent, an arylcarbamoyl group which may have a substituent, a carboxy group, a sulfamoyl group or a sulfo group.
The alkylcarbamoyl group which may have a substituent is represented by —CO—NR ⁵⁶ R ⁵⁷ , and R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom or an alkyl group which may have a substituent. Represents. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a phenethylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a 2-ethoxyethylcarbamoyl group, a 2- (2-ethoxyethoxy) ethylcarbamoyl group, and the like. .

The arylcarbamoyl group which may have a substituent is represented by —CO—NR ⁵⁸ R ⁵⁹ , and R ⁵⁸ represents an aryl group which may have a substituent. R ⁵⁹ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the arylcarbamoyl group include phenylcarbamoyl group, naphthylcarbamoyl group, p-tolylcarbamoyl group, p-methoxyphenylcarbamoyl group and the like.

(About R ^3a )
R ^3a has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and a substituent. May be an aralkyl group having 7 to 20 carbon atoms, an optionally substituted heterocyclic group having 3 to 20 carbon atoms, a carbamoyl group, or an optionally substituted alkyl carbamoyl group having 2 to 20 carbon atoms. An arylcarbamoyl group having 7 to 30 carbon atoms which may have a substituent, a sulfamoyl group having 1 to 20 carbon atoms, an alkylsulfamoyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent. An optionally substituted arylsulfamoyl group having 6-30 carbon atoms, an optionally substituted alkyloxycarbonyl group having 2-20 carbon atoms, and an optionally substituted 7-30 carbon atoms. Aryloxycarbonyl group, substituent An optionally substituted acyl group having 2 to 30 carbon atoms, an optionally substituted alkylsulfonyl group having 1 to 30 carbon atoms or an optionally substituted aryl having 6 to 30 carbon atoms Represents a sulfonyl group.

  The alkyl group having 1 to 20 carbon atoms which may have a substituent has usually 1 or more, usually 20 or less, preferably 15 or less. Examples of the group that may be substituted on the alkyl group include an alkoxy group having 1 to 15 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. . Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2 -(2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group and the like can be mentioned.

  The aryl group having 6 to 30 carbon atoms which may have a substituent usually has 6 or more carbon atoms, usually 30 or less, preferably 25 or less. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group that may be substituted on the aryl group include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, and A carboxy group etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a naphthyl group, and an anthracenyl group.

  The aralkyl group having 7 to 20 carbon atoms which may have a substituent usually has 7 or more carbon atoms, usually 20 or less, preferably 15 or less. Examples of the group that may be substituted for the aralkyl group include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, and A carboxy group etc. are mentioned. Specific examples of the aryl group include benzyl group, phenethyl group, α-methylbenzyl group, α-methylphenylethyl group, β-methylphenylethyl group, fluorenyl group and the like.

  The C3-C20 heterocyclic group which may have a substituent usually has 3 or more carbon atoms, usually 20 or less, and preferably 15 or less. Examples of the monovalent heterocyclic group include pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, triazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiazolinyl Group, phthalimidoyl group, benzimidazolonyl group, furyl group, thiophenyl group and the like. Examples of the group that may be substituted on the monovalent heterocyclic group include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, and a halogen atom. , Sulfo group and carboxy group. Specific examples of the monovalent heterocyclic group include a 2-pyrrolyl group, a 2-imidazolyl group, a 1-pyrazolyl group, a 2-thiazolyl group, a 2-oxazolyl group, a 1,2,4-triazol-1-yl group, 4-pyridinyl group, 2-pyrimidinyl group, 4,6-diamino-2-triazinyl group, 8-quinolinyl group, 8-isoquinolinyl group, 2-benzothiazolinyl group, 6-methyl-7-sulfo-2-benzo Examples include thiazolinyl group, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl group, 1H-benzimidazol-2-yl group, 2-furyl group, and 2-thiophenyl group.

The C2-C20 alkylcarbamoyl group which may have a substituent is represented by -CO-NR
⁶⁰ R ⁶¹ , and R ⁶⁰ and R ⁶¹ each independently represent a hydrogen atom or an alkyl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a phenethylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a 2-ethoxyethylcarbamoyl group, a 2- (2-ethoxyethoxy) ethylcarbamoyl group, and the like. .

The arylcarbamoyl group having 7 to 30 carbon atoms which may have a substituent is represented by —CO—NR ⁶² R ⁶³ , and R ⁶² represents an aryl group which may have a substituent. R ⁶³ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the arylcarbamoyl group include phenylcarbamoyl group, naphthylcarbamoyl group, p-tolylcarbamoyl group, p-methoxyphenylcarbamoyl group and the like.

Substituents alkylsulfamoyl group having 1 to 20 carbon atoms which may have a _is represented by ^{-SO 2 -NR 64 R 65, R} 64 and ^{R 65} are each independently a hydrogen atom or a substituent Represents an alkyl group which may have Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Specific examples of the alkylfurfamoyl group include a methylsulfamoyl group, an ethylsulfamoyl group, a phenethylsulfamoyl group, a 2-ethylhexylsulfamoyl group, a 2-ethoxyethylsulfamoyl group, 2- ( And 2-ethoxyethoxy) ethylsulfamoyl group.

The arylsulfamoyl group having 6 to 30 carbon atoms which may have a substituent is represented by —SO ₂ —NR ⁶⁶ R ⁶⁷ , and R ⁶⁶ represents an aryl group which may have a substituent. . R ₆₇ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the arylsulfamoyl group include a phenylsulfamoyl group, a naphthylsulfamoyl group, a p-tolylsulfamoyl group, and a p-methoxyphenylsulfamoyl group.

Alkyloxycarbonyl group having carbon atoms of 2 to 20 which may have a substituent group is represented by ^{-CO-OR 68,} R ⁶⁸ represents an alkyl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Specific examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a phenethyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a 2-ethoxyethoxycarbonyl group, and a 2- (2-ethoxyethoxy) ethoxycarbonyl group. Is mentioned.

The aryloxycarbonyl group having 7 to 30 carbon atoms which may have a substituent is represented by —CO—OR ⁶⁹ , and R ⁶⁹ represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the aryloxycarbonyl group include phenoxycarbonyl group, naphthoxycarbonyl group, p-tolyloxycarbonyl group, p-methoxyphenoxycarbonyl group and the like.

Acyl group optionally 2 to 30 carbon atoms which may have a substituent group is represented by -COR ^70, R ⁷⁰ is an alkyl group which may have a substituent and may have a substituent Represents an aryl group. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the acyl group include an acetyl group, a benzoyl group, and a 2-ethylhexylcarbonyl group.

An alkylsulfonyl group having 1 to 30 carbon atoms which may have a substituent group _is represented by -SO 2 ^{-R 71,} R ⁷¹ represents an alkyl group which may have a substituent. Examples of the preferred carbon number of the alkyl group and the optionally substituted substituent are the same as those exemplified for the alkyl groups of R ⁴¹ and R ⁴² . Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a phenethylsulfonyl group, a 2-ethylhexylsulfonyl group, a 2-ethoxyethylsulfonyl group, and a 2- (2-ethoxyethoxy) ethylsulfonyl group. .

The arylsulfonyl group having 6 to 30 carbon atoms which may have a substituent is represented by —SO ₂ —R ⁷² , and R ⁷² represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴³ . Specific examples of the arylsulfonyl group include a phenylsulfonyl group, a naphthylsulfonyl group, a p-tolylsulfonyl group, and a p-methoxyphenylsulfonyl group.

<Specific example>
Although the preferable specific example of compound (I) is shown below, this invention is not limited to these.

  In addition to the above structure, JP 2002-14223, JP 2005-126529, JP 2005226602, JP 2006-58701, JP 2006-124634, JP 2009-280691, JP 2009-299030, JP 2010-1469, JP 2010-152160, JP 2010-168531, JP 2010-275533, JP 2011-148899, JP 2011-148990, JP The pyridone azo compound described in each publication of 2011-148991, the complexed pyridone azo compound described in each publication of JP2011-148992A, JP2011-148993A, and the polymer described in JP2006-265495A Pyridone azo compounds, JP 2010-17 Pyridone azo compounds dimerization described in JP 073 JP and JP 2010-275531 are exemplified.

<Synthesis method>
The compound represented by the formula (I) can be produced according to a known method. For example, using a primary amine having a substituent as A and a 6-hydroxy-2-pyridone derivative, “precise organic synthesis [Experiment Manual] (Revised Second Edition) "(Lutz Friedjan Tietze, Theophil Eicher, Seiichi Takano, Kunio Ogasawara, pp. 403-405, January 15, 1995, published by Minami Edo) (Diazotization, coupling step).

(Content)
The colored resin composition of the present invention comprises (B) a yellow dye in a total solid content of usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, and usually 30% by weight or less. , Preferably 20% by weight or less, more preferably 10% by weight or less.
In the colored resin composition of the present invention, the (B) yellow dye is preferably 1% by weight or more, more preferably 5% by weight or more, particularly preferably 10%, based on the above-mentioned (A) halogenated metal phthalocyanine pigment. It is contained in a proportion of not less than wt%, preferably not more than 200 wt%, more preferably not more than 100 wt%, particularly preferably not more than 80 wt%.

It is preferable for it to be less than or equal to the above upper limit because the curability of the coating film is unlikely to decrease and the film strength is sufficient. Moreover, since it is sufficient for coloring power to be more than the said minimum, since the chromaticity of a desired density | concentration is easy to be obtained and it is hard to become thick, it is preferable.
In the colored resin composition of the present invention, only one kind of (B) yellow dye may be contained, or two or more kinds thereof may be contained.

In addition, as (B) yellow dye, it is preferable to contain only compound (I), and it is preferable to contain compound (I) in the said range in the colored resin composition of this invention.
[(C) Binder resin]
(C) What preferable binder resin changes with the hardening means of a colored resin composition.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-2072111, JP-A-8-259876, and JP-A-10-300922. The polymer compounds described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used. However, among them, the following resins (C-1) to (C-5) are preferable.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item of 2009-025813 gazette. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.

  The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among them, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content of the repeating unit derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and the strength of the film are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be within the above range because the colored resin composition has excellent temporal stability. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. Within the above range, heat resistance, film strength, and solubility in a developer are preferable.
Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g. If the acid value is too low, the solubility in the developer may be reduced. Conversely, if it is too high, film roughening may occur.
Content of (C) binder resin in a colored resin composition is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 60 weight%.

Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.
[(D) Solvent]
The colored resin composition of the present invention contains (D) a solvent. (D) The solvent has a function of dissolving or dispersing each component contained in the colored resin composition and adjusting the viscosity.

The solvent (D) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin composition, and a solvent having a boiling point in the range of 100 to 200 ° C. is preferably selected. More preferably, it has a boiling point of 120-170 ° C.
Examples of such solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

These solvents may be used alone or in combination of two or more.
Among the above solvents, glycol monoalkyl ethers are preferred from the viewpoint of the solubility of the (B) yellow dye according to the present invention. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of various components in the composition.
In addition, (A) in terms of including a halogenated metal phthalocyanine pigment, there is a good balance of coatability, surface tension, etc., and in terms of relatively high solubility of the constituent components in the composition, glycol alkyl ether acetates are further used as solvents It is more preferable to use a mixture of these. In a composition containing a pigment, glycol monoalkyl ethers have a high polarity, tend to aggregate the pigment, and may reduce storage stability such as increasing the viscosity of the colored resin composition. For this reason, it is preferable that the amount of glycol monoalkyl ethers used is not excessively large. (D) The proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 50% by weight, more preferably 5 to 30% by weight. .

  Further, from the viewpoint of suitability for a slit coat method corresponding to a recent large substrate or the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher. In this case, the content of such a high boiling point solvent is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight based on the total amount of the solvent (D). If the amount of the high boiling point solvent is too small, for example, a dye component may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying speed of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .
The colored resin composition of the present invention may be used for color filter production by the ink jet method, but in color filter production by the ink jet method, the ink emitted from the nozzle is very small, from several to several tens pL, There is a tendency for the solvent to evaporate and the ink to concentrate and dry before landing on the periphery of the nozzle opening or in the pixel bank. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that the solvent (D) contains a solvent having a boiling point of 180 ° C. or higher. In particular, it is preferable to contain a solvent having a boiling point of 200 ° C. or higher, particularly 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 weight% or more in (D) solvent. When the ratio of such a high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

In the colored resin composition of the present invention, the content of the solvent (D) is not particularly limited, but the upper limit is usually 99% by weight. When the content of the (D) solvent in the composition exceeds 99% by weight, the concentration of each component excluding the (D) solvent becomes too small and may be inappropriate for forming a coating film. . On the other hand, (D) the lower limit of the content of the solvent, considering the viscosity suitable for coating,
Usually 75% by weight, preferably 80% by weight, more preferably 82% by weight.

[(E) Dispersant]
The colored resin composition of the present invention preferably contains (E) a dispersant in that the pigment is well dispersed and the luminance of the resulting pixel is improved.
As the (E) dispersant in the present invention, a known dispersant can be used regardless of the type as long as the pigment can be dispersed and kept stable. For example, a cationic, anionic, nonionic, amphoteric, etc. The dispersant may be a polymer dispersant. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. A block copolymer is particularly preferable. Among them, the block copolymer is composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom, and the amine value thereof is 80 mg-KOH / g or more and 150 mg-KOH. / G or less (in terms of effective solid content) is particularly preferable. More preferably 100 mg-KOH / g or more, 140 m
It is g-KOH / g or less.

Within the above range, the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.
As the block copolymer, an acrylic block copolymer is preferable. The acrylic block copolymer can disperse the yellow pigment (B) very efficiently. This is presumably because the molecular arrangement is controlled, so that there are few structures that obstruct the dispersant when adsorbing to the pigment.

In the present invention, the acrylic block copolymer is preferably an AB block composed of an A block and a B block and / or an ABA block copolymer.
The B block constituting the acrylic block copolymer preferably has a primary to tertiary amino group as a functional group containing a nitrogen atom, and the amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ And R ⁴² are each independently a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. What is preferable as a partial structure containing this is represented by the following formula (II), for example.

^{(However, R 41} and ^{R 42} has the same meaning as above ^{R 41} and ^{R 42, R 43} is one or more alkylene groups having a carbon ^{number, R 44} represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a methyl group. Examples of such a compound include a partial structure represented by the following formula.

  Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B block within a range not impairing the effects of the present invention. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer.

On the other hand, in the present invention, the A block of the (E) dispersant is not particularly limited as long as it is a solvent-soluble substance and is composed of a monomer copolymerizable with the monomer constituting the B block described above.
Examples of the A block include polymer structures obtained by copolymerizing comonomers such as styrene monomers, (meth) acrylate monomers, (meth) acrylate monomers, vinyl acetate monomers, glycidyl ether monomers, and the like. It is done.

  The (E) dispersant contained in the colored resin composition of the present invention is an AB block or ABA block copolymeric polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.

The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.
The amine value of the dispersant (in terms of effective solid content) is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mg-KOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
Further, the acid value of this block copolymer is preferably lower, although it depends on the presence and type of acidic groups that form the acid value, and is usually 50 mg-KOH / g or less, preferably 40 or less, more preferably. Is 30 or less.

When the average primary particle size of the pigment is small, the specific surface area increases and the amount of adsorbing dispersant per unit area decreases. In this case, the dispersant made of the copolymer is preferably used because it is more effective than the other dispersants.
The dispersant in the present invention is preferably 5 to 200 with respect to the total amount of the pigment in the colored resin composition.
% By weight, more preferably about 10 to 100% by weight.

The colored resin composition of the present invention may contain other dispersants as long as the effects of the present invention are not impaired. Examples of other dispersants include those described in JP-A-2006-343648, for example.
[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

  The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total solid content of the pigment. Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less. By controlling the addition amount within the above range, it is preferable in that the effect as a dispersion aid is exhibited and the dispersibility and dispersion stability are better.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of the resin selected from the (C) binder resin or other binder resins as the following dispersion resin.
Specifically, in [Preparation Method of Colored Resin Composition] to be described later, by including (C) binder resin together with the above-mentioned components (E), the (C) binder resin is ( E) It contributes to the dispersion stability of (A) brominated zinc phthalocyanine pigment and other pigments by a synergistic effect with the dispersant. As a result, the amount of (E) dispersant added may be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the colored resin composition.
As the dispersion resin, various (C) binder resins described later can be used.
The acid value of the dispersion resin is preferably 0.5 mg-KOH / g or more, more preferably 1 mg-KOH / g or more, most preferably 5 mg-KOH / g or more, and preferably 300 mg-KOH / g or less, 200 mg-KOH / G or less is more preferable, and 150 mg-KOH / g or less is most preferable. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

  The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

[(F) polymerizable monomer]
The colored resin composition of the present invention may contain a polymerizable monomer (F) other than the compound (1).
(F) The polymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized, but it may be referred to as an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiating component (G) described later when the colored resin composition of the present invention is irradiated with actinic rays. It is. In addition, the (F) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.
(F) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may be a single substance or a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (F) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content of these (F) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of the (F) polymerizable monomer to the (B) yellow dye is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. Moreover, it is 200 weight% or less normally, Preferably it is 100 weight% or less, More preferably, it is 80 weight% or less.

Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.
In addition, since the colored resin composition of this invention contains a compound (1), it is preferable to contain the (G) photoinitiator component.

[(G) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (G) a photopolymerization initiation component and / or a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, when the colored resin composition of the present invention contains a resin having an ethylenic double bond as the component (C), or contains an ethylenic compound as the component (F), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (G) as the photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(G1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(G2) component”). ")", And a sensitizing dye (hereinafter also referred to as "(G3) component").

[(G) Photopolymerization initiation component]
The (G) photopolymerization initiating component in the present invention is usually a mixture of (G1) a photopolymerization initiator and, if necessary, (G2) a polymerization accelerator and (G3) an additive such as a sensitizing dye. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation component (G1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922; Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

  The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and a compound represented by the following formula (XI).

(In the formula (XI),
n represents an integer of 0 or 1.
m represents an integer of 0 to 20.
X ¹ represents a divalent aromatic hydrocarbon ring group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.

X ² is 1 selected from the group consisting of —CR ⁹⁴ R ⁹⁵ —, —C (═CR ⁹⁶ R ⁹⁷ ) —, —CR ⁹⁸ = CR ⁹⁹ —, —C≡C— and —C (═O) —. One group or a group formed by bonding two or more of these.
R ^{96 to} R ⁹⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁹⁴ and ^{R 95, R 101} are each independently a hydrogen atom, a halogen atom, each of which may have a substituent, an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon A heteroaryl group having 2 to 20 carbon atoms, a monovalent non-aromatic heterocyclic group having 2 to 20 carbon atoms, and 1 carbon atom
˜20 alkoxy group, C6-C20 aryloxy group, C2-C20 acyl group, C2-C20 acyloxy group, C1-C20 N-substituted amino group, C3-C3 20 cycloalkyl groups, C1-C20 alkylsulfonyl groups, C6-C20 arylsulfonyl groups, C1-C20 alkylsulfinyl groups, C6-C20 arylsulfinyl groups, carbamoyl groups, carbon C2-C20 alkylcarbamoyl group, C7-C20 arylcarbamoyl group, C1-C20 aminooxycarbonyl group, cyano group, nitro group, C1-C12 alkylsulfanyl group, C2-C2 12 alkoxycarbonyl groups, 3 to 12 alkenyloxycarbonyl groups, 3 to 12 alkynyloxycarbonyl groups, An aryloxycarbonyl group having 7 to 12 prime atoms, a heteroaryloxycarbonyl group having 3 to 12 carbon atoms, an alkylsulfanylcarbonyl group having 2 to 12 carbon atoms, an alkenylsulfanylcarbonyl group having 3 to 12 carbon atoms, and 3 to 12 carbon atoms alkynyl Nils Alpha alkenyl group, arylsulfanyl group of 7 to 12 carbon atoms, heteroaryl sulfanyl group having 3 to 12 carbon atoms, alkylsulfanyl alkoxy group having 2 to 12 carbon ^{atoms, -O-N = CR 30 R} 31, - N (OR ³⁰ ) —OCO—R ³¹ or a group represented by the following formula (2):

(R ³⁰ and R ³¹ each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.)
Represents. R ¹⁰¹ may be bonded to X ¹ or Z to form a ring.
R ¹⁰² may have a substituent, which may have a substituent, an alkylcarbonyl group having 2 to 20 carbon atoms, an alkenylcarbonyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 4 to 8 carbon atoms, or a carbon number having 7 to 20 carbon atoms. An arylcarbonyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroarylcarbonyl group having 3 to 20 carbon atoms, or 2 carbon atoms Represents an alkylaminocarbonyl group of ˜20.

Z represents an aromatic ring group which may have a substituent. )
Of the compounds represented by the formula (XI), compounds in which X ¹ is an optionally substituted carbazole ring are preferred, and specifically, compounds represented by the following formula (XII), etc. Is mentioned.

(In the above formula (XII),
n, m, X ² , R ^101, R ¹⁰² , and Z are as defined in the above formula (XI).
R ¹⁰³ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ^{104 to} R ¹⁰⁹ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. )
(About n)
n represents an integer of 0 or 1.

(About m)
m represents an integer of 0 to 20.
M is preferably 0 to 5 in that the amount of radically active species generated per gram is high and the production is simple.
(For ^{X 2} and ^{R 101)}
X ² is 1 selected from the group consisting of —CR ⁹⁴ R ⁹⁵ —, —C (═CR ⁹⁶ R ⁹⁷ ) —, —CR ⁹⁸ = CR ⁹⁹ —, —C≡C— and —C (═O) —. One group or a group formed by bonding two or more of these.

When m is 2 or more, the plurality of X ² contained in one molecule may be the same or different.
R ^{96 to} R ⁹⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁹⁴ , R ⁹⁵ and R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon atom, each of which may have a substituent. C2-C20 heteroaryl group, C2-C20 monovalent non-aromatic heterocyclic group, C1-C20 alkoxy group, C6-C20 aryloxy group, C2-C20 Acyl group, C2-C20 acyloxy group, C1-C20 N-substituted amino group, C1-C20 cycloalkyl group, C1-C20 alkylsulfonyl group, C6-C20 Arylsulfonyl group, alkylsulfinyl group having 1 to 20 carbon atoms, arylsulfinyl group having 6 to 20 carbon atoms, carbamoyl group, alkylcarbamoyl group having 2 to 20 carbon atoms, arylcarbamoy having 7 to 20 carbon atoms Group, an aminooxycarbonyl group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkylsulfanyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an alkenyloxycarbonyl group having 3 to 12 carbon atoms, C3-C12 alkynyloxycarbonyl group, C7-C12 aryloxycarbonyl group, C3-C12 heteroaryloxycarbonyl group, C2-C12 alkylsulfanylcarbonyl group, C3-C12 Alkenylsulfanylcarbonyl group, C3-C12 alkynylsulfanylcarbonyl group, C7-C12 arylsulfanylcarbonyl group, C3-C12 heteroarylsulfanylcarbonyl group, C2-C12 alkylsulfanylalkoxy group , -O-N = ^{CR 30} R ^1, a group represented by ^{-N (OR 30) -OCO-R} 31 or a group represented by the following formula (2):

(R ³⁰ and R ³¹ each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.)
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom that are relatively stable against a nucleophilic substitution reaction are preferable.
The aryl group having 6 to 20 carbon atoms that may have a substituent preferably has 6 to 12 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, A sulfo group, a carboxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a mesityl group, a naphthyl group, and an anthracenyl group.

  The heteroaryl group having 2 to 20 carbon atoms which may have a substituent is an aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a heteroatom, and preferably has 2 or more carbon atoms , 12 or less. When the heteroaryl group has a plurality of atoms constituting a ring other than carbon, these may be the same or different. The monovalent non-aromatic heterocyclic group may be monocyclic or condensed, and may be a pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, oxazolyl group, triazolyl group, thiadiazolyl group, pyridinyl group. , Pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, benzothiazolinyl group, phthalimidoyl group, benzimidazolyl group, furyl group, thiophenyl group, pyranyl group, indolinyl group, isoindolinyl group and the like. Examples of the group that may be substituted on the heteroaryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and a sulfo group. And a carboxy group. Specific examples of the heteroaryl group include 2-pyrrolyl group, 2-imidazolyl group, 1-pyrazolyl group, 2-thiazolyl group, 2-oxazolyl group, 1,2,4-triazol-1-yl group, and 4-pyridinyl. Group, 2-pyrimidinyl group, 4,6-diamino-2-triazinyl group, 8-quinolinyl group, 8-isoquinolinyl group, 2-benzothiazolinyl group, 6-methyl-7-sulfo-2-benzothiazolinyl Group, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl group, 1H-benzimidazol-2-yl group, 2-furyl group, 2-thiophenyl group, 1-indolinyl group, 2 -An isoindolinyl group is mentioned.

The monovalent non-aromatic heterocyclic group having 2 to 20 carbon atoms which may have a substituent is a non-aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom, Preferably, the carbon number is 2 or more and 12 or less. When the monovalent non-aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different. The monovalent non-aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include a piperidinyl group, a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a piperazinyl group, and a morpholinyl group. Examples of the substituent that the monovalent non-aromatic heterocyclic group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, and diethylamino. Group, halogen atom, sulfo group and carboxy group. Specific examples of the monovalent non-aromatic heterocyclic group include 1-piperidinyl group, 1-pyrrolidinyl group, 1-imidazolidinyl group, 1-pyrazolidinyl group, 1-piperazinyl group and 1-morpholinyl group.

  The alkoxy group having 1 to 20 carbon atoms which may have a substituent preferably has 1 to 10 carbon atoms. Examples of the substituent that the alkoxy group may have include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Etc. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-amyloxy group, t-amyloxy group, n- Hexyloxy group, n-heptyloxy group, n-octyloxy group, hydroxyethoxy group, 1,2-dihydroxypropoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2- (2 -Methoxyethoxy) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 2- (2-butoxyethoxy) ethoxy group, benzyloxy group, phenethyloxy group, etc., linear or branched alkoxy having 1 to 18 carbon atoms Groups.

  The aryloxy group having 6 to 20 carbon atoms which may have a substituent preferably has 6 to 14 carbon atoms. Examples of the aryloxy group include a phenoxy group, a naphthoxy group, and an anthracenyloxy group. Examples of the substituent that the aryloxy group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and cyano. Group, sulfo group, carboxy group and the like. Specific examples of the aryloxy group include aryls optionally having a substituent such as a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, a 3-tolyloxy group, a 4-methoxyphenoxy group, and a 4-cyclohexylphenoxy group. An oxy group is mentioned.

Optionally substituted acyl group having 2 to 20 carbon atoms is represented by ^{-COR 15b,} R ^15b may have an optionally substituted alkyl group or a substituted group Represents an aryl group. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable number of carbon atoms of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴⁸ . Specific examples of the acyl group include acetyl group, ethylcarbonyl group, n-butylcarbonyl group, benzoyl group, p-tolylcarbonyl group, m-tolylcarbonyl group, p-methoxyphenylcarbonyl group and the like.

The acyloxy group having 2 to 20 carbon atoms that may have a substituent is represented by -O-COR ^16b , and R ^16b has an alkyl group or a substituent that may have a substituent. Represents a good aryl group. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the acyl group include an acetoxy group, an ethylcarbonyloxy group, an n-butylcarbonyloxy group, a benzoyloxy group, a p-tolylcarbonyloxy group, an m-tolylcarbonyloxy group, and a p-methoxyphenylcarbonyloxy group. Is mentioned.

The N-substituted amino group having 1 to 20 carbon atoms which may have a substituent is —NR ^17b R ^18.
is represented by ^b, R ^17b represents a hydrogen atom, an optionally substituted alkyl group, an aryl group which may have a substituent. R ^18b represents an alkyl group which may have a substituent and an aryl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the N-substituted amino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, a cyclohexylethyl group, and a phenylamino group. , Diphenylamino group, di (p-tolyl) amino group, di (p-methoxyphenyl) amino group, ethylphenylamino group, n-butylphenylamino group and the like.
The cycloalkyl group having 3 to 20 carbon atoms which may have a substituent preferably has 3 to 12 carbon atoms. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decalinyl group. Examples of the group which may be substituted on the cycloalkyl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and a cyano group. , Sulfo group and carboxy group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decalinyl group.

An alkylsulfonyl group having 1 to 20 carbon atoms that may have a substituent group _is represented by -SO ^{2 -R 19b, R 19b} represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a phenethylsulfonyl group, a 2-ethylhexylsulfonyl group, a 2-ethoxyethylsulfonyl group, a 2- (2-ethoxyethoxy) ethylsulfonyl group, and trifluoromethyl. A sulfonyl group etc. are mentioned.

The arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent is represented by —SO ₂ —R ^20b , and R ^20b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the arylsulfonyl group include a phenylsulfonyl group, a naphthylsulfonyl group, a p-tolylsulfonyl group, and a p-methoxyphenylsulfonyl group.

Alkylsulfinyl groups having 1 to 20 carbon atoms that may have a substituent group is represented by ^{-SO-R 21b, R 21b} represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a phenethylsulfinyl group, a 2-ethylhexylsulfinyl group, a 2-ethoxyethylsulfinyl group, a 2- (2-ethoxyethoxy) ethylsulfinyl group, and trifluoromethyl. Examples thereof include a sulfinyl group.

The arylsulfinyl group having 6 to 20 carbon atoms which may have a substituent is represented by —SO—R ^22b , and R ^22b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the arylsulfinyl group include phenylsulfinyl group, naphthylsulfinyl group, p-tolylsulfinyl group, p-methoxyphenylsulfinyl group and the like.

The alkylsulfanyl group having 1 to 12 carbon atoms that may have a substituent is represented by —S—R ^23.
represented by ^b , R ^23b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfanyl group include a methylsulfanyl group, an ethylsulfanyl group, a phenethylsulfanyl group, a 2-ethylhexylsulfanyl group, a 2-ethoxyethylsulfanyl group, a 2- (2-ethoxyethoxy) ethylsulfanyl group, and trifluoromethyl. And a sulfanyl group.

Alkylcarbamoyl group of 3 to 20 carbon atoms which may have a substituent group ^is represented by ^{-CO-NR 11b R 12b, R} 11b and ^{R 12b} are, each independently, a hydrogen atom or a substituent Represents an optionally substituted alkyl group. The alkyl group usually has 1 or more carbon atoms and usually 19 or less, preferably 12 or less. Examples of the group that may be substituted with the alkyl group include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group. 2-butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like. Specific examples of the alkylamino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, and a cyclohexylethyl group. Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a phenethylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a 2-ethoxyethylcarbamoyl group, a 2- (2-ethoxyethoxy) ethylcarbamoyl group, and a dimethylcarbamoyl group. Etc.

Which may have a substituent arylcarbamoyl group of 2 to 20 carbon atoms ^is represented by ^{-CO-NR 13b R 14b, R} 13b represents an aryl group which may have a substituent. R ^14b represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b .

  The aryl group usually has 6 or more carbon atoms, usually 19 or less, preferably 12 or less, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, A sulfo group, a carboxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a naphthyl group, and an anthracenyl group. Specific examples of the arylcarbamoyl group include a phenylcarbamoyl group, a naphthylcarbamoyl group, a p-tolylcarbamoyl group, a p-methoxyphenylcarbamoyl group, and a phenylmethylcarbamoyl group.

The C2-C12 alkoxycarbonyl group which may have a substituent is represented by -CO-OR ^24b , and R ^24b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, phenethyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 2-ethoxyethoxycarbonyl group and the like.

The optionally substituted alkenyloxycarbonyl group having 3 to 12 carbon atoms is —CO
-OR ^25b , R ^25b represents an alkenyl group which may have a substituent. The alkenyl group usually has 1 or more carbon atoms and usually 11 or less, preferably 8 or less. Examples of the group that may be substituted with the alkenyl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned.

Specific examples of the alkenyl group include a vinyl group, an allyl group, and a methanyl group. Specific examples of the alkenyloxycarbonyl group include alkenyloxycarbonyl groups having 3 to 12 carbon atoms such as vinyloxycarbonyl group and allyloxycarbonyl group.
May have a substituent group alkynyloxy group having 3 to 12 carbon atoms is represented by ^{-CO-OR 26b, R 26b} represents an alkynyl group which may have a substituent. The alkynyl group usually has 1 or more carbon atoms and usually 11 or less, preferably 8 or less. Examples of the group which may be substituted on the alkynyl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group and a carboxy group. Is mentioned. Specific examples of the alkynyl group include a methynyl group, a propynyl group, and a butynyl group. Specific examples of the alkynyloxycarbonyl group include alkynyloxycarbonyl groups having 3 to 12 carbon atoms such as methynyloxycarbonyl group and propynyloxycarbonyl group.

The aryloxycarbonyl group having 7 to 12 carbon atoms which may have a substituent is represented by —CO—OR ^27b , and R ^27b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the aryloxycarbonyl group include those having 7 to 12 carbon atoms such as phenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, p-tolyloxycarbonyl group, p-methoxyphenyloxycarbonyl group and the like. An aryloxycarbonyl group is mentioned.

Which may have a substituent heteroaryloxy group having 3 to 12 carbon atoms is represented by ^{-CO-OR 28b,} R ^28b represents a heteroaryl group which may have a substituent. Examples of preferred carbon number, having optionally be substituent of the heteroaryl group is the same as the above R ^94, R ⁹⁵ and the substituent which may be a heteroaryl group optionally having at R ^101. Specific examples of the heteroaryloxycarbonyl group include 8-quinolinyloxycarbonyl group, 2-furanyloxycarbonyl group, 3-furanyloxycarbonyl group, 2-pyridyloxycarbonyl group, 3-pyridyloxycarbonyl group, 4 -Heteroaryloxycarbonyl groups having 3 to 12 carbon atoms such as a pyridyloxycarbonyl group and a 2-benzothiazolyloxycarbonyl group.

The C2-C12 alkylsulfanylcarbonyl group which may have a substituent is represented by -CO-SR ^29b , and R ^29b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfanylcarbonyl group include methylsulfanylcarbonyl group, ethylsulfanylcarbonyl group, n-propylsulfanylcarbonyl group, isopropylsulfanylcarbonyl group, n-butylsulfanylcarbonyl group, n-hexylsulfanylcarbonyl group, n-octyl. Examples thereof include an alkylsulfanylcarbonyl group having 2 to 12 carbon atoms such as a sulfanylcarbonyl group and an n-dodecylsulfanylcarbonyl group.

The alkenylsulfanylcarbonyl group having 3 to 12 carbon atoms which may have a substituent is represented by —CO—SR ^30b , and R ^30b represents an alkenyl group which may have a substituent. Examples of the preferable carbon number of the alkyl group and the substituent which may be included are the same as those exemplified for the alkenyl group of R ^25b . Specific examples of the alkenylsulfanylcarbonyl group include alkenylsulfanylcarbonyl having 3 to 12 carbon atoms such as vinylsulfanylcarbonyl group and allylsulfanylcarbonyl group.

Alkynyl Nils Alpha alkenyl group having 3 to 12 carbon atoms which may have a substituent group is represented by ^{-CO-SR 31b,} R ^31b represents an alkenyl group which may have a substituent. Examples of the preferable carbon number of the alkyl group and the substituent which may be included are the same as those exemplified for the alkenyl group of R ^26b . Specific examples of the alkynylsulfanylcarbonyl group include alkynylsulfanylcarbonyl groups having 3 to 12 carbon atoms such as methynyloxycarbonyl group and propynyloxycarbonyl group.

The arylsulfanylcarbonyl group having 7 to 12 carbon atoms which may have a substituent is represented by —CO—SR ^32b , and R ^32b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the arylsulfanylcarbonyl group include 7 to 12 carbon atoms such as a phenylsulfanylcarbonyl group, a 1-naphthylsulfanylcarbonyl group, a 2-naphthylsulfanylcarbonyl group, a p-tolylsulfanylcarbonyl group, and a p-methoxyphenylsulfanylcarbonyl group. An arylsulfanylcarbonyl group is mentioned.

Heteroaryl sulfanyl group having 3 to 12 carbon atoms which may have a substituent group is represented by ^{-CO-SR 33b,} R ^33b represents a heteroaryl group which may have a substituent. Examples of preferred carbon number, having optionally be substituent of the heteroaryl group is the same as the above R ^94, R ⁹⁵ and the substituent which may be a heteroaryl group optionally having at R ^101. Specific examples of the heteroarylsulfanylcarbonyl group include 8-quinolinylsulfanylcarbonyl group, 2-furanylsulfanylcarbonyl group, 3-furanylsulfanylcarbonyl group, 2-pyridylsulfanylcarbonyl group, 3-pyridylsulfanylcarbonyl group, 4 -C3-C12 heteroaryl sulfanyl carbonyl groups, such as a pyridyl sulfanyl carbonyl group and 2-benzothiazolyl sulfanyl carbonyl group, are mentioned.

  The C2-C12 alkyl sulfanyl alkoxy group which may have a substituent refers to the alkoxy group which the C1-C10 alkyl sulfanyl group substituted. The alkylsulfanyl group in the alkylsulfanylalkoxy group may be substituted with an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group or the like. The alkoxy group in the alkylsulfanylalkoxy group may be substituted with an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or the like in addition to the alkylsulfanyl group. Specific examples of the alkylsulfanylalkoxy group include an alkylthioalkoxy group having 2 to 12 carbon atoms such as a methylthiomethoxy group, a methylthioethoxy group, an ethylthiomethoxy group, an ethylthioethoxy group, a methylthiopropoxy group, and an ethylthiopropoxy group.

R ¹⁰¹ may be bonded to Z to form a ring, and the ring may have a substituent.
Examples of the substituent that these groups may have include the following [substituent group W ¹ ].
[Substituent Group W ¹ ]
An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group;

Each group described above as R ¹⁰¹ preferably has no substituent.
(About ^R102 )
R ¹⁰² may have a substituent, which may have a substituent, an alkylcarbonyl group having 2 to 20 carbon atoms, an alkenylcarbonyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 4 to 8 carbon atoms, or a carbon number having 7 to 20 carbon atoms. An arylcarbonyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroarylcarbonyl group having 3 to 20 carbon atoms, or 2 carbon atoms Represents an alkylaminocarbonyl group of ˜20.

Examples of the alkylcarbonyl group having 2 to 12 carbon atoms include an acetyl group, a propanoyl group, and a butanoyl group, and an acetyl group is preferable. Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-7.
Examples of the alkenylcarbonyl group having 3 to 25 carbon atoms include a crotonoyl group and an acryloyl group, and a crotonoyl group is preferable. Carbon number becomes like this. Preferably it is 3-12, More preferably, it is 3-7.

Examples of the cycloalkylcarbonyl group having 4 to 8 carbon atoms include a cyclohexylcarbonyl group, a methylcyclohexylcarbonyl group, a cyclopentylcarbonyl group, and the like, and a cyclohexylcarbonyl group is preferable. The number of carbon atoms is preferably 4-7.
Examples of the arylcarbonyl group having 7 to 20 carbon atoms include a benzoyl group, a methylbenzoyl group, and a naphthoyl group, and a benzoyl group is preferable. Carbon number becomes like this. Preferably it is 7-12, More preferably, it is 7-10.

Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group, and a methoxycarbonyl group is preferable. The number of carbon atoms is preferably 2-8.
Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include a phenoxycarbonyl group, a p-methylphenoxycarbonyl group, and a naphthoxycarbonyl group, and a phenoxycarbonyl group is preferable. Carbon number becomes like this. Preferably it is 7-15, More preferably, it is 7-10.

Examples of the heteroaryl group having 2 to 20 carbon atoms include a thienyl group, a pyrrolyl group, and a pyridyl group, and a thienyl group is preferable. Carbon number becomes like this. Preferably it is 2-12, More preferably, it is 2-7.
Examples of the heteroarylcarbonyl group having 3 to 20 carbon atoms include a thiophenecarbonyl group, a pyrrolylcarbonyl group, and a pyridinecarbonyl group, and a thiophenecarbonyl group is preferable. Carbon number becomes like this. Preferably it is 5-15, More preferably, it is 7-10.

Examples of the alkylaminocarbonyl group having 2 to 20 carbon atoms include a morpholinocarbonyl group, a dimethylaminocarbonyl group, a methylaminocarbonyl group and the like, and a dimethylaminocarbonyl group is preferable. Carbon number becomes like this. Preferably it is 2-12, More preferably, it is 2-10.
Of the above groups, from the viewpoint of exposure sensitivity, R ¹⁰² is preferably an alkylcarbonyl group, a cycloalkylcarbonyl group, or an arylcarbonyl group, and more preferably an alkylcarbonyl group or an arylcarbonyl group.

As each group substituent which may be possessed by the above as R ^102, for example, the there may be mentioned those described in the section [Substituent group W ^1], each group described above as R ¹⁰² is , It preferably has no substituent.
(About R ¹⁰³ )
R ¹⁰³ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2 -Butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like can be mentioned. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

Examples of the alkenyl group include allyl group and methanyl group. The number of carbon atoms is preferably 3-4.
The aryl group is the same as that described in the above section (for X and R ¹⁰¹ ).
Examples of the substituent that each group described above as R ¹⁰³ may have include those described in the above section [Substituent group W ¹ ], but each group described above does not have a substituent. Those are particularly preferred.

R ¹⁰³ is preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group, from the viewpoint that the generation amount of radical active species per gram is high and the production is simple.
(For ^R 104 ^{to R 109)}
R ^{104 to} R ¹⁰⁹ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

R ^{104 to} R ¹⁰⁹ are particularly preferably hydrogen atoms from the viewpoint that the generation amount of radical active species per gram is high and the production is simple.
(About Z)
Z represents an aromatic ring group which may have a substituent.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

  The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 18, but for example, one free valence Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, indene ring, etc. .

  In addition, the aromatic heterocyclic group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, but for example, one free atom Having a valence, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole Ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, Synoline ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, azulene ring, an acridine ring, a xanthene ring, a phenazine ring, a phenothiazine ring, a phenoxazine ring, groups such as a benzothiazole ring.

As the aromatic substituent which may be ring group optionally having in Z, for example, those described in the section below [Substituent Group W ^1].
[Substituent Group W ¹ ]
An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, and a carboxy group;

[Specific Examples of Compound (XI)]
Although the preferable specific example of compound (XI) in this invention is shown below, this invention is not limited to these.

  In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like. Specifically, IRGACURE 651, IRGACURE 184, DAROCUR 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE 819, and IRGACURE 819, IRGACURE 819, IRGACURE 819

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (G2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

These (G1) photopolymerization initiators and (G2) polymerization accelerators may be used alone or in combination of two or more.
Further, (G3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(G3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content of these (G) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight based on the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less.

Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed part in the development station is good, and it is preferable in that it is difficult to induce poor development.
((G) Thermal polymerization initiating component)
Specific examples of the thermal polymerization initiating component (G) that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiating component described in International Publication No. 2009/107734 can be used.

These thermal polymerization initiating components may be used alone or in combination of two or more.
[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, (A) a halogenated metal phthalocyanine pigment, (B) a yellow dye, (C) a binder resin, and compound (1). (D) It can prepare by mixing with a solvent and the arbitrary component used as needed.

  Preferably, (A) a metal halide phthalocyanine pigment is added in a solvent in the presence of (E) a dispersant and optionally a dispersing aid, optionally with (C) a part of a binder resin, for example paint Using a shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like, a pigment dispersion is prepared by mixing and dispersing while grinding.

In the pigment dispersion, (B) yellow dye, (C) binder resin and compound (1), (F) polymerizable monomer other than compound (1), if necessary, (G) photopolymerization initiation component and / or Alternatively, a method of preparing a colored resin composition by adding a thermal polymerization initiating component and the like and mixing them can be mentioned.
[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.

Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display device using them will be described.
<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.

The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.
First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made, an epoxy resin, a thermosetting resin, and various glasses.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.

Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

  The light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is, and is used as a part of a component such as a color display or a liquid crystal display device. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Further, a column structure (photo spacer) by a photolithography method may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble according to a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.
(Synthesis of color materials)
<Synthesis Example 1: Synthesis of Compound (1-i)>
To a four-necked flask, 117 parts by weight of 4-acetamidobenzenesulfonyl chloride, 1600 parts by weight of methylene chloride, 56 parts by weight of triethylamine, and 3 parts by weight of 4-dimethylaminopyridine were added and cooled to 5 ° C. Subsequently, 71 parts by weight of 1,5-dimethylhexylamine was added dropwise over 15 minutes, followed by stirring at room temperature for 6 hours. The organic layer was washed twice with 1000 parts by weight of 1 mol / L hydrochloric acid, followed by washing with 1000 parts by weight of a saturated aqueous sodium hydrogen carbonate solution, and the resulting organic layer was dried over anhydrous sodium sulfate. After the desiccant was filtered off, the solvent was distilled off to obtain 154 parts by weight of a white solid intermediate (ia).

  When 33 parts by weight of intermediate (ia) and 250 parts by weight of 5% by weight hydrochloric acid were added to a four-necked flask and stirred at 90 ° C. for 5 hours, white solid (1-b) was obtained. This white solid was used in the next reaction without purification.

To the suspension containing the above (ib), 1000 parts by weight of water and 24 parts by weight of concentrated hydrochloric acid were added, cooled to 5 ° C., 8 parts by weight of sodium nitrite was added, and stirred for 30 minutes.
26 parts by weight of 1- (2-ethylhexyl) -1,2-dihydro-6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile was added to a mixed solution of 800 parts by weight of methanol and 500 parts by weight of water; The solution containing the diazonium salt was dropped while maintaining the pH at 8 with sodium hydroxide. The reaction solution was subjected to suction filtration to obtain an orange solid. This solid was purified by silica gel chromatography to obtain 14 parts by weight of yellow solid compound (1-i).

The maximum absorption wavelength (λmax) of this compound in a 10 ppm chloroform solution is 431 nm.
The gram extinction coefficient was 87. The results of NMR are shown below.
¹ H NMR (CDCl ₃ , 400 MHz) δ 7.96 (d, 2H, J = 8.8 Hz), 7.57 (d, 2H, J = 8.8 Hz), 4.26 (d, 2H, J = 8.4 Hz), 4.00-3.83 (m, 2H), 3.45-3.30 (m, 1H) 2.64 (s, 3H), 1.87-1.75 (m, 1H) ), 1.48-1.00 (m, 18H), 0.97-0.86 (m, 6H), 0.81 (dd, 6H, J = 6.4, 2.4 Hz).

<Synthesis Example 2: Synthesis of Compound (1-ii)>
When 33 parts by weight of intermediate (ia) and 250 parts by weight of 5% by weight hydrochloric acid were added to a four-necked flask and stirred at 90 ° C. for 5 hours, white solid (1-b) was obtained. This white solid was used in the next reaction without purification. To the suspension containing the above (ib), 1000 parts by weight of water and 24 parts by weight of concentrated hydrochloric acid were added, cooled to 5 ° C., 8 parts by weight of sodium nitrite was added, and stirred for 30 minutes.

30 parts by weight of the above (ii-a) (purity 80%) is added to a mixed solution of 500 parts by weight of methanol and 1000 parts by weight of water, cooled to 5 ° C., and the liquid containing the diazonium salt is adjusted to pH with sodium hydroxide. While keeping at 8, the solution was dropped. The reaction solution was subjected to suction filtration to obtain an orange solid. This solid was purified by silica gel chromatography to obtain 12 parts by weight of a yellow solid compound (ii-b).

32 parts by weight of the above (ii-b) were dissolved in 800 parts by weight of methylene chloride, 12 parts by weight of triethylamine and 1 part by weight of 4-dimethylaminopyridine were added, and the mixture was stirred at 5 ° C. 10 parts by weight of methacryloyl chloride was added and stirred at room temperature for 12 hours. After completion of the reaction, the mixture was washed with 600 parts by weight of a saturated aqueous sodium carbonate solution, 600 parts by weight of a saturated aqueous ammonium chloride solution and 1000 parts by weight of a saturated saline solution, and the organic layer was dried over anhydrous magnesium sulfate. The desiccant was filtered off and the solvent was distilled off with an evaporator to obtain a brown liquid. This solid was purified by silica gel chromatography to obtain 6 parts by weight of a yellow solid compound (1-ii).

The maximum absorption wavelength (λmax) of this compound in a 10 ppm chloroform solution was 431 nm, and the Gram extinction coefficient was 83.
<Synthesis Example 3: Synthesis of Compound (1-iii)>
5 parts by weight of the above (1-ii) and 0.7 parts by weight of methyl methacrylate are dissolved in 120 parts by weight of PEGMA, and 0.02 part by weight of 2,2′-azobis (2-methylbutyronitrile) (V-59). Was added. The mixture was stirred at 90 ° C. for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was discharged into 1800 parts by weight of hexane, subjected to reprecipitation purification, and 0.5 parts by weight of yellow solid (1-iii) was obtained by filtration.

The weight average molecular weight Mw measured by GPC of this compound was about 1100, the maximum absorption wavelength (λmax) in a 10 ppm chloroform solution was 430 nm, and the gram extinction coefficient was 67.
<Synthesis Example 4: Synthesis of Compound (1-iv)>
When 33 parts by weight of intermediate (ia) and 250 parts by weight of 5% by weight hydrochloric acid were added to a four-necked flask and stirred at 90 ° C. for 5 hours, white solid (1-b) was obtained. This white solid was used in the next reaction without purification. To the suspension containing the above (ib), 1000 parts by weight of water and 24 parts by weight of concentrated hydrochloric acid were added, cooled to 5 ° C., 8 parts by weight of sodium nitrite was added, and stirred for 30 minutes.

22 parts by weight of the above (iii-a) was dissolved in a mixed solution of 350 parts by weight of N-methylpyrrolidone and 350 parts by weight of water, cooled to 10 ° C., and the diazonium salt solution was added with an aqueous sodium hydroxide solution. The solution was added dropwise while maintaining the pH of the solution at 8. After further stirring for 2 hours at 10 ° C., the precipitate was filtered to obtain a brown solid. This solid was purified by silica gel chromatography to obtain 26 parts by weight of a yellow solid compound (1-iv).

The maximum absorption wavelength (λmax) of this compound in a 10 ppm chloroform solution is 429 nm.
The gram extinction coefficient was 88.
<Synthesis Example 5: Synthesis of Compound (1-v)>
5 parts by weight of the above (1-ii), 0.7 parts by weight of methyl methacrylate and 5 parts by weight of cyclohexyl methacrylate are dissolved in 300 parts by weight of PEGMA, and 2,2′-azobis (2-methylbutyronitrile) (V— 59) 0.04 part by weight was added. The mixture was stirred at 90 ° C. for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was discharged to 1800 parts by weight of hexane, reprecipitation purification was performed, and 0.5 parts by weight of yellow solid (1-v) was obtained by filtration.

The weight average molecular weight Mw measured by GPC of this compound was about 1500, the maximum absorption wavelength (λmax) in a 10 ppm chloroform solution was 431 nm, and the gram extinction coefficient was 52.
<Synthesis Example 6: Synthesis of Compound (1-vi)>
After adding 60 parts by weight of trifluoromethanesulfonamide and 111 parts by weight of potassium carbonate to 800 parts by weight of acetonitrile, 79 parts by weight of 4-acetamidobenzenesulfonyl chloride was added and stirred under reflux for 4.5 hours. After cooling to room temperature, the suspension was suspended in 5000 parts by weight of acetonitrile, and the filtrate obtained by suction filtration was concentrated to obtain 136 parts by weight of (vi-a) as a white solid.

  (Vi-a) 100 parts by weight of water and 30 parts by weight of concentrated hydrochloric acid were added to 17 parts by weight and stirred at 90 ° C. for 8 hours to obtain a solution of (vi-b). This solution was used for the next reaction without purification.

To the obtained transparent solution, 500 parts by weight of water and 200 parts by weight of N-methylpyrrolidone are added, 10 parts by weight of concentrated hydrochloric acid is added, the mixture is cooled to 5 ° C., 3 parts by weight of sodium nitrite is added, and stirred at 10 ° C. for 1 hour. did.
11 parts by weight of 1- (2-ethylhexyl) -1,2-dihydro-6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile is added to a mixed solution of 500 parts by weight of methanol and 200 parts by weight of water; The solution containing the diazonium salt was dropped while maintaining the pH at 8 with sodium hydroxide. The reaction solution was suction filtered to obtain a yellow solid. This solid was purified by silica gel chromatography to obtain 16 parts by weight of a yellow solid compound (1-vi).

The maximum absorption wavelength (λmax) of this compound in a 10 ppm chloroform solution was 429 nm, and the Gram extinction coefficient was 69.
[Synthesis of resin]
(Synthesis Example 7: Synthesis of Binder Resin A)
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate and 66 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and 2.2′-azobis-2-methyl 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 8400 and an acid value of 80 mg-KOH / g.

Further, propylene glycol monomethyl ether acetate was added to adjust the solid content concentration to 40% by weight.
[Preparation of green pigment dispersion]
As a pigment, C.I. I. Pigment Green 58 (manufactured by DIC), 12.7 parts by weight, “BYK-LPN6919” (methacrylic acid AB block copolymer, amine value 121 mg-KOH / g, acid value 1 mg-KOH / g or less) is 3.2 parts by weight in terms of solid content, and 4.2 parts by weight in terms of solid content is mixed with binder resin A synthesized in Synthesis Example 7, using propylene glycol monomethyl ether acetate as a solvent, and the solid content concentration Adjusted to 20%. A stainless steel container was filled with 100.5 parts by weight of the mixed solution and 300 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours to prepare a green pigment dispersion.

[Preparation of colored resin composition]
(Examples 1-4, Comparative Example 1)
The dye synthesized in Synthesis Example 1, the green pigment dispersion, the binder resin A, pentaerythritol tetraacrylate, pentaerythritol triacrylate, or dipentaerythritol hexaacrylate as a polymerizable monomer, and “IRGACURE OXE02” as a photopolymerization initiation system component ( Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF) and fluorosurfactant as surfactant F-475 (manufactured by DIC) was mixed in the proportions shown in Table 1, and examples and comparisons were made using propylene glycol monomethyl ether acetate and 1-methoxy-2-propanol as the solvent so that the solid content concentration was 20% by weight. Example colored resin compositions were prepared. The green pigment dispersion inside is 20 parts by weight of PGMEA liquid, (B) yellow dye (C) binder resin: resin A, polymerizable monomer, photopolymerization initiating component, surfactant is part by weight of solid content. Represent.

  In addition, the structure of the compound used as a polymerizable monomer is as follows, respectively.

(Examples 5 to 10)
Dye synthesized in Synthesis Examples 1-6, green pigment dispersion, binder resin A, pentaerythritol tetraacrylate or pentaerythritol triacrylate as a polymerizable monomer, OXE02 as a photopolymerization initiation system component, and fluorine-based interface as a surfactant Activator F-475 (manufactured by DIC) was mixed in the proportions shown in Table 2, and using propylene glycol monomethyl ether acetate and 1-methoxy-2-propanol as solvents, the solid content concentration was 20% by weight. A colored resin composition was prepared. In addition, the green pigment dispersion in the table is 20 parts by weight of PGMEA liquid, (B) yellow dye (C) binder resin: resin A, polymerizable monomer, photopolymerization initiating component, surfactant is solid content Represents parts by weight.

[Contrast measurement substrate creation]
A colored resin composition was applied to a cleaned glass substrate AN100 (Asahi Glass Co., Ltd.) by a spin coating method so as to have a dry film thickness of 2.0 μm and dried under reduced pressure.
Next, it exposed at 60 mj / cm < ² > with the high pressure mercury lamp, and obtained the substrate before a heating. Then 230
Post-baking was performed in an oven at 20 ° C. for 20 minutes to obtain a substrate after heating.

[Contrast ratio measurement and calculation of contrast ratio retention]
The substrate obtained before and after heating is sandwiched between two polarizing plates, and the polarizing plate on the front side is rotated while irradiating with light in the wavelength range of 380 to 780 nm from the back side, and the transmitted light intensity is measured by the luminance meter BM The maximum and minimum values were measured with -5AS (Topcon). A value obtained by dividing the maximum value by the minimum value was evaluated as the contrast ratio. Furthermore, the value obtained by dividing the contrast ratio of the obtained substrate after heating by the contrast ratio of the substrate before overheating was defined as the contrast ratio retention rate.

As shown in Tables 3 and 4, pixels formed using the colored resin composition of the present invention have high contrast and high heat resistance (contrast ratio retention).
Therefore, the color filter including the pixel of the present invention, the liquid crystal display device, and the organic EL display device are of high quality.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (10)

(A) a halogenated metal phthalocyanine pigment, (B) a yellow dye, (C) a binder resin and (D) a solvent, and further containing a compound represented by the following formula (1): Colored resin composition.

(In the formula (1),
m represents an integer of 3 or 4.
n represents an integer of 1 to 3.
R ¹ represents a hydrocarbon group which may have a substituent,
R ² represents a hydrogen atom or a hydrocarbon group which may have a substituent.
X represents a direct bond, a 3 or quaternary carbon atom, a 3 or 4 valent heterocyclic group or a 3 or 4 valent aromatic ring group.
However, when X is a quaternary carbon atom, m is 3 and may have a hydroxyl group as a substituent.
In addition, a plurality of molecules contained in one molecule

May be the same or different. )   The colored resin composition according to claim 1, wherein the yellow dye (B) is a pyridone azo compound. The colored resin composition according to claim 2, wherein the pyridone azo compound is a compound represented by the following formula (I).

(In the above formula (I), A represents an aromatic hydrocarbon ring group which may have a substituent or a heterocyclic group which may have a substituent.
R ^1a represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a carboxy group, or a trifluoromethyl group.
R ^2a represents a hydrogen atom, a cyano group, a carbamoyl group, an alkylcarbamoyl group which may have a substituent, an arylcarbamoyl group which may have a substituent, a carboxy group, a sulfamoyl group or a sulfo group.
R ^3a has a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and a substituent. 7 to 7 carbon atoms
20 aralkyl groups, optionally substituted heterocyclic groups having 3 to 20 carbon atoms, carbamoyl groups, optionally substituted alkyl carbamoyl groups having 2 to 20 carbon atoms, and substituents. An optionally substituted arylcarbamoyl group having 7 to 30 carbon atoms, a sulfamoyl group, an optionally substituted alkylsulfamoyl group having 1 to 20 carbon atoms, and an optionally substituted carbon number An arylsulfamoyl group having 6 to 30 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, an aryloxycarbonyl group having 7 to 30 carbon atoms which may have a substituent, The C2-C30 acyl group which may have a substituent, the C1-C30 alkylsulfonyl group which may have a substituent, or the C6-C3 which may have a substituent. 30 arylsul It represents a group. )   (A) The metal halide phthalocyanine pigment is C.I. I. It is pigment green 58, The colored resin composition as described in any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, (E) A dispersing agent is contained, The colored resin composition as described in any one of Claims 1-4 characterized by the above-mentioned.   The colored resin composition according to any one of claims 1 to 5, further comprising (G) a photopolymerization initiation component and / or a thermal polymerization initiation component.   The colored resin composition according to claim 6, wherein the (G) photopolymerization initiation component contains an oxime compound.   It has a pixel formed using the colored resin composition as described in any one of Claims 1-7, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 8.   An organic EL display device comprising the color filter according to claim 8.

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