JP2015124378A - Coloring composition, color filter and liquid crystal display, organic el display, and solid state imaging element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition which hardly causes color migration to an adjacent layer and has high brightness, a color filter having preferable color reproductivity and high brightness, and a liquid crystal display, an organic EL display and a solid state imaging element which can display an image which is excellent in color reproductivity and has high brightness.SOLUTION: The coloring composition includes a phthalocyanine compound and a methine compound.

Description

  The present invention relates to a coloring composition, a color filter, a liquid crystal display device, an organic EL display device, and a solid-state imaging device.

  As a method for producing a color filter used for a liquid crystal display device, an organic EL (Electro Luminescence) display device, and a solid-state imaging device, a staining method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method of producing a color filter by a photolithography method using a colored curable composition in which a pigment is dispersed in various curable compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by the pigment dispersion method, a colored curable composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is colored by pattern exposure and development. By performing this operation repeatedly for each color, a color filter can be obtained.

  Conventionally, pigments excellent in heat resistance and weather resistance have been used as color materials. However, there is a demand for color materials with high luminance, and the introduction of dyes with a high degree of freedom in spectral design is progressing. When a dye is used as a coloring material, it is generally said that it is inferior in heat resistance and light resistance, and various studies have been made.

  As a colored curable composition having excellent heat resistance and solvent resistance and capable of forming a color filter that does not deteriorate contrast and light resistance, a phenyl group having a predetermined substituent via an oxygen atom, sulfur atom or -NR- A colored curable composition containing a coloring material containing a phthalocyanine dye to which is bonded and a polymerizable compound has been proposed (see, for example, Patent Document 1).

  As a color filter composition having improved heat resistance, light resistance and contrast, a color filter composition containing a phthalocyanine derivative having a specific structure and a yellow dye has been proposed (for example, see Patent Document 2).

JP 2009-051896 A JP 2011-197670 A

  Since the dye is scattered in the cured film of the colored curable composition and is not fixed, the dye tends to move to the adjacent layer. For this reason, color mixing occurs between adjacent cured films of colored curable compositions having different colors, so that the intended color cannot be obtained. Therefore, there is a demand for a dye that does not cause color transfer between adjacent layers.

  The present invention has been made in view of the circumstances as described above, a color composition that is less likely to cause color transfer to an adjacent layer, has a high luminance, has a good color reproducibility, and exhibits a high luminance, and a color reproduction. It is an object of the present invention to provide a liquid crystal display device, an organic EL display device, and a solid-state imaging device that are capable of displaying an image with excellent brightness and high luminance.

The above problem is solved by the following means.
<1> A colored composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (11).

(In the general formula (1), X represents a halogen atom, M represents a non-metal atom, a metal atom, a metal oxide or a metal halide. R ¹ represents a group represented by the following general formula (2). R represents a hydrogen atom or a substituent, a plurality of n's each independently represents an integer of 0 to 4, a plurality of m's each independently represents an integer of 0 to 4; Independently represents an integer of 0 to 4, provided that at least one of n is 1 or more and at least one of m is 1 or more, and the sum of n, m and r is 16.)

(In General Formula (2), R ² and R ³ each independently represent a monovalent substituent, or a group represented by General Formula (3) or General Formula (4) below, and R ² and R ³ At least one of the groups represents a group represented by the following general formula (3) or general formula (4), and * represents a site bonded to the phthalocyanine ring in the general formula (1).

(In General Formulas (3) and (4), L ₁ and L ₂ each independently represent a single bond or a divalent linking group, and R ^{4 to} R ⁹ each independently represent a hydrogen atom or a monovalent group. Represents a substituent. * Represents a site that binds to N in the general formula (2).

(In the general formula (11), each R ₇₁ independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an aryl group, or a heteroaryl group. In formula (11), R ₇₂ and R ₇₃ each independently represent a monovalent substituent, or a group represented by the following general formula (12) or general formula (13), and R ₇₂ and R ₇₃ (At least one represents a group represented by the following general formula (12) or general formula (13).)

(In General Formulas (12) and (13), L ₁ and L ₂ each independently represent a single bond or a divalent linking group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and * represents a site bonded to the methine structure in the general formula (11).

<2> The colored composition according to <1>, further comprising a polymerizable compound and a photopolymerization initiator.
<3> The colored composition according to <2>, wherein the photopolymerization initiator includes an oxime ester compound.
<4> The colored composition according to any one of <1> to <3>, further including an alkali-soluble binder.
<5> A color filter having a colored layer formed using the colored composition according to any one of <1> to <4>.

<6> A liquid crystal display device comprising the color filter according to <5>.
<7> An organic EL display device comprising the color filter according to <5>.
<8> A solid-state imaging device comprising the color filter according to <5>.

  According to the present invention, a color composition that is less likely to cause color transfer to an adjacent layer and has high luminance, a color filter that exhibits good color reproducibility and high luminance, and an image display that has excellent color reproducibility and high luminance can be displayed. A possible liquid crystal display device, organic EL display device, and solid-state imaging device can be provided.

6 is a chart showing the results of MALDI-TOF-MASS (negative) of Intermediate 5. It is a chart which shows the result of MALDI-TOF-MASS (nega) of exemplary compound A-11. It is the ethyl acetate solution and chloroform solution spectrum of exemplary compound A-11.

Hereinafter, the coloring composition of the present invention, and a color filter, a solid-state imaging device, and a display device using the coloring composition will be described in detail.
In the present specification, “to” represents a range from the lower limit value to the upper limit value.
In addition, in the notation of groups in the present specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent.
Moreover, in this specification, (meth) acryl means containing both acryl and methacryl.

[Coloring composition]
The coloring composition of this invention contains at least 1 sort (s) of the compound represented by General formula (1), and at least 1 sort (s) of the compound represented by General formula (11).
The colored composition of the present invention may contain a heterocyclic ring-containing compound as necessary, and may further contain a coloring material, a polymerizable compound, and a photopolymerization initiator.

<< Compound Represented by Formula (1) >>
The coloring composition of this invention contains at least 1 type of the compound (phthalocyanine compound) represented by General formula (1). This phthalocyanine compound has a structure in which curable groups (including unsaturated double bonds and epoxy groups) are substituted through an aryloxy group containing a halogen atom and substituted with a sulfonamide group in the molecule. Therefore, the solubility in a solvent and the color purity (hue) as cyan are high, the absorption in an unnecessary wavelength region other than the cyan region is small (transmittance is high), and the luminance is excellent. Therefore, it has a good absorption waveform as a dye for green filters, and when it is made into a cured film, it absorbs less in the wavelength region unnecessary for the green filter and has excellent transmittance, heat resistance and light resistance, Excellent solvent resistance.

In the general formula (1), X represents a halogen atom, and M represents a nonmetal atom, a metal atom, a metal oxide, or a metal halide. R ¹ represents a group represented by the following general formula (2), and R represents a hydrogen atom or a substituent. A plurality of n each independently represents an integer of 0 to 4, a plurality of m each independently represents an integer of 0 to 4, and a plurality of r each independently represents an integer of 0 to 4. However, at least one of n is 1 or more, and at least one of m is 1 or more. The sum of n, m and r is 16.

  X represents a halogen atom, preferably a chlorine atom or a fluorine atom, and more preferably a chlorine atom. The substitution position of X is preferably the α position of the phthalocyanine skeleton in that the absorption wavelength becomes longer and the dye can be suitably used as a green filter dye.

Several m represents the integer of 0-4 each independently, and the integer of 2-4 is preferable. At least 1 of m is an integer greater than or equal to 1, and 4-15 are preferable, 2-15 are preferable, 6-15 are more preferable, 9-15 are especially preferable, Furthermore, 11-14 are preferable.
The “total of m” in the present invention is an average value of the total of m of each compound included.

M represents a nonmetal atom, a metal atom, a metal oxide, or a metal halide, preferably a metal atom, metal oxide, or metal halide, and more preferably a metal atom.
As a metal atom, Cu, Zn, Pb, Fe, Ni, or Co is preferable, and Cu and Zn are more preferable. As a metal oxide, Ti (= O) or V (= O) is preferable. As the metal _{halide, AlCl, AlI, InCl, InI} , GaCl, GaI, TiCl 2, VCI 2, SnCl 2, SiCl 2 or GeCl ₂ is preferred.
Moreover, a nonmetallic atom means the case where M is two hydrogen atoms, and specifically, when M represents a nonmetallic atom, General formula (1) is represented as follows.

R ¹ represents a group represented by the following general formula (2).
The substitution position of R ¹ is preferably the β position of the phthalocyanine skeleton in that the association of the phthalocyanine compound is promoted and the absorption intensity ratio is easily obtained. In addition, the α position of the phthalocyanine skeleton is preferable in that precipitation in the colored curable composition is suppressed and storage stability is improved.

Several n represents the integer of 0-4 each independently, the integer of 0-2 is preferable, and 0 or 1 is more preferable. At least one of n is an integer of 1 or more, and the total of four n is preferably 1 to 8, more preferably 1 to 4, and further preferably 2 to 4.
The “total of n” in the present invention is an average value of the total of n of each compound included.

  R represents a hydrogen atom or a substituent. Examples of the substituent include the substituent T described later. R is preferably a hydrogen atom, an alkyl group, an alkoxy group, a phenoxy group, an aryl group or an aryloxy group, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a phenoxy group. A hydrogen atom is more preferable.

Several r represents each independently the integer of 0-4, Preferably it is an integer of 0-2, More preferably, it is 0 or 1.
The “total of r” in the present invention is an average value of the total of r of each compound included.

The sum of m, n and r is 16. In the general formula (1), when all R ¹ represent the same substituent, all n may not be the same number, and all m may not be the same number.

  Examples of the substituent T include an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methyl group, an ethyl group, and the like. Group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1 -Norbornyl group, 1-adamantyl group), alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, for example, vinyl group, allyl group, 3-buten-1-yl group ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. A pargyl group, a 3-pentynyl group, etc.), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group. (Preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, Trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, A tro group or an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, t -Butoxy group, dodecyloxy group, cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group), aryloxy group (preferably 6-48 carbon atoms, more preferably 6-24 carbon atoms aryloxy group) , For example, a phenoxy group, 1-naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 1-phenyltetrazole-5-oxy Group, 2-tetrahydropyranyloxy group), silyloxy group (preferably having 1 to 32 carbon atoms, more preferably carbon A silyloxy group having 1 to 18 primes, for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group, an acyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). An acyloxy group, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, For example, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, a cycloalkyloxycarbonyloxy group, such as a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably having a carbon number of 7 to 32, more preferably carbon Aryloxycarbonyloxy groups having 7 to 24, for example, a phenoxycarbonyl group),

Carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group) N-ethyl-N-phenylcarbamoyloxy group), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethyl A sulfamoyloxy group, an N-propylsulfamoyloxy group), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group). , Hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably Is an acyl group having 1 to 24 carbon atoms, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably Is an alkoxycarbonyl group having 2 to 24 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, or a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group) , Aryloxycarbonyl group ( An aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Carbamoyl group such as carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclo A hexylamino group), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, an anilino group or an N-methylanilino group), a heterocyclic amino group (preferably having 1 to 32 carbon atoms). More preferably a heterocyclic amino group having 1-18, for example, 4-pyridylamino group, a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2-24, for example, an acetamide group, Benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethyl group) Ureido group, N-phenylureido group), imide group (preferably having 36 or less carbon atoms, more preferably carbon 24 or less imide group, for example, N-succinimide group, N-phthalimide group), alkoxycarbonylamino group (preferably C2-48, more preferably C2-C24 alkoxycarbonylamino group, for example, Methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonylamino group), a sulfonamide group (preferably having 1 to 48 carbon atoms, More preferably, it is a C1-C24 sulfonamide group, for example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably A sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo Group (preferably having 1 to 32 carbon atoms, more preferably carbon number) -24 azo group, for example, phenylazo group, 3-pyrazolylazo group), alkylthio group (preferably C1-C48, more preferably C1-24 alkylthio group, for example, methylthio group, ethylthio group) , An octylthio group, a cyclohexylthio group), an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms, for example, a phenylthio group), a heterocyclic thio group (preferably having a carbon number of 1 to 32, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably having 1 carbon atom) 32, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group An arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably an arylsulfinyl group having 6 to 24 carbon atoms, for example, a phenylsulfinyl group), an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably carbon An alkylsulfonyl group of 1 to 24, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group ), An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyl group or a 1-naphthylsulfonyl group), a sulfamoyl group (preferably having 3 carbon atoms). A sulfamoyl group having 2 or less, more preferably 24 or less carbon atoms, such as a sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfuryl group (Famoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenoxyphosphonyl group, octyloxyphospho Nyl group, phenylphosphonyl group), phosphinoylamino group (preferably phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, diethoxyphosphinoylamino group, dioctyl Oxyphosphinoylamino group) and the like.
These substituents may be further substituted. When there are two or more substituents, the two substituents may be the same or different, and the two substituents may be connected to each other to form a ring, if possible.

In the general formula (2), R ² and R ³ are each independently a monovalent substituent (not including a hydrogen atom), or a group represented by the following general formula (3) or general formula (4) And at least one of R ² and R ³ represents a group represented by General Formula (3) or General Formula (4). * Represents the site | part couple | bonded with the phthalocyanine ring in General formula (1).

In General Formula (3) and General Formula (4), L ₁ and L ₂ each independently represent a single bond or a divalent linking group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , And R ⁹ each independently represents a hydrogen atom or a monovalent substituent. * Represents the site | part couple | bonded with N in General formula (2).

When R ² and R ³ represent a monovalent substituent, examples of R ² and R ³ include the above-described substituent T. Preferably, the alkyl may be unsubstituted or have a substituent. Represents an aryl group which may be substituted or unsubstituted.
Examples of the substituent of the alkyl group and aryl group having a substituent include the above-described substituent T, among which an alkoxy group, an aryl group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, or A halogen atom and the like are preferable, an alkoxy group and an acyloxy group are preferable, and a 2-ethylhexanoyloxy group, a pivaloyloxy group, a 2-methylpropanoyloxy group, a 2-methylbutanoyloxy group, a methoxy group, and an ethoxy group are more preferable.
Moreover, the aspect in which the alkyl group and aryl group represented by R ² and R ³ do not have a substituent is also preferable.
Examples of alkyl groups and the like that may have a substituent are described below.

The suitable example of the alkyl group which may be unsubstituted or may have a substituent is shown.
As the alkyl group which may have a substituent, an alkyl group having 1 to 15 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Examples of alkyl groups include methyl, ethyl, isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadodecyl, cyclopropyl, cyclopentyl. Group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, phenoxyethyl group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl Group, ethoxyethoxyethyl group, 2-chloroethyl group and the like, more preferably, methyl group, ethyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, phenoxyethyl group, benzyl group, phenylethyl group, N-butylaminosulfur Nylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, and ethoxyethoxyethyl group are preferable, and methyl group, ethyl group, isopropyl group, tert-butyl group, 2-ethylhexyl are particularly preferable. Group, phenoxyethyl group, benzyl group, phenylethyl group, N, N-dibutylaminosulfonylpropyl group, ethoxyethoxyethyl group.

The suitable example of the aryl group which may be substituted even if unsubstituted is shown.
As the aryl group which may have a substituent, an aryl group having 1 to 20 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable. Examples of the aryl group include phenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N-butylaminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group and the like can be mentioned, more preferably, phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N-butylaminosulfonylphenyl group. Group, 4-N, N-dibutylaminosulfonylphenyl group, particularly preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N, N-dibutyl. An aminosulfonylphenyl group is mentioned.

In General Formula (3), L ₁ represents a single bond or a divalent linking group, and is preferably a divalent linking group. As the divalent linking group, —O—, —S—, —C (═O) —, —CH ₂ —, —C ₆ H ₄ —, —CH (OH) —, —C (═S) — , —NR ^A —, —SO—, and —SO ₂ — are preferably a divalent linking group consisting of one or a combination of two or more, —O—, —C (═O) —. It is more preferably a divalent linking group composed of one or a combination of two or more selected from among —, —CH ₂ —, —C ₆ H ₄ —, —CH (OH) —, and —NR ^A —.
Furthermore, it is preferable that General formula (3) has a (meth) acrylic ester structure. For example, L ₁ in the general formula (3) is more preferably a (meth) acrylic acid ester structure having an ester group (—OC (═O) —) bonded to a carbon atom forming a double bond. preferable.

R ^A represents a hydrogen atom, an alkyl group or an aryl group. The alkyl group represented by ^RA is preferably an alkyl group having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, a hexyl group, a cyclohexyl group). The aryl group represented by R ^A is preferably an aryl group having 6 to 10 carbon atoms (such as a phenyl group or a naphthyl group). R ^A is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

In General Formula (3), R ^{4 to} R ⁶ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the above-described substituent T, and an alkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, hexyl group, cyclohexyl group) is more preferable.
R ^{4 to} R ⁶ are more preferably a hydrogen atom or a methyl group, R ⁴ is particularly preferably a hydrogen atom or a methyl group, and R ⁵ and R ⁶ are particularly preferably a hydrogen atom.

In particular, the general formula (3) represented by R ² and R ³ is * -L _1A- (meth) acrylic group (* represents a site bonded to N in the general formula (2)). It is more preferable. Here, L _1A has the same definition as the divalent linking group represented by L ₁ , and —O—, —C (═O) —, —CH ₂ —, —C ₆ H ₄ —, —CH ( OH)-, and a group consisting of one or a combination of two or more selected from -NR ^A- (two or more types may be combined, or two or more of the same types may be combined; the same shall apply hereinafter). More preferably, a group consisting of one or a combination of two or more selected from —O—, —C (═O) —, and —CH ₂ — is more preferable.
As the general formula (3) represented by R ² and R ³ , “* —R ^Z- (meth) acryloyloxy group (R ^Z : carbon number 1 to 1) having an ester group (—OC (═O) —)” is used. 10 represents an alkylene group, * represents a site bonded to N in the general formula (2).) ”(= * — R ^Z —OC (═O) —CH═CH ₂ ) or * —R ^Z —OC ( ═O) —C (CH ₃ ) ═CH ₂ ).

In General Formula (4), L ₂ represents a single bond or a divalent linking group, and the divalent linking group has the same meaning as the divalent linking group represented by L ₁ , and the preferred range is also the same. .
In General Formula (4), R ^{7 to} R ⁹ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the above-described substituent T, and an alkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, hexyl group, cyclohexyl group) is more preferable. R ^{7 to} R ⁹ are more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

In the general formula (2), when both R ² and R ³ represent a group represented by the general formula (3) or the general formula (4), they may be the same or different, preferably Are the same. In general formula (2) R ² and R ³ in the, if it represents a group represented by formula (3) or general formula (4), is preferably represented by the above general formula (3) It is a group.
Thereby, when a color filter is produced, the fixing property of the dye in the film becomes good, the color change is small, and the solvent resistance and the like are good.

  Among the compounds represented by the general formula (1) (phthalocyanine compounds), a preferred embodiment includes a compound represented by the following general formula (5).

In the general formula (5), X represents a chlorine atom or a fluorine atom, and M represents Cu or Zn. R ¹ represents the following general formula (6), and R represents a hydrogen atom. A plurality of n each independently represents an integer of 0 to 2, a plurality of m each independently represents an integer of 0 to 4, and a plurality of r independently represents an integer of 0 to 4. However, at least one of n is 1 or more, and at least one of m is 1 or more. The sum of n, m and r is 16.
In General Formula (6), R ² and R ³ are each independently a monovalent substituent (not including a hydrogen atom), or a group represented by General Formula (3) or General Formula (4) below. And at least one of R ² and R ³ represents a group represented by General Formula (3) or General Formula (4). * Represents the site | part couple | bonded with the phthalocyanine ring in General formula (5).
In General Formulas (3) and (4), L ₁ and L ₂ each independently represent a single bond or a divalent linking group, and R ^{4 to} R ⁹ each independently represent a hydrogen atom or a monovalent group. Represents a substituent. * Represents the site | part couple | bonded with N in General formula (6).
In the above, the monovalent substituent represented by R ² and R ³ , the divalent linking group represented by L ₁ and L ₂ , and the monovalent substituent represented by R ^{4 to} R ⁹ are generally It is synonymous with the case in Formula (2)-(4), and its preferable aspect is also the same.

Among the compounds represented by the general formula (1) (phthalocyanine compound), as another preferred embodiment, X is a chlorine atom or a fluorine atom, M is a non-metal atom, Cu, or Zn, and R ¹ is a group represented by the general formula (2), R is a hydrogen atom or a phenoxy group, a plurality of n, a plurality of m, and a plurality of r are each independently an integer of 0 to 4 ( Provided that at least one of n is 1 or more and at least one of m is 1 or more), and in the general formula (2), R ² is an alkyl group having 1 to 15 carbon atoms, and R ³ is In the general formulas (3) and (4), L ₁ and L ₂ are each independently an alkylene group or * —R ^Z —OC ( = O) - ^{[R Z:} alkylene group having 1 to 10 carbon atoms, : A portion for coupling with the N in the general formula (2)], aspect R ⁴ to R ⁹ are each independently hydrogen atom or a methyl group is more preferable.

  The molecular weight of the compound represented by the general formula (1) is preferably 1,000 to 5,000, more preferably 1,100 to 3,500.

  The content of the compound represented by the general formula (1) in the colored composition varies depending on the molecular weight and the extinction coefficient, but is 1% by mass to 70% by mass with respect to the total solid content of the colored composition. Is preferable, and 10 mass%-50 mass% is more preferable. When the content of the dye is 10% by mass or more, a good color density (for example, a color density suitable for liquid crystal display) is obtained, and when the content is 50% by mass or less, the patterning of the pixels becomes better. This is advantageous.

The production method of the phthalocyanine compound is not particularly limited, and a conventionally known method such as “phthalocyanine as a functional dye, issued by IPC Co., Ltd.”, “phthalocyanine-chemistry and function-, IPC Co., Ltd.” It can be synthesized according to the method described in “Issued by company”.
The phthalocyanine compound can be synthesized by condensation cyclization of an optionally substituted phthalonitrile in the presence of a metal source. In that case, the phthalocyanine by which the various substituent was introduce | transduced is compoundable by mixing a some phthalonitrile.

The phthalocyanine compound is synthesized by mixing raw materials (phthalonitrile derivatives) for producing phthalocyanine at a desired ratio, for example, as in the following reaction formulas (1) and (2).
In the following reaction formula (1), the sum of a, b, and c is 16. However, a, b, and c can arbitrarily be decimal numbers such as 0.1. This is because a, b, and c are values defined from the charging ratio of the raw material phthalonitrile derivative to be mixed, and the reaction of the mixed phthalonitrile derivative proceeds in a complicated manner, and the synthesized phthalocyanine derivatives are various. This is because it is in the form of a mixture having a substituent. R ¹ in the reaction formula (1) has the same meaning as the general formula (1) R ¹ in, by adjusting the number of substituents and charge ratio of R ¹ substituted into phthalonitrile A, substituted in the phthalocyanine compound The number of substitutions of the radical R ¹ can be adjusted to the desired number. In the reaction formula (1), a = 4x, b = 16-4x-4z, and c = 4z (x + y + z = 1).
In the reaction formula (1), when the preparation ratio (x) of phthalonitrile A introduced with substituent R ¹ is large, the solubility of the resulting phthalocyanine is improved, and the dye has the characteristics of substituent R ¹ having a polymerizable substituent. When the charge ratio (y) of phthalonitrile B is increased, the associability of the obtained phthalocyanine can be increased, and the absorption waveform can be adjusted.
Similarly, in the reaction formula (2), the sum of a ′, b ′ and c ′ is 16, and a ′ = 4x ′, b ′ = 16-4x′−16z ′, c ′ = 16z ′ (x '+ Y' + z '= 1).

[Reaction Formula (1)]

[Reaction Formula (2)]

Hereinafter, specific examples (exemplary compounds A-1 to A-80) of the compound represented by the general formula (1) described above are shown. However, the present invention is not limited to these.
In each of the following specific examples, p represents the average value of the total of n in the general formula (1), and q represents the average value of the total of m in the general formula (1). Moreover, since “16-pq” is a value obtained by subtracting two average values, it is an average value in a plurality of types of compounds.

In each of the specific examples below, at least one R ¹ substitution position in p is α-position (the others are β-position), and at least one X substitution position in q pieces is β-position (the others are α position), the substitution position of p R ¹ is the α position and the substitution position of q X is the β position, and the substitution position of p R ¹ is the β position, and the like, where q substitution positions of X are in the α-position. Here, “16-pq” Rs are substituted at any substitution position at the α-position and / or the β-position.
For example, in each specific example, as a substitution mode of R ¹ and X to the following four benzene rings of the phthalocyanine ring, the structure A1 having X at two α positions and R ¹ and X at the β position ( And a structure A2 (structure derived from the following phthalonitrile A2) having X at two β-positions and R ¹ and X at the α-position (structure derived from the following phthalonitrile A1) are preferable. The ratio of the structure A1 to the structure A2 (A1: A2 [molar ratio]) is preferably 100: 0 to 20:80, more preferably 100: 0 to 50:50, and even more preferably. Is 100: 0 to 70:30.

Each group described in the column of R ¹ in the exemplary compounds A-1 to A-80 represents a group shown below.

<< Compound Represented by Formula (11) >>
The coloring composition of this invention contains at least 1 type of the compound (methine compound) represented by General formula (11). Therefore, it has a good absorption waveform as a dye for a green filter, and when it is a cured film, it has high heat resistance and light resistance and is excellent in overcoat suitability.

In General Formula (11), a plurality of R ₇₁ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an aryl group, or a heteroaryl group. In General Formula (11), R ₇₂ and R ₇₃ each independently represent a monovalent substituent, and at least one of R ₇₂ and R ₇₃ is represented by the following General Formula (12) or General Formula (13). Represents a group. * Represents the site | part couple | bonded with the methine structure in General formula (11). )

The monovalent substituent represented by R ₇₂ and R ₇₃ is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a cyano group, an aryl group, or a heteroaryl group. It is preferable.

In general formula (12) and general formula (13), L ₁ , L ₂ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same as those in general formula (3) and general formula (4). L ₁ , L ₂ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are synonymous, and preferred embodiments are also synonymous.

A preferred substituent in the compound represented by the general formula (11) will be described.
The alkyl group represented by R ₇₁ , R ₇₂ , and R ₇₃ is an alkyl group having 1 to 48 carbon atoms (more preferably 1 to 18 carbon atoms), which is linear, branched, or cyclic. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl Group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group and the like, preferably methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl. A group, a heptyl group, an octyl group, and a 2-ethylhexyl group.
The alkoxy group represented by R ₇₁ , R ₇₂ and R ₇₃ is an alkoxy group having 1 to 48 carbon atoms (more preferably 1 to 12 carbon atoms), and includes a methoxy group, an ethoxy group, a 1-butoxy group, 2- A butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxy group, a cycloalkyloxy group (for example, a cyclopentyloxy group, a cyclohexyloxy group, etc.) and the like are preferable, and a methoxy group, an ethoxy group, and a 1-butoxy group are preferable. 2-butoxy group, isopropoxy group, t-butoxy group.
The alkoxycarbonyl group represented by R ₇₁ , R ₇₂ and R ₇₃ is an alkoxycarbonyl group having 2 to 48 carbon atoms (more preferably 2 to 12 carbon atoms), and includes a methoxycarbonyl group, an ethoxycarbonyl group, and octadecyloxycarbonyl. Group, cyclohexyloxycarbonyl group and the like, and preferred are methoxycarbonyl group and ethoxycarbonyl group.

The carbamoyl group represented by R ₇₁ , R ₇₂ and R ₇₃ is a carbamoyl group having 1 to 48 carbon atoms (more preferably 1 to 12 carbon atoms), and includes a carbamoyl group, N, N-diethylcarbamoyl group, N— And ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group and the like. N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group and N-phenylcarbamoyl group are preferable.
The sulfamoyl group represented by R ₇₁ , R ₇₂ and R ₇₃ is a sulfamoyl group having 32 or less carbon atoms (more preferably 16 or less carbon atoms), and is a sulfamoyl group, N, N-dipropylsulfamoyl group, N- And ethyl-N-dodecylsulfamoyl group, N-ethyl-N-hexylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group and the like. -Ethyl-N-hexylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group.

The aryl group represented by R ₇₁ , R ₇₂ , and R ₇₃ is an aryl group having 6 to 48 carbon atoms (more preferably 6 to 12 carbon atoms), and examples thereof include a phenyl group and a naphthyl group. It is a phenyl group.
The heteroaryl group represented by R ₇₁ , R ₇₂ , and R ₇₃ is a heteroaryl group having 1 to 32 carbon atoms (more preferably 1 to 12 carbon atoms), a 2-thienyl group, a 4-pyridyl group, 2 -Furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group, and the like, preferably 2-benzothiazolyl group, 1 -Imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group.

R ₇₁ is preferably a substituted alkyl group having 1 to 8 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms, or a cyano group, more preferably a methyl group, an ethyl group, an isopropyl group, t- A butyl group, a phenyl group, or an o-methylphenyl group, more preferably a t-butyl group.
R ₇₂ and R ₇₃ are not particularly limited in structure, but include substituted alkyl groups, substituted aryl groups, PEO (polyethylene glycol) chains, PPO (polypropylene glycol) chains, ammonium salts, sulfamoyl groups, sulfonamide groups, or polymerizable groups. Is preferably a group composed of one or more selected from the group consisting of at least one of R ₇₂ and R ₇₃ represented by the general formula (12) or the general formula (13). It is preferable to include a group.

  The compound represented by the general formula (11) is more preferably a compound represented by the following general formula (14). This compound has a structure in which a curable group (including an unsaturated double bond and an epoxy group) is substituted via a sulfonamide group in the molecule. Has high color purity (hue), little absorption (high transmittance) in an unnecessary wavelength region other than the yellow region, and excellent luminance. Therefore, it has a good absorption waveform as a dye for a green filter, and when it is a cured film, it has high heat resistance and light resistance and is excellent in overcoat suitability.

In the general formula _{(14), R 71} is each the same meaning as _{R 71} in the general formula (11), preferable embodiments thereof are also the same.

A preferred substituent in the compound represented by the general formula (14) will be described.
Specific examples of R _71, and preferred ranges are the same meanings as _{R 71} in the general formula (11).
R ₇₅ and R ₇₇ represent an alkyl group, an aryl group, or a heteroaryl group.
Specific examples and preferred ranges of the alkyl group represented by R ₇₅ and R ₇₇ are also the same as the alkyl group represented by R ₇₂ and R ₇₃ in the general formula (11), respectively.
Specific examples and preferred ranges of the aryl group represented by R ₇₅ and R ₇₇ are also the same as the aryl group represented by R ₇₂ and R ₇₃ in the general formula (11), respectively.
Specific examples and preferred ranges of the heteroaryl group represented by R ₇₅ and R ₇₇ are also the same as the heteroaryl group represented by R ₇₂ and R ₇₃ in formula (11), respectively.

A particularly preferred substituent of the dye represented by the general formula (14) will be described.
R ₇₁ is particularly preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a phenyl group, or an o-methylphenyl group.
The R ₇₅ and _{R 77,} a substituted alkyl group is constituted by combining a substituted aryl group, PEO (polyethylene glycol) chain, PPO (polypropylene glycol) chain, ammonium salts, one or more selected from polymerizable groups is preferably that _{group, R 75} and _{R 77} are unsubstituted or substituted, more preferably an alkyl group, or an aryl group having 6 to 20 carbon atoms having 1 to 10 carbon _{atoms, R 75} and R It is preferable that at least one of each terminal of ₇₇ is a group represented by the general formula (12) or the general formula (13).

  Next, specific examples of the dye represented by the general formula (11) are shown below. However, the present invention is not limited to these.

  As content in the coloring composition of the compound represented by General formula (11), although it changes with molecular weight and its light absorption coefficient, it is 1 mass%-70 mass% with respect to the total solid of a coloring composition. It is preferably 10% by mass to 50% by mass. When the content of the dye is 10% by mass or more, a good color density (for example, a color density suitable for liquid crystal display) is obtained, and when the content is 50% by mass or less, the patterning of the pixels becomes better. This is advantageous.

  The method for producing the methine compound is not particularly limited. For example, it is preferable to produce the corresponding compound by using the production method shown in the following scheme because a dye compound with high purity can be obtained.

  The dye compound of the general formula (11) according to the present invention comprises an aniline compound represented by the general formula (15) and a halogen compound represented by the general formula (16), as shown in the following scheme. After making it react under coexistence and manufacturing the intermediate body of the dye compound represented by following General formula (17), the dye compound of General formula (18) can be manufactured using this intermediate body.

In the above scheme, R ¹ represents an alkyl group having 1 to 4 carbon atoms. R ² represents SO ₂ R ³ or COR ⁴ . R ³ and R ⁴ represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.

(Method for producing compound represented by formula (17))
A compound represented by the general formula (15) and a synthesis method thereof are described in European Patent Application No. 0571959. The compound represented by the general formula (15) is dropped into a mixed solution obtained by dissolving the compound represented by the general formula (15) and the picoline in a reaction solvent such as a mixed solvent of tetrahydrofuran and ethyl acetate. After the reaction solution is stirred, the compound represented by the general formula (17) is obtained by crystallization using a poor solvent. When reacting the compound represented by the general formula (15) and the compound represented by the general formula (16), the compound represented by the general formula (17) crystallized by coexisting picoline. Is suppressed, and the compound represented by the general formula (17) can be obtained with high purity. When the compound represented by the general formula (17) is colored, the purity of the dye compound is also lowered, and the brightness of the dye compound is lowered. Therefore, the high purity general formula (17) in which coloring is suppressed. ), That is, a method for producing an intermediate of a dye compound is preferable.

  The amount of picoline is preferably 0.4 to 2 parts by mass with respect to 1 part by mass of the compound represented by the general formula (15). The reaction temperature is preferably 0 ° C. to 50 ° C., and the amount of the reaction solvent is preferably 1 to 20 times on a mass basis with respect to the amount of the compound represented by the general formula 1.

  The reaction solvent is not particularly limited as long as it does not react with the compound represented by the general formula (15) or the compound represented by the general formula (16). For example, toluene, ethyl acetate, tetrahydrofuran, acetonitrile and the like can be mentioned. Two or more reaction solvents may be mixed and used.

(Method for producing dye compound)
A mixed solution of the compound represented by the general formula (17), triethyl orthoformate, toluene, and acetic acid is stirred and then crystallized using a poor solvent to obtain a dye compound.

[Preferred combinations and mixing ratios]
In the colored composition of the present invention, the compound represented by the general formula (1) (phthalocyanine compound) and the compound represented by the general formula (11) (methine compound) are preferably used in the following manner.

  In the coloring composition of this invention, it is preferable that the compound represented by General formula (5) and the compound represented by General formula (14) are included. By including the compound represented by the general formula (5) and the compound represented by the general formula (14), the color transfer to the other layer is suppressed, the luminance is excellent, and the color development is further excellent.

  The content ratio (mass ratio) of the phthalocyanine compound of the general formula (1) and the methine compound of the general formula (11) in the colored composition of the present invention varies depending on the compound to be selected, but the phthalocyanine compound / methine compound is 90 / It is preferably 10 to 10/90, and more preferably 70/30 to 30/70.

  The total content of the phthalocyanine compound of the general formula (1) and the methine compound of the general formula (11) in the coloring composition of the present invention is the total solid content of the coloring composition from the viewpoint of heat resistance, color reproducibility, and luminance. On the other hand, 1 mass%-60 mass% are preferable, 5 mass%-60 mass% are more preferable, 10 mass%-50 mass% are still more preferable.

(Heterocycle-containing compound)
The colored composition of the present invention may further contain a heterocyclic ring-containing compound.
The heterocyclic compound is preferably a compound having a pyridine ring, and more preferably a compound having a pyridine ring substituted with a carboxyl group (hereinafter sometimes referred to as a specific pyridine compound).

  The pyridine skeleton of the pyridine compound includes a condensed ring. In this case, the condensed ring preferably has one carbocyclic aromatic ring, that is, a quinoline skeleton or an isoquinoline skeleton, and the carboxyl group is a ring containing a nitrogen atom (other than the carbon atom constituting the condensed ring). It is preferable that it is bonded to a carbon atom constituting carbon (a carbon atom other than the carbon atom constituting the condensed ring).

  The specific pyridine compound may further have a substituent other than a carboxyl group. Preferred substituents include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, silyl groups, halogeno groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylcarbonyloxy groups, arylcarbonyloxy groups, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group Anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, Zo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, phosphonyl group, and phosphinoylamino group. Of these, preferred substituents are an alkyl group, an aryl group, a halogen group, an alkoxy group, and an aryloxy group.

Specific pyridine compounds include those having a polymerizable group (hereinafter also referred to as “specific pyridine monomers”).
As the polymerizable group, a cationic polymerizable group and a radical polymerizable group are preferable, and a radical polymerizable group is particularly preferable.
The cationic polymerizable group includes an epoxy group, an oxetane group and the like.
The radically polymerizable group includes those having an ethylenically unsaturated double bond at the terminal.
The ethylenically unsaturated double bond is preferably bonded to the pyridine skeleton via a linking group. Especially, what has an acryloyl group or a methacryloyl group at the terminal is preferable.

  The specific pyridine monomer may further have a substituent other than the carboxyl group and the radical polymerizable group, and examples of the substituent in this case include the above-described substituent flags.

The specific pyridine compound includes a polymer containing a repeating unit derived from a specific pyridine monomer (hereinafter also referred to as “specific pyridine polymer”).
The specific pyridine polymer may further contain a repeating unit derived from a copolymerizable vinyl monomer in addition to the repeating unit derived from the specific pyridine monomer.

The specific pyridine polymer may be a copolymer including at least one monomer having an acidic group. (Hereinafter, these are also referred to as “specific pyridine copolymers”.)
The specific pyridine copolymer can give a colored composition having excellent interaction with the specific phthalocyanine compound and excellent developability.

Since the specific pyridine copolymer has the advantage of improving stability to light and heat, particularly heat, a graft polymer containing a repeating unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal (Hereinafter also referred to as “graft-type specific pyridine copolymer”).
The polymerizable oligomer having an ethylenically unsaturated double bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight (hereinafter, this polymerizable oligomer is sometimes referred to as “macromonomer”).
The macromonomer preferably includes a polymer chain portion and a polymerizable functional group portion having an ethylenically unsaturated double bond at the terminal thereof. It is preferable from the viewpoint of obtaining a desired graft polymer that such a polymerizable functional group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

[Other color materials]
The colored composition of the present invention may further contain a colorant in addition to the compound represented by the general formula (1) and the compound represented by the general formula (11) as long as the effects of the present invention are not impaired. .
Examples of the color material include dyes and pigments.

〔dye〕
As long as the effect of the present invention is not impaired, the coloring composition may further contain a dye.
The dye used in the present invention can be used without particular limitation, and can be selected from known solvent-soluble dyes.
For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828.
Chemical structure includes anilinoazo, arylazo, pyrazolotriazole azo, etc., triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene , Phthalocyanine-based, benzopyran-based, indigo-based, pyromethene-based, and coumarin-based dyes can be used.

[Pigment]
In the present invention, a known pigment can be used as the green pigment, but a phthalocyanine pigment is preferred from the viewpoint of heat resistance.

  In the present invention, specific examples of the green pigment used include C.I. I. Pigment Green 7, 36, 58. However, the present invention is not limited to these.

In the present invention, various conventionally known organic pigments can be used as the yellow pigment.
In consideration of the fact that the pigment used in the present invention preferably has a high transmittance, it is preferable to use a pigment having a particle size as small as possible and a particle size as small as possible. A pigment having an average particle size of 0.01 μm to 0.3 μm, more preferably 0.01 μm to 0.15 μm. When the particle size is within the range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.

Examples of yellow pigments include:
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, and the like.

The pigment (green pigment, yellow pigment) used in the present invention may be subjected to a miniaturization treatment as necessary.
In order to refine the organic pigment, it is preferable to use a method including a step of grinding the organic pigment as a highly viscous liquid composition together with the water-soluble organic solvent and the water-soluble inorganic salts.
In the present invention, it is more preferable to use the following method for refining the organic pigment.
That is, first, for a mixture (liquid composition) of an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single The organic pigment in the mixture is ground by applying a strong shearing force using a kneader such as a twin or twin screw extruder, and then the mixture is put into water and made into a slurry with a stirrer or the like. Next, this slurry is filtered, washed with water, the water-soluble organic solvent and the water-soluble inorganic salt are removed, and then dried to obtain a refined organic pigment.

Water-soluble organic solvents used in the micronization method include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Examples include glycol and propylene glycol monomethyl ether acetate.
Also, if it is adsorbed to the pigment by using a small amount and does not run away in the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate , Hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. May be. Moreover, you may mix and use 2 or more types of solvents as needed.
The amount of these water-soluble organic solvents used is preferably in the range of 50% by mass to 300% by mass and more preferably in the range of 100% by mass to 200% by mass with respect to the organic pigment.

In the present invention, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like are used as the water-soluble inorganic salt.
The use amount of the water-soluble inorganic salt is preferably 1 to 50 times the amount of the organic pigment on a mass basis, and a larger amount has a grinding effect, but from the viewpoint of productivity, a more preferable amount is 1 to 10 times the mass.
In order to prevent dissolution of the water-soluble inorganic salt, the water content in the liquid composition to be ground is preferably 1% by mass or less.

In the present invention, when a liquid composition containing an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is ground, a wet grinding device such as the kneader described above may be used. There are no particular restrictions on the operating conditions of this wet pulverizer, but the operating conditions when the apparatus is a kneader are used to rotate the blades in the apparatus in order to effectively proceed grinding with pulverizing media (water-soluble inorganic salt). The number is preferably 10 rpm to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 ° C to 150 ° C. Further, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 μm to 50 μm, a sharp particle size distribution, and a spherical shape.
The mixture after milling as described above is mixed with warm water at 80 ° C. to dissolve the water-soluble organic solvent and the water-soluble inorganic salts, and then filtered, washed with water, dried in an oven, Organic pigments can be obtained.

When forming the coloring composition in this invention, when a yellow pigment or a green pigment is contained, a pigment dispersion composition is prepared and it is preferable to use this.
The pigment dispersion composition is obtained by dispersing a pigment in a solvent together with a dispersant and a pigment derivative.
The dispersant used here is used for improving the dispersibility of the pigment. For example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many types of compounds can be used as the dispersant. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.) such as 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Kasei Co., Ltd.), Disperbyk-101, -103, -106, -108, -109, -111, -112, -116, -130 -140, -142, -161, -162, -163, -164, -166, -167, -170, -171, -174, -176, -180, -182, -2000, -2001, -2050 , -2150 (manufactured by Big Chemie Japan Co., Ltd.). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  The amount of the dispersant used is preferably 0.5 parts by mass or more and 100 parts by mass or less, and more preferably 3 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the total amount of pigment contained in the pigment dispersion composition. When the amount of the dispersant is within this range, a sufficient pigment dispersing effect can be obtained. In addition, even if it adds more dispersant than 100 mass parts, the further improvement effect of a pigment dispersion effect may not be expectable.

Moreover, a pigment derivative is added to a pigment dispersion composition as needed.
In the present invention, a portion having affinity with the dispersant or a pigment derivative having a polar group introduced is adsorbed on the pigment surface, and this is used as an adsorption point of the dispersant, whereby the pigment is made into fine particles. It can be dispersed in the dispersion composition and re-aggregation can be prevented. That is, the pigment derivative has an effect of promoting the adsorption of the dispersant by modifying the pigment surface.

  Specifically, the pigment derivative used in the present invention is a compound in which an organic pigment is used as a base skeleton and an acidic group, a basic group, or an aromatic group is introduced as a substituent in the side chain. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, and benzimidazolone pigments. It is done. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.

  Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 1 mass% or more and 30 mass% or less are preferable with respect to the mass of a pigment, and 3 mass% or more and 20 mass% or less are more preferable. If the content is within the range, the viscosity can be kept low and the dispersion can be performed well and the dispersion stability after the dispersion can be improved. When manufactured, it can be configured to have high contrast with good color characteristics.

As a solvent which comprises a pigment dispersion composition, the thing similar to the solvent which comprises the colored curable composition mentioned later is mentioned.
The pigment concentration in the pigment dispersion composition is preferably 5% by mass or more and 30% by mass or less, and more preferably 10% by mass or more and 25% by mass or less.

The pigment dispersion composition in the present invention can be prepared by performing a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

Specifically, for example, a bead disperser using zirconia beads or the like (for example, manufactured by GETZMANN Co., Ltd.) is prepared by previously mixing a pigment and a dispersant as necessary, and further dispersing in advance with a homogenizer or the like. The pigment dispersion composition can be prepared by finely dispersing using a disperse mat).
The dispersion time is preferably about 3 hours or more and 6 hours or less.
The fine dispersion treatment with beads is mainly made of vertical or horizontal sand grinders, pin mills, slit mills, ultrasonic dispersers, etc., beads made of glass having a particle diameter of 0.01 mm to 1 mm, zirconia, etc. Can be used.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

〔solvent〕
Generally the coloring composition used for this invention can be suitably prepared using a solvent with the said component.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropio Acid ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2 -Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, cyclohexyl acetate, etc .; ketones such as Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, butyl methoxyacetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferable.
You may use a solvent in combination of 2 or more types besides using independently.

The coloring composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored composition, the respective components may be mixed at once, or may be sequentially mixed after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component is appropriately made into two or more solutions / dispersions, and these are mixed at the time of use. And may be prepared as a composition.
However, when a pigment is used as a component, it is preferable to prepare a colored composition after previously dispersing the pigment to obtain a pigment dispersion.
The colored composition prepared as described above is preferably used after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm, more preferably about 0.05 μm to 1.0 μm. Can be provided.

The coloring composition in the present invention is a curable composition comprising a compound represented by the above general formula (1), a compound represented by the general formula (11), a polymerizable compound, and a photopolymerization initiator. It is preferable to be composed of a composition (hereinafter referred to as “colored curable composition”).
The colored curable composition in the present invention preferably further contains an alkali-soluble binder.
Moreover, the colored curable composition in this invention may also contain another additive as needed.
The content of the coloring material (including general formula (1) and general formula (11)) in the colored curable composition is 20% by mass to 60% by mass with respect to the total solid content of the colored curable composition. It is preferably 30% by mass to 60% by mass, and more preferably 35% by mass to 50% by mass.
When the density of the color material is within the above range, the color density is sufficient to ensure excellent color characteristics.
When a pigment derivative is used for the pigment dispersion composition, the pigment concentration including the pigment derivative amount is used.

(Polymerizable compound)
Hereinafter, each component which comprises a colored curable composition is demonstrated.
The colored curable composition of the present invention preferably contains at least one polymerizable compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.

  Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or a mixture thereof and a (co) polymer thereof.

  Examples of monomers and their (co) polymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and their (co) It is a polymer. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

  Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethylmethane bis - [p- (methacryloxyethoxy) phenyl] dimethylmethane.

Further, as the itaconic acid ester, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc. For example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. To, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.
Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula to a polyisocyanate compound having two or more isocyanate groups. Can be mentioned.
_{CH 2 = C (R) COOCH} 2 CH (R ') OH
[In the general formula, R and R ′ each independently represent H or CH ₃ . ]

  Among these monomers, a monomer represented by the following general formula (A) is preferable from the viewpoint of good curing.

(In general formula (A), X represents a hydrogen atom or a methyl group. N represents an integer of 2 to 6. A represents a hydrogen atom of n hydroxy groups from an m-valent polyhydric alcohol. Represents an excluded n-valent group, where m represents an integer of 2 or more and 6 or less, and m ≧ n.

The m-valent polyhydric alcohol includes aliphatic alcohols and aromatic polyhydroxy compounds.
Examples of m-valent aliphatic alcohols include ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, and 1-methyl-1,3-propane. Diol, 2,2-dimethyl-1,3-propanediol, 1,4-dimethylolcyclohexane, 1,2,3-trihydroxypropane, 1,1,1-trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Is mentioned.
Examples of the m-valent aromatic polyhydroxy compound include bisfer A, 1,4-dimethanolcyclohexane and the like.
Of these m-valent polyhydric alcohols, aliphatic alcohols are preferred because the lower the viscosity of the system during polymerization, the better the progress of polymerization. On the other hand, when importance is attached to the hardness of the crosslinked film, an aromatic polyhydroxy type may be preferable, and it is preferable to use them properly depending on the required performance.
Hereinafter, preferred specific examples of the compound represented by the general formula (A) will be given.
In addition, although the following compound (35) is not contained in the compound represented by general formula (A), it is preferable.

  About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount and the like can be arbitrarily set in accordance with the final performance design of the colored curable composition. The selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, coloring material (dye, pigment), binder polymer, etc.) contained in the colored curable composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  The content of the polymerizable compound in the total solid content of the colored curable composition (total content in the case of 2 or more types) is not particularly limited, and is 10 from the viewpoint of more effectively obtaining the effects of the present invention. % By mass to 80% by mass is preferable, 15% by mass to 75% by mass is more preferable, and 20% by mass to 60% by mass is particularly preferable.

(Photopolymerization initiator)
The colored curable composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a biimidazole compound, a benzophenone compound, an acetophenone compound, and Examples thereof include cyclopentadiene-benzene-iron complexes and salts thereof, and oxime ester compounds. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime ester compound and a biimidazole compound are preferable from the viewpoint of rapid polymerization reaction.

  There is no limitation in particular as an oxime ester compound (henceforth "oxime ester photoinitiator"), For example, Unexamined-Japanese-Patent No. 2000-80068, international publication 2002/100903 pamphlet, Unexamined-Japanese-Patent No. 2001-233842 Examples include oxime ester compounds described in publications and the like.

  Specific examples of the oxime ester compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4. -(Phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime)- 1- [4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O— Benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylpheny Thio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyl) Oxime) -1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6 2-butyl benzoyl) -9H- carbazol-3-yl] ethanone, and the like. However, it is not limited to these.

  Moreover, in this invention, the compound represented by the following general formula (B-1) and the following general formula (B-2) as an oxime ester compound from a viewpoint of a sensitivity, temporal stability, and the coloring at the time of post-heating. Is more preferable.

In the general formula (B-1), examples of the halogen atom when X ¹ , X ² , and X ³ represent a halogen atom include fluorine, chlorine, bromine, and iodine, and X ¹ , X ² , and X Examples of the alkyl group when ³ represents an alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propylethoxyethoxyethyl, Methoxypropyl, monofluoromethyl, diflu Examples include olomethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl, and the like.
Especially, it is preferable that all of X < ¹ >, X < ² > and X < ³ > represent a hydrogen atom, or X < ¹ > represents an alkyl group and X < ² > and X < ³ > all represent a hydrogen atom.
In General Formula (B-1), R ¹ represents —R, —OR, —COR, —SR, —CONRR ′, or —CN, and R ² and R ³ each independently represent —R, —OR, -COR, -SR, or -NRR 'is represented. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.

In the general formula (B-1), examples of the alkyl group represented by R and R ′ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, Triamyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl Ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.
Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.

R ² and R ^{3 including} R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—. Br is a particularly preferred embodiment.

Among the photopolymerization initiators, in the above general formula (B-1), X ¹ , X ² and X ³ are all hydrogen atoms; R ¹ is an alkyl group, particularly a methyl group; R Those in which ² is an alkyl group, particularly a methyl group; those in which R ³ is an alkyl group, particularly an ethyl group, are particularly suitable as a photopolymerization initiator.

  Moreover, as a preferable oxime ester compound of this invention, the compound which has a fluorene structure represented by the following general formula (B-2) is mentioned.

In formula (B-2), R ¹⁰¹ represents an alkyl group, an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkylthiocarbonyl group, an aryl. It represents a ruthiocarbonyl group, a heterocyclic thiocarbonyl group, a heteroarylthiocarbonyl group or —CO—CO—Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

R ¹⁰² represents an alkyl group, an aryl group, or a heterocyclic group, which may be substituted.
R ¹⁰³ and R ¹⁰⁴ each independently represents an alkyl group, an aryl group or a heterocyclic group, and these groups are further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like. Also good.

R ^{105 to} R ¹¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloyl group, a heteroaryloyl group, an alkylthio group, an aryloylthio group, or a heteroaryloyl group. , Alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, nitro group, amino group, sulfonic acid group, hydroxy group, carboxylic acid group, amide group, carbamoyl Represents a group or a cyano group.
One or two of R ^{105 to} R ¹¹¹ are electron-withdrawing substituents, that is, a nitro group, a cyano group, a halogeno group, an alkylcarbonyl group, or an arylcarbonyl group, which has a much higher curability. Since a colored curable composition is obtained, it is preferable.

  Specific examples of the compound having a fluorene structure represented by the general formula (B-2) are given below. However, it is not limited to these compounds.

Examples of the biimidazole compound include hexaarylbisimidazole. Specific examples of hexaarylbisimidazole are shown below.
Among the following specific examples, (I-1), (I-2), (I-4), and (I-11) are preferable in terms of solubility in a solvent, reactivity, and transparency.

  Examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl- Preferable examples include 2-hydroxy-2-methyl-propiophenone.

  Examples of the benzophenone compound include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl- Preferred examples include 1- [4- (methylthio) phenyl] -2-morpholinopropanone-1.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2 , 4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2 , 4-Bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (Trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-triazine, 4 Benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) Preferred examples include -s-triazine, 4- (p-N, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like.

  Examples of halomethyloxadiazole compounds include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxa. Diazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxadi An azole etc. can be mentioned suitably.

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

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples of the photopolymerization initiator in the present invention include carbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt and the like.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethylol-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A 2000-66385.
Moreover, these photoinitiators can also be used together.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content (total content in the case of two or more) of the colored curable composition of the photopolymerization initiator in the total solid content is 3% by mass to 20% by mass from the viewpoint of obtaining the effect of the present invention more effectively. % Is preferable, 4% by mass to 19% by mass is more preferable, and 5% by mass to 18% by mass is particularly preferable.

  If necessary, the colored curable composition used in the present invention includes a sensitizer, a hydrogen donating compound, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, and other fillers. Various additives such as a polymer compound other than the above-described alkali-soluble resin (binder polymer), a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

(Alkali-soluble binder)
The colored curable composition of the present invention preferably contains at least one alkali-soluble binder.
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to the above, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group added with an acid anhydride, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth)), and the like. Acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. As the alkali-soluble binder having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the alkali-soluble binder containing the above-described polymerizable group include a dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), a Photomer 6173 (manufactured by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Viscoat R-264. KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like.
In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka). Organic Chemical Industry Co., Ltd.), Cyclomer P Series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

  The alkali-soluble binder used in the present invention is unsaturated by copolymerizing at least a monomer represented by the general formula (C) and at least a monomer having an acidic group, and, if necessary, a hydroxyalkyl (meth) acrylate. A copolymer having a group can be obtained.

In general formula (C), R represents a hydrogen atom or a methyl group, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group. .

  Examples of the alkyl group of the hydroxyalkyl (meth) acrylate include an ethylene group, a propylene group, and a butylene group. Monomers used to introduce this structural unit include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy Examples include butyl methacrylate.

  Examples of the (meth) acrylate-containing compound that reacts with an acidic group and / or a hydroxy group of a hydroxyalkyl (meth) acrylate include (meth) acrylate having an epoxy group or (meth) acrylate having an oxetane group.

  As the (meth) acrylate having an epoxy group, for example, a compound represented by the following structural formula (C-1) is preferable.

However, in Structural Formula (C-1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group. L ¹ is a linear, branched or cyclic, substituted or unsubstituted alkylene group or a combination of an alkylene group and at least one of —O—, —C (═O) — and —NH—. Group is preferred, and an alkylene group is more preferred. Examples of the substituent that the alkylene group may have include a hydroxyl group. 1-15 are preferable and, as for carbon number of an alkylene group, 1-4 are more preferable.

  As the (meth) acrylate having an oxetane group, for example, a compound represented by the following structural formula (C-2) is preferable.

Alkali-soluble binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

(Sensitizer)
It is preferable to further add a sensitizer to the colored curable composition of the present invention from the viewpoint of improving sensitivity. The exposure of the wavelength that can be absorbed by the sensitizer accelerates the radical generation reaction of the photopolymerization initiator component and the polymerization reaction of the ethylenically unsaturated compound.
Examples of such a sensitizer include a known spectral sensitizer or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

Preferred sensitizers that can be used in the present invention include spectral sensitizing dyes or dyes exemplified below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

Other preferred embodiments of the sensitizer include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 nm to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  The content of the sensitizer is preferably 0.01% by mass or more and less than 5% by mass, more preferably 0.1% by mass or more and 5% by mass with respect to the total solid content of the colored curable composition. %, Particularly preferably 0.3% by mass or more and 2% by mass or less. Within this range, it is possible to obtain a colored curable composition having no coloration, high sensitivity, and good pattern formation.

-Hydrogen donating compound-
The colored curable composition used in the present invention preferably contains a hydrogen donating compound. In the present invention, the hydrogen-donating compound has functions such as further improving the sensitivity of the sensitizing dye and the photopolymerization initiator to actinic radiation, or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
Examples of such hydrogen donating compounds include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of the hydrogen donating compound include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, and JP-A-5-142277, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. Naphthalene, ethylene glycol bis (3-mercaptobutyrate), 1,2-propylene glycol bis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1,2-propylene glycol bis (2- Mercaptoisobutyrate) and the like.

  Further examples of the hydrogen donating compound include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B-55. -34414, a hydrogen donor described in JP-A-6-308727, and a sulfur compound (eg, trithiane).

  The content of these hydrogen-donating compounds is 0.1% by mass or more and 30% by mass with respect to the mass of the total solid content of the colored curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The following range is preferable, the range of 1% by mass to 25% by mass is more preferable, and the range of 0.5% by mass to 20% by mass is further preferable.

-Fluorine organic compounds-
The colored curable composition used in the present invention can also contain a fluorine-based organic compound.
By containing this fluorine-based organic compound, the liquid properties (particularly fluidity) when the colored curable composition used in the present invention is used as a coating liquid can be improved, and the uniformity of coating thickness and liquid saving can be achieved. Can improve sex. That is, since the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the coating property to the surface to be coated is improved. Even when a thin film is formed, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  The fluorine content in the fluorine-based organic compound is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. . When the fluorine content is within the range, it is effective in terms of coating thickness uniformity and liquid-saving property, and the solubility in the composition is also good.

  Examples of the fluorine-based organic compounds include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, F437, and F554 (above, Dainippon Ink and Chemicals, Inc.). Manufactured by Co., Ltd.), FLORAD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

  As described above, the fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Furthermore, it is also effective when applied to slit coating that easily causes liquid breakage.

  The addition amount of the fluorine-based organic compound is preferably 0.001% by mass or more and 2.0% by mass or less, more preferably 0.005% by mass or more and 1.0% by mass with respect to the total mass of the colored curable composition. It is as follows.

-Thermal polymerization initiator-
It is also effective to add a thermal polymerization initiator to the colored curable composition used in the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketone peroxides. Peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates and the like.

-Thermal polymerization component-
It is also effective to add a thermal polymerization component to the colored curable composition used in the present invention in order to increase the strength of the film. As the thermal polymerization component, an epoxy compound is preferable.
The epoxy compound is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) These similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

  The cresol novolac type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), Biphenyl As alicyclic epoxy compounds, such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302 , GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Toto Kasei) and the like. . 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid In addition to diglycidyl ester, amine-type epoxy resins such as Epototo YH-434 and YH-434L, glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resin, and the like can also be used.

-Surfactant-
The colored curable composition used in the present invention is preferably composed of various surfactants from the viewpoint of improving coatability, and uses nonionic, cationic and anionic surfactants. it can. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

  Moreover, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Paluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, manufactured by BASF Nonionic surfactants such as 150R1 and anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) can also be used.

-Other additives-
In addition to the above, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, Alkali-soluble resins such as those obtained by adding an acid anhydride to a polymer having a hydroxyl group, alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; EFKA-46, EFKA-47, EFKA-47EA, EFKA High polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco) Molecular dispersant; Solsperse 3000 Various Solsperse dispersants such as 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95 , F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by Asahi Denka Co., Ltd.), and Isonet S-20 (above, made by Sanyo Kasei); 2- (3-t- UV absorbers such as butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

Further, when the alkali solubility of the uncured part is promoted and the developability of the colored curable composition is further improved, the colored curable composition may have an organic carboxylic acid, preferably a low molecular weight of 1000 or less. It is preferable to add an organic carboxylic acid.
Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc. Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, Aromatic polymers such as terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid Rubonic acid; Phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid Examples include acids.

-Thermal polymerization inhibitor-
In addition to the above, a thermal polymerization inhibitor can also be added to the colored curable composition used in the present invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

-Preparation method of colored curable composition-
The coloring composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored curable composition, the components constituting the colored composition may be combined at once, or may be sequentially mixed after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
However, when a pigment is used as a component, it is preferable to prepare a colored composition after previously dispersing the pigment to obtain a pigment dispersion.
The content of the coloring material in the colored composition of the present invention is preferably an amount that is in the range of 20% by mass to 60% by mass with respect to the total solid content (mass) of the colored curable composition, preferably 30% by mass or more. An amount that is in the range of 60% by mass or less is more preferable, and an amount in which the content of the coloring material is in the range of 35% by mass to 50% by mass is further preferable.
When the content of the coloring material of the colored curable composition is within this range, the color density is sufficient and it is effective to ensure excellent color characteristics.
The colored curable composition prepared as described above is preferably filtered using a filter having a pore size of 0.01 μm to 3.0 μm, more preferably a pore size of about 0.05 μm to 0.5 μm. Can be used for use.

  Since the colored curable composition of the present invention can form a colored cured film having high luminance and excellent hue and contrast, a liquid crystal display device (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.) It can be suitably used for forming colored pixels such as a color filter used for printing and for producing printing ink, inkjet ink, paint, and the like.

<Color filter and manufacturing method thereof>
The color filter of the present invention includes a substrate, and a colored pixel made of a colored composition containing a phthalocyanine compound represented by the general formula (1) and a methine compound represented by the general formula (11) on the substrate. It is configured. The colored region on the substrate is composed of colored films such as red (R), green (G), and blue (B) that form each pixel of the color filter. Since the color filter of the present invention is formed including the phthalocyanine compound represented by the general formula (1) and the methine compound represented by the general formula (11), the image has high brightness, and the hue and contrast are improved. It is excellent and is particularly suitable for liquid crystal display devices, organic EL display devices, and solid-state imaging devices.
The color filter of the present invention may be formed by any method as long as it has a colored region (colored pattern) obtained by curing the colored curable composition of the present invention.

The method for producing a color filter of the present invention includes the step (1) of applying a colored curable composition as described above on a support and forming a colored layer (also referred to as a colored cured composition layer). The colored cured composition layer formed in step (1) was exposed in a pattern-like manner (preferably through a mask) to form a latent image, and the latent image was formed. And a step (3) of forming a colored region (colored pattern) by developing the colored layer.
In the method for producing a color filter of the present invention, in particular, the step (4) of irradiating the colored pattern formed in the step (3) with ultraviolet rays and the colored pattern irradiated with the ultraviolet rays in the step (3) are applied. On the other hand, the aspect which further provided the process (5) which heat-processes is preferable.
In addition, a color filter can be produced by a method such as a transfer method described in Japanese Patent Application Laid-Open No. 2009-116078 and an ink jet method described in Japanese Patent Application Laid-Open No. 2009-134263.

Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.
-Step (1)-
In the method for producing a color filter of the present invention, first, the colored curable composition of the present invention described above is applied on a support by a coating method such as spin coating, cast coating, roll coating, and the like. After forming a physical layer, if necessary, preliminary curing (prebaking) is performed, and the colored cured composition layer is dried.

As the support, for example, soda glass, non-alkali glass, borosilicate glass, quartz glass, resin substrate, etc. used for liquid crystal display devices, etc., CCD, CMOS, photoelectric conversion element substrate in organic CMOS, A silicon substrate etc. are mentioned.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

  The colored curable composition of the present invention is applied to the substrate directly or via other layers by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and ink jet. A coating film can be formed.

Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
The thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, the range of 1.0 μm to 4.0 μm is more preferable, and the range of 1.5 μm to 3.5 μm is the most preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, The range of 0.3 micrometer-2.5 micrometers is more preferable, The range of 0.3 micrometer-1.5 micrometers is the most preferable.
In addition, the thickness of the colored curable composition layer is a film thickness after pre-baking.

-Step (2)-
Then, in the manufacturing method of the color filter of this invention, exposure is performed through a photomask, for example with respect to the colored hardening composition layer formed on the support body. As light or radiation applicable to exposure, g-line, h-line, i-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{30mJ / cm 2 ~10000mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light etc. can also be used.

~ Exposure process using laser light source ~
In an exposure method using a laser light source, an ultraviolet laser is used as the light source.
The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the curing wavelength of the colored curable composition. This is preferable. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen) can be used. In addition, devices other than those described above are also preferably used.

The colored cured composition layer exposed as described above can be heated.
The exposure can be performed while flowing a nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored curable composition layer.

-Step (3)-
Subsequently, the colored cured composition layer after exposure is developed with a developer. Thereby, a colored pattern (resist pattern) can be formed.
As long as the developing solution dissolves the uncured portion (unexposed portion) of the colored cured composition layer and does not dissolve the cured portion (exposed portion), a combination of various organic solvents or an alkaline aqueous solution can be used. . When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 11 to 13, more preferably pH 11.5 to 12.5. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium. Examples include alkaline aqueous solutions such as hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.

  Thereafter, in the method for producing a color filter of the present invention, if necessary, post-heating and / or post-exposure can be performed on the colored pattern formed by development to promote curing of the colored pattern.

-Step (4)-
In the method for producing a color filter of the present invention, in particular, post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored composition.

-Step (5)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having a plurality of hue pixels, the above-described step (1), step (2), step (3), and step (4) or step (5) as necessary, the desired number of colors. You may repeat according to.
Each time the formation, exposure, and development of the monochromatic colored curable composition layer is completed (for each color), the step (4) and / or the step (5) may be performed, or the desired number of colors may be determined. After all the colored cured composition layers have been formed, exposed, and developed, step (4) and / or step (5) may be performed collectively.

Since the color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) uses the colored curable composition of the present invention, it has high brightness and excellent hue and contrast. .
The color filter of the present invention can be used for a liquid crystal display element or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image excellent in high luminance and contrast while achieving a good hue.

<Liquid crystal display device, organic EL display device>
The liquid crystal display device and the organic EL display device of the present invention are provided with the above-described color filter of the present invention.
For the definition of liquid crystal display devices and organic EL display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Device (written by Junaki Ibuki, Sangyo Tosho (issued in 1989) ”. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system.

  When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold-cathode tube. By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  The color filter of the present invention can be used for a solid-state image sensor such as a CCD or CMOS. When used in a solid-state image sensor, a color filter having high luminance and good color separation can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

[Example 1]
-Synthesis of Exemplified Compound A-11-
Synthesis was performed according to the following scheme.

Synthesis of (Intermediate 1) In a flask, 26.6 g (0.1 mol) of tetrachlorophthalonitrile, 19.6 g (0.1 mol) of sodium p-hydroxybenzenebenzenesulfonate, 250 ml of N, N-dimethylformamide, After stirring at room temperature for 30 minutes, 11.1 g (0.11 mol) of triethylamine was added and reacted at 60 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to 25 ° C., 200 ml of ethyl acetate and 200 ml of ion-exchanged water were added, and celite filtration was performed. 50 ml of ion-exchanged water was further added to the obtained filtrate, and the organic layer was removed by a liquid separation operation.
The obtained aqueous layer was added to 500 ml of ion exchange water and 180 g of sodium chloride. The precipitated crystals were filtered, washed successively with 200 ml of a 15% by mass aqueous sodium chloride solution and 100 ml of ethyl acetate, and blown and dried at 50 ° C. to obtain 33.5 g of intermediate 1 (yield: 84%).

Synthesis of (Intermediate 2) 21.3 g (50 mmol) of Intermediate 1 was added to 100 ml of acetonitrile and 20 ml of N, N-dimethylacetamide and stirred in an ice bath, and 23.0 g (150 mmol) of phosphorus oxychloride was added. It was dripped. After completion of dropping, the mixture was stirred at 60 ° C. for 4 hours. After completion of the reaction, the solution was cooled to 5 ° C., and extracted with 150 ml of ethyl acetate and 150 ml of ion-exchanged water. To the obtained organic layer, 150 ml of a 5% by mass aqueous sodium hydrogen carbonate solution was added and stirred at room temperature for 1 hour. Thereafter, the aqueous layer was removed by a liquid separation operation. The obtained organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. In this way, 16.9 g (80%) of Intermediate 2 was obtained.

The details of ¹ H-NMR (CDCl ₃ ) were δ: 8.07 to 8.10 (d, 2H) and 7.09 to 7.00 (m, 2H).

  Further, from the proton ratio of the NMR peak, it was confirmed that the intermediate 2 was a mixture of the following intermediate 2-1 and intermediate 2-2 (intermediate 2-1: intermediate 2-2 (molar ratio). ) = 83: 17).

Synthesis of (Intermediate 3) 21.1 g (50 mmol) of Intermediate 2 was added to 60 ml of N, N-dimethylacetamide, stirred in an ice bath, and 8.9 g of N-ethylethanolamine maintained at 10 ° C. or lower. (100 mmol) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 2 hours in an ice bath, and extracted with 100 ml of ethyl acetate, 100 ml of ion-exchanged water, and 3 ml of concentrated hydrochloric acid. The organic layer was washed with a saturated aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate, and then the solvent was distilled off. Then, it refine | purified by silica gel column chromatography (hexane / ethyl acetate = 1/1), and obtained 19.0g of intermediate 3 (yield 80%).

The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 7.88 to 7.84 (m, 2H), 7.01 to 6.93 (m, 2H), 3.81 to 3.78 ( t, 2H), 3.33 to 3.28 (q, 4H), and 1.18 to 1.15 (t, 3H).

Synthesis of (Intermediate 4) Add 16.9 g (36 mmol) of Intermediate 3 and 4.2 g (53 mmol) of pyridine to 60 ml of tetrahydrofuran, stir in an ice bath, and maintain acetyl chloride 3. 4 g (43 mmol) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 3 hours in an ice bath, and extracted with 100 ml of ethyl acetate, 100 ml of ion-exchanged water, and 3 ml of concentrated hydrochloric acid. The organic layer was washed successively with a saturated aqueous sodium hydrogen carbonate solution, ion-exchanged water, and a saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate, and the solvent was distilled off. Thereafter, the product was purified by silica gel column chromatography (hexane / ethyl acetate = 1/1) to obtain 17.2 g of intermediate 4 (yield: 94%).

The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 7.86 to 7.82 (m, 2H), 7.00 to 6.92 (m, 2H), 4.22 to 4.19 ( t, 2H), 3.42 to 3.39 (t, 2H), 3.31 to 3.26 (q, 2H), 2.08 (s, 3H), 1.18 to 1.14 (t, 3H).

Synthesis of (Intermediate 5) 8.5 g (16.5 mmol) of intermediate 4, 1.1 g (4.1 mmol) of tetrachlorophthalonitrile, and 9.6 ml of benzonitrile were added. Stir for hours. Thereafter, 1.9 g (6.0 mmol) of zinc iodide was added, and the mixture was stirred at 135 ° C. for 48 hours. After completion of the reaction, 100 ml of methanol was added to the reaction solution cooled to 60 ° C. or lower and stirred. The precipitated crystals were filtered, and the obtained crystals were added to 200 ml of methanol and stirred at room temperature for 1 hour. Then, 9.2g (yield: 93%) of intermediate bodies 5 were obtained by filtering and air-drying at 50 degreeC.

Formation of the intermediate 5 was confirmed by MALDI-TOF-MASS (apparatus: Voyager DE STR (AB Sciex), sample: matrix = 1: 20).
The result of MALDI-TOF-MASS (negative) is shown in FIG.
From the result of MALDI-TOF-MASS (nega), it was confirmed that the obtained intermediate 5 was a mixture of phthalocyanines in which 1 to 4 phenoxy substituents were introduced into phthalocyanine.

Synthesis of (Exemplary Compound A-11) 40 g of tetrahydrofuran, 40 ml of methanol, and 1.7 g (12.4 mmol) of potassium carbonate were added to 4 g (2.1 mmol) of Intermediate 5 and stirred at room temperature for 12 hours. Thereafter, 300 ml of ion-exchanged water was added to the reaction solution, and the precipitated crystals were filtered and air-dried at 50 ° C.
The obtained solid was dissolved in 30 ml of tetrahydrofuran, stirred in an ice bath, and 3.2 g (31.5 mmol) of triethylamine and 1 drop of nitrobenzene were added. Thereafter, 2.9 g (31.5 mmol) of acryloyl chloride was added dropwise in an ice bath so as to keep the internal temperature at 5 ° C. or lower, followed by stirring for 3 hours.
After completion of the reaction, the reaction solution was extracted with 60 ml of ethyl acetate and 60 ml of ion exchange water. The organic layer was washed with a saturated aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate, and then the solvent was distilled off. Then, it refine | purified by silica gel column chromatography (ethyl acetate), 2.5g (yield: 61%) of exemplary compound A-11 was obtained by wash | cleaning the obtained solid, filtering, and drying at room temperature. .

The production of Exemplary Compound A-11 was confirmed by MALDI-TOF-MASS (apparatus: Voyager DE STR (AB Sciex), sample: matrix = 1: 20).
The result of MALDI-TOF-MASS (negative) is shown in FIG.
From the results of MALDI-TOF-MASS (nega), it was confirmed that the obtained exemplary compound A-11 was a mixture of phthalocyanines in which 1 to 4 phenoxy substituents were introduced into phthalocyanine.

Moreover, the ethyl acetate solution and chloroform solution spectrum of exemplary compound A-11 were measured using spectrophotometer UV-1800PC (made by Shimadzu Corporation). The measured spectrum is shown in FIG.

-Synthesis of Exemplified Compound Y-1-
Synthesis was performed according to the following scheme.

(Synthesis of Intermediate A-1)
Compound (A) (synthesized by the method described in European Patent Application No. 0571959) was prepared, and according to the above synthesis scheme, first, 100 parts of compound (A), 55 parts of γ-picoline, 300 parts of tetrahydrofuran were prepared. , And a mixed solution of 600 parts of ethyl acetate was cooled to 5 ° C., and 114 parts of p-styrenesulfonyl chloride was added dropwise thereto at a reaction temperature of 20 ° C. or less. The reaction solution was stirred at room temperature for 3 hours, and then the precipitate was filtered and washed with acetonitrile to obtain 150 parts of Intermediate A-1. The yield was 91%.
The results of confirming the structure of the obtained intermediate A-1 by NMR are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.3 (s, 9H), 5.4 (d, 1H), 5.6 (s, 1H), 6.0 (d, 1H), 6.8 ( q, 1H), 7.2 (d, 2H), 7.6 (d, 2H), 7.8 (t, 4H), 10.8 (s, 1H), 12.9 (s, 1H)

-Preparation of colored curable composition-
Pc-1: 20 parts of phthalocyanine compound (A-11) Mt-1: 20 parts of methine compound (Y-1) B-1: benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio])
Copolymer Mw: 10,000) propylene glycol monomethyl
Ether acetate solution (solid content 25%) 100 parts · DPHA (manufactured by Nippon Kayaku Co., Ltd.) 32 parts · C-1: 2- (acetoxyimino) -4- (4-chlorophenylthio) -1-
[9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-
3-yl] -1-butanone (manufactured by BASF) 3 parts ・ Polymerization inhibitor: 0.001 part of p-methoxyphenol ・ fluorine-based surfactant (trade name: manufactured by MegaFac F-554 DIC) 0.5 Parts ・ Propylene glycol monomethyl ether acetate 225 parts ・ Propylene glycol monomethyl ether 100 parts

[Example 2] to [Example 15]
In Examples 2 to 15, each component described in Example 1 was changed to each component described in Table 1, and a colored curable composition was prepared in the same manner as Example 1.
Example 7 and Example 8 which do not contain B-1 of Example 1 were prepared using 25 parts of DPHA and 75 parts of propylene glycol monomethyl ether acetate instead of 100 parts of B-1.

-Synthesis of Exemplified Compound A-70-
In the synthesis example of exemplary compound A-11 described above, N-ethylethanolamine used in the process of synthesizing intermediate 3 was changed to N-methoxyethylglycidylamine (100 mmol), and the process of synthesizing intermediate 4 was not performed. In addition, in the process of synthesizing the intermediate 5, the intermediate 3 is used in place of the intermediate 4 and the reaction is carried out in the same manner except that the preparation ratio in the step of phthalocyanination is adjusted to obtain an exemplary compound A-70. It was.

-Synthesis of Exemplified Compound A-51-
In the synthesis example of the exemplary compound A-11 described above, N-ethylethanolamine used in the process of synthesizing the intermediate 3 was changed to diethanolamine (100 mmol), and 86 mmol of acetyl chloride used in the process of synthesizing the intermediate 4 was used. The compound was reacted in the same manner except that the charge ratio in the step of phthalocyanination in the process of synthesizing the intermediate 5 was adjusted to obtain Exemplified Compound A-51.

-Synthesis of Exemplified Compound A-2-
In the synthesis example of Exemplified Compound A-11 described above, the reaction was conducted in the same manner except that N-ethylethanolamine used in the process of synthesizing Intermediate 3 was changed to N-methylethanolamine (100 mmol). Exemplified Compound A -2 was obtained.

-Synthesis of Exemplified Compound A-18-
In the synthesis example of the exemplary compound A-11 described above, the zinc iodide used in the process of synthesizing the intermediate 3 is changed to copper (II) chloride, and charged in the process of phthalocyanation in the process of synthesizing the intermediate 5 Except that the ratio was adjusted, the reaction was performed in the same manner to obtain Exemplified Compound A-18.

-Synthesis of Exemplified Compound Y-4-
Illustrative compound Y-4 was synthesized as follows.

-Synthesis of Intermediate A-4-
Intermediate A-4 was synthesized in the same manner as in the synthesis of Intermediate A-1 in Synthesis Example 1, except that the following compound (2-B) was used instead of p-styrenesulfonyl chloride.

The results of confirming the structure of the resulting intermediate A-4 by NMR are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.3 (s, 9H), 1.6 (d, 3H), 3.5 (m, 1H), 4.5 (m, 4H), 5.9 ( t, 1H), 6.1 (m, 1H), 6.5 (t, 1H), 7.3 (d, 2H), 7.8 (d, 4H), 10.5 (s, 1H), 12.7 (s, 1H)

-Synthesis of Exemplified Compound Y-4-
Exemplified Compound Y-4 was synthesized in the same manner as Exemplified Compound Y-1, except that Intermediate A-4 was used instead of Intermediate A-1.
The results of confirming the structure of the obtained exemplary compound Y-4 by NMR are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.3 (s, 18H), 1.6 (d, 6H), 3.7 (m, 2H), 4.5 (m, 8H), 5.6 ( s, 1H), 5.9 (t, 2H), 6.1 (m, 2H), 6.5 (t, 2H), 7.3 (d, 4H), 7.4 (t, 1H), 7.8 (d, 4H), 8.1 (d, 1H)

[Comparative Examples 1 to 4]
In Comparative Examples 1 to 4, each component described in Example 1 was changed to each component described in Table 1 and adjusted in the same manner as in Example 1 to prepare a colored curable composition.

-Evaluation-
About each colored curable composition obtained above, the residual rate was evaluated by the following method. The evaluation results are shown in Table 1 below.

About the colored curable composition prepared in each Example and comparative example, after apply | coating the colored curable composition obtained above on the glass (EAGLE XG; made by Corning) by a spin coat method, it is 2 at 100 degreeC. Volatile components were volatilized for a minute to form a colored film. After cooling, the colored film was exposed using an ultrahigh pressure mercury lamp. The amount of irradiation light was 100 mJ / cm ² . Subsequently, post-baking was performed at 230 ° C. for 20 minutes to obtain a glass substrate having a colored layer having a thickness of 2 μm.

The absorbance of the colored layer was measured using a spectrophotometer (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.) for the glass substrate having the obtained colored layer, and a resin solution (benzyl methacrylate / methacrylic acid = 70/30). (Molar ratio), Mw30000 copolymer (15% by mass) of propylene glycol monomethyl ether acetate (50% by mass) and diethylene glycol methyl ethyl ether (35% by mass)), and volatilized at 100 ° C. for 2 minutes. Minutes removed. Subsequently, the resin film was removed with a 0.05% KOH aqueous solution at 25 ° C., and the absorbance after removing the resin film was measured. The absorbance of the colored layer before and after the treatment of the resin film was compared at the maximum absorption wavelength. The residual rate was calculated | required by the following formula.
The smaller the change in absorbance before and after the treatment of the resin film, the higher the residual color rate and the better the performance.

Residual color rate = absorbance after treatment / absorbance before treatment (in Table 1, results are expressed in%)

The description in Table 1 will be described below.
C-1: 2- (acetoxyimino) -4- (4-chlorophenylthio) -1-
[9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-
3-yl] -1-butanone (BASF)
C-2: The following polymerization initiator

C-3: 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl]
-2,6-di (trichloromethyl) -s-triazine,
C-4: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra
Phenylbiimidazole (B-CIM Hodogaya Chemical Co., Ltd.) /
2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (= 2 parts by mass / 1 part by mass)
B-2: Allyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer

Pc-A: Intermediate 5

Pc-2: Phthalocyanine compound (Exemplary Compound A-70)
Pc-3: Phthalocyanine compound (Exemplary Compound A-51)
Pc-4: Phthalocyanine compound (Exemplary Compound A-2)
Pc-5: Phthalocyanine compound (Exemplary Compound A-18)

Mt-2: Methine compound (Exemplary Compound Y-4)

Mt-A: Methine compound (the following structure)

  As shown in Table 1, the coloring composition containing the compound represented by the general formula (1) (phthalocyanine compound) and the compound represented by the general formula (11) (methine compound) has a residual color ratio. It can be seen that it is high and shows good performance.

Claims (8)

A coloring composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (11).


In general formula (1), X represents a halogen atom, and M represents a nonmetal atom, a metal atom, a metal oxide, or a metal halide. R ¹ represents a group represented by the following general formula (2), and R represents a hydrogen atom or a substituent. A plurality of n each independently represents an integer of 0 to 4, a plurality of m each independently represents an integer of 0 to 4, and a plurality of r each independently represents an integer of 0 to 4. However, at least one of n is 1 or more, and at least one of m is 1 or more. The sum of n, m and r is 16.


In General Formula (2), R ² and R ³ each independently represent a monovalent substituent, or a group represented by General Formula (3) or General Formula (4) below, and R ² and R ³ At least one represents a group represented by the following general formula (3) or general formula (4). * Represents the site | part couple | bonded with the phthalocyanine ring in General formula (1).


In General Formulas (3) and (4), L ₁ and L ₂ each independently represent a single bond or a divalent linking group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ Each independently represents a hydrogen atom or a monovalent substituent. * Represents the site | part couple | bonded with N in General formula (2).



In the general formula (11), R ₇₁ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an aryl group, or a heteroaryl group. In General Formula (11), R ₇₂ and R ₇₃ each independently represent a monovalent substituent, or a group represented by General Formula (12) or General Formula (13) below, and R ₇₂ and R ₇₃ At least one of represents a group represented by the following general formula (12) or general formula (13).

In General Formulas (12) and (13), L ₁ and L ₂ each independently represent a single bond or a divalent linking group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ Each independently represents a hydrogen atom or a monovalent substituent. * Represents a site that binds to the methine structure in the general formula (11).   Furthermore, the coloring composition of Claim 1 containing a polymeric compound and a photoinitiator.   The colored composition according to claim 2, wherein the photopolymerization initiator includes an oxime ester compound.   Furthermore, the coloring composition of any one of Claims 1-3 containing an alkali-soluble binder.   The color filter which has a colored layer formed using the coloring composition of any one of Claims 1-4.   A liquid crystal display device comprising the color filter according to claim 5.   An organic EL display device comprising the color filter according to claim 5.   A solid-state imaging device comprising the color filter according to claim 5.