JP2016153481A - Coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition which is excellent in fastness (heat resistance, light resistance, and solvent resistance), is excellent in brightness and contrast ratio when used for a color filter, and is free from generation of foreign matter, and to provide a color filter.SOLUTION: The coloring composition contains at least a colorant, a binder resin, and an organic solvent. The colorant contains a phthalocyanine pigment represented by general formula (1). (X is a halogen atom; n is an integer of 4-16; Y is OP(=O)RR, OC(=O)R, or OS(=O)R; and Rto Rare each a hydroxyl group, a substituted/unsubstituted alkyl group, a substituted/unsubstituted aryl group, or a substituted/unsubstituted heterocyclic group.)SELECTED DRAWING: None

Description

  The present invention relates to a coloring composition and a color filter used for producing a color filter used for a color liquid crystal display device, an organic EL display device, a color image pickup tube element and the like.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes are provided on one substrate and an electric field is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method that vertically aligns nematic liquid crystal with optical properties, and optically converged bend (OCB) method that optically compensates by making the optical axes of uniaxial retardation films orthogonal to each other Etc., and each has been put to practical use.

  The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. In recent years, since it has been used for a wide range of applications such as televisions and personal computer monitors, color filters have high transmittance (high brightness) for high contrast and low power consumption in order to improve image quality. Is required. In particular, due to the recent increase in environmental awareness, demand for high brightness is high, and a wide color reproduction region and high reliability are also required.

In addition, a color image pickup device represented by C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc. has a red filter layer (R) on the light receiving element. In general, color filters each including a primary color filter segment of an additive mixture of a green filter layer (G) and a blue filter layer (B) are disposed and separated. Further, since high sensitivity can be obtained compared to the primary color filter, a color filter having filter segments of cyan, magenta, and yellow (CMY) corresponding to the complementary colors of red, green, and blue is often used. Complementary color filters are often used in video cameras and the like that are difficult to use an auxiliary light source such as a flash.
In recent years, there has been an increasing demand for high transmittance, that is, lightness and high reliability even in color filters used in color image pickup tube elements.

  The color filter is a fine band (striped) filter segment (strip) formed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. Pixels) are arranged in parallel or intersecting with each other, or fine filter segments are arranged in a constant arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue. Recently, in addition to a red filter layer (R), a green filter layer (G), and a blue filter layer (B), a filter segment including a yellow filter layer (Y) is also used.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Conventional dyeing methods and dye dispersion methods are slightly inferior in fastness (mainly heat resistance and light resistance), so pigments with excellent fastness are often used as colorants for color filters. In many cases, the pigment dispersion method is used because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive into a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  In the production of a green filter, it is common to use various phthalocyanine compounds as colorants, and among them, many color filter colorants using copper phthalocyanine compounds and zinc phthalocyanine compounds have been proposed. In order to achieve high brightness with the phthalocyanine compound, it is necessary to precisely control the absorption wavelength of the phthalocyanine compound itself and the absorption wavelength / absorbance derived from the aggregate formed at the time of coating. , A method of changing the central metal species, and a method of introducing a functional group into the phthalocyanine ring.

    Patent Document 1 proposes a color filter composition using a halogenated phthalocyanine compound substituted with at least four halogen atoms as a green colorant.

  In Patent Document 2, as a green pigment, a halogenated copper phthalocyanine pigment and a central metal are selected from the group consisting of Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. There has been proposed a color filter composition comprising a green colorant composed of at least one halogenated dissimilar metal phthalocyanine pigment.

  However, all of these phthalocyanine compounds are materials for producing a high brightness color filter. However, in recent years, the demand for high brightness has further increased, and in the composition using these proposed colorants, the brightness is high. Was insufficient.

  Patent Document 3 discloses a pigment composition that maintains a clear hue, high light resistance, and high heat resistance by using a blue aluminum phthalocyanine pigment containing no halogen and a green pigment containing halogen. Yes.

  In Patent Document 4, as a coloring composition for a green color filter segment, an aluminum phthalocyanine pigment is used as a main pigment, and high brightness can be obtained with high chromaticity even with a relatively small content, and both color density and color purity are achieved. Disclosed techniques are disclosed.

  As the aluminum phthalocyanine pigment, in addition to the monomer aluminum phthalocyanine pigment described in Patent Document 4, in Patent Document 5, bis (phthalocyanylalumino) tetraphenyl obtained by dimerizing an aluminum phthalocyanine pigment with diphenylchlorosilane is used. Bis (phthalocyanylaluminum) phenylphosphonate pigments dimerized with disiloxane pigments or phenylphosphonic acid are disclosed.

  However, the pigment compositions containing these aluminum phthalocyanine compounds are not sufficient in heat resistance at 230 ° C. or higher and long-term light resistance, which are required for color filter applications, and the spectral shape changes. was there. Furthermore, problems such as an increase in viscosity of the colored composition and generation of foreign matters on the coating film due to poor dispersibility have not been sufficiently improved.

JP 2002-131521 A JP 2002-250812 A JP 2003-4930 A JP 2004-333817 A Japanese Unexamined Patent Publication No. 57-90058

  The problem to be solved by the present invention is a coloring composition which is excellent in fastness (heat resistance, light resistance, solvent resistance), excellent in color characteristics (brightness) and contrast ratio when used in a color filter, and does not generate foreign matters. Object and color filter.

  As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have reached the present invention. That is, the present invention is a coloring composition containing at least a colorant, a binder resin, and an organic solvent, wherein the colorant contains a phthalocyanine pigment represented by the following general formula (1). It is related with the coloring composition characterized.

(In the formula, X represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X is 6 to 15, and the halogen distribution width is Y is 4 or more, Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , wherein R ₁ and R ₂ are each independently In addition, a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or an aryloxy which may have a substituent R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Represents a heterocyclic group which may have a reel group or a substituent.)

  Moreover, this invention relates to the said coloring composition formed by containing a green pigment | dye and / or a yellow pigment | dye further.

  In the present invention, the green pigment is C.I. I. Pigment Green 7, 36 and 58, which is at least one selected from the group consisting of C.I. I. It is related with the said coloring composition which is at least 1 sort (s) chosen from the group which consists of pigment yellow 138, 139, 150 and 185.

  The present invention further relates to the colored composition comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  In the color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one green filter segment is formed of the colored composition. It relates to a color filter.

  The colored composition of the present invention can provide a color filter that is excellent in fastness (heat resistance, light resistance, solvent resistance), has high brightness and high contrast ratio, and does not generate foreign matter.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ".
Further, “CI” mentioned in the present specification means a color index (CI).

<Colorant>
The coloring composition of the present invention contains at least a coloring agent, a binder resin, and an organic solvent, and the coloring agent contains a phthalocyanine pigment represented by the following general formula (1).

(In the formula, X represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X is 6 to 15, and the halogen distribution width is Y is 4 or more, Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , wherein R ₁ and R ₂ are each independently In addition, a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or an aryloxy which may have a substituent R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Represents a heterocyclic group which may have a reel group or a substituent.)

  Here, examples of the “halogen” include fluorine, bromine, chlorine and iodine, with bromine and chlorine being preferred. Two or more kinds of halogen atoms may be used in combination as long as they are within the range of the average value of the number of substitutions and the distribution width. In particular, it is preferable to use bromine and chlorine in combination.

  In the phthalocyanine pigment represented by the general formula (1), the average value of the number of substitutions of the halogen atom represented by X is 6 to 15, and 8 to 15 is preferable from the viewpoint of hue and fastness. The halogen distribution width is 4 or more, and preferably 4-9. It is clear that when the halogen distribution width is 4 or more, the association between phthalocyanine molecules is remarkably suppressed, which greatly contributes to the increase in particle size due to the association between molecules, and further to the reduction in contrast. became. Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the phthalocyanine pigment represented by the general formula (1). In the mass spectrum obtained by mass spectrometry, the halogen distribution width calculates the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value (total peak value) obtained by integrating each peak value, The number of peaks having a ratio of each peak value to 1% or more with respect to the total peak value was counted as a halogen distribution width.

The alkyl group in R ₁ to R _4, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, tert- butyl group, neopentyl group, hexyl group n-, n-octyl group, stearyl group , A straight-chain or branched alkyl group such as 2-ethylhexyl group, and an alkyl group having 1 to 6 carbon atoms is preferable.
Examples of the substituent of the alkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups such as methoxy group, aryl groups such as phenyl group and tolyl group, and nitro groups. Further, there may be a plurality of substituents. Accordingly, examples of the alkyl group having a substituent include, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and 2-butoxy. Ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl Groups and the like.

Examples of the aryl group in R _{1 to} R ₄ include monocyclic aromatic hydrocarbon groups such as a phenyl group and a p-tolyl group, and condensed aromatic hydrocarbon groups such as a naphthyl group and an anthryl group. A hydrocarbon group is preferred. Moreover, a C6-C12 aryl group is preferable.
Examples of the substituent of the aryl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryl group having a substituent, for example, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylaminophenyl group, Examples include 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

Examples of the alkoxyl group in R ₁ and R ₂ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3- Examples thereof include linear or branched alkoxyl groups such as a pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, and an alkoxyl group having 1 to 6 carbon atoms is preferable.
Examples of the substituent of the alkoxyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Therefore, examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2- Examples include ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

As the aryloxy group in R ₁ and R _2, an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group or a p-methylphenoxy group, or a condensed aromatic hydrocarbon such as a naphthaloxy group or an anthryloxy group An aryloxy group comprising a group, and an aryloxy group comprising a monocyclic aromatic hydrocarbon group is preferred. Moreover, a C6-C12 aryloxy group is preferable.
Examples of the substituent of the aryloxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryloxy group having a substituent, for example, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, etc. Can be mentioned.

Examples of the cycloalkyl group in R ₃ include a monocyclic aliphatic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, a bornyl group, an adamantyl group, and the like. A condensed aliphatic hydrocarbon group is mentioned. Moreover, a C5-C12 cycloalkyl group is preferable.
Examples of the substituent of the cycloalkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Examples of the heterocyclic group in R ₃ and R ₄ include aliphatic heterocyclic groups such as pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group, acridinyl group, and aromatic heterocyclic groups. Moreover, a C4-C12 heterocyclic group is preferable and a C5-C13 heterocyclic group is preferable.
Examples of the substituent of the heterocyclic group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Examples of the heterocyclic group having a substituent include a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

As the phthalocyanine compound represented by the general formula (1), at least one of R ₁ and R ₂ has an aryl group or a substituent which may have a substituent from the viewpoint of dispersibility and color characteristics. May be an aryloxy group, R ₁ and R ₂ are both aryl groups or aryloxy groups, and R ₁ and R ₂ are both phenyl groups or phenoxy groups. More preferably. R ₃ and R ₄ are preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

  In the present invention, the phthalocyanine compound represented by the general formula (1) is represented by [AlPc (Y)] Xn (4 ≦ n ≦ 16) (where Pc is a phthalocyanine ring, X is a halogen atom, and n is 4 to 16). Are represented by [AlPc (Y)] Brn (4 ≦ n ≦ 16), [AlPc (Y)] Cln (4 ≦ n) as representative examples of the general formula (1). ≦ 16), [AlPc (Y)] In (4 ≦ n ≦ 16), [AlPc (Y)] Fn (4 ≦ n ≦ 16), and the like, but the present invention is not limited to these. Absent. Further, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

  Typical examples of Y in the general formula (1) include the structures shown below (* represents the bonding position of the substituent with Al in the general formula (1)). It is not limited to. Further, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

(Green pigment)
The coloring composition of the present invention may further contain a green pigment within a range not impairing the effects of the present invention, for example, in order to adjust the chromaticity. Although there is no restriction | limiting in particular as a green pigment | dye, Generally, a green pigment or a green dye is mentioned.
Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, JP2008- The zinc phthalocyanine pigment described in JP 19383, JP 2007-320986 A, JP 2004-70342 A, and the like, and the aluminum phthalocyanine pigment described in JP 4893859 A, and the like can be mentioned. It is not limited. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36, and 58.

  Examples of the green dye include C.I. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dyes, C.I. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes, C.I. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes, C.I. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Examples include modern dyes. Examples of green pigments include C.I. I. It is preferably at least one selected from the group consisting of CI Pigment Green 7, 36 and 58.

(Yellow pigment)
The colored composition of the present invention may further contain a yellow pigment within a range not impairing the effects of the present invention, for example, in order to adjust the chromaticity. Although there is no restriction | limiting in particular as a yellow pigment | dye, Generally, a yellow pigment or a yellow dye is mentioned.

  As the yellow pigment, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

  Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,192,193,194,196,198,199,213,214, may be used yellow pigment quinophthalone pigments described in Japanese Patent No. 4,993,026 discloses. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, examples of the yellow pigment include C.I. I. It is preferably at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150 and 185.

  Yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes , Naphthoquinone dyes and oxazine dyes.

  Therefore, specific examples of yellow dyes include C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 And the like.

  In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 etc. are also mentioned.

  In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

  In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like are also included.

  In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

  When a green pigment is used in combination with the phthalocyanine pigment represented by the general formula (1), the mass ratio of the green pigment / the phthalocyanine pigment represented by the general formula (1) is 10/90 from the viewpoint of brightness and hue. A range of ˜70 / 30 is preferred. More preferably, it is the range of 20 / 80-40 / 60, More preferably, it is the range of 20 / 80-35 / 65.

  When a yellow dye is used in combination with the phthalocyanine pigment represented by the general formula (1), the weight ratio of the yellow dye / the phthalocyanine pigment represented by the general formula (1) is 70/30 to 70% from the viewpoint of brightness and hue. A range of 10/90 is preferred. More preferably, it is the range of 70 / 30-25 / 75, More preferably, it is the range of 70 / 30-40 / 60.

(Miniaturization of colorant)
The colorant used in the coloring composition of the present invention is suitable as a color filter colorant by obtaining finer colorant particles by a salt milling process or the like as necessary in order to obtain high brightness and high contrast. Can be used for The volume average primary particle diameter of the colorant is preferably 10 nm or more in order to enhance dispersibility in the colorant carrier. Moreover, in order to obtain a filter segment with high contrast, the thickness is preferably 80 nm or less. A particularly preferred range is 20 to 60 nm.

  Salt milling is a process of heating a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the colorant is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the colorant, it is possible to obtain a colorant having a sharp particle size distribution in which the volume average primary particle diameter is very fine and the distribution width is wide. .

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass) in terms of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the colorant and water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, those having a high boiling point of 120 ° C. or higher are preferable from the viewpoint of safety. Such as, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by mass, and most preferably 50 to 500% by mass, based on the total mass of the colorant (100% by mass).

  When salt milling the colorant, a resin may be added as necessary. Here, the type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the water-soluble organic solvent. The amount of resin used is preferably in the range of 2 to 200% by mass based on the total mass of the colorant (100% by mass).

<Binder resin>
The binder resin disperses a colorant such as a pigment or a pigment, particularly a phthalocyanine pigment represented by the general formula (1), and examples thereof include a thermoplastic resin and a thermosetting resin.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. Furthermore, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used for the purpose of further improving photosensitivity and improving solvent resistance.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development resist for color filters, no coating film foreign matter is generated after the colorant is applied. The stability of the colorant is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant is not easily trapped in the resin and the colorant mixture, and has a degree of freedom. The colorant component easily aggregates and precipitates, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the colorant is converted into a resin in a mixture of resin and colorant. Because it is easily trapped, it is difficult for the dye to elute in the solvent resistance test, the colorant component does not easily aggregate and precipitate, and the resin is three-dimensionally crosslinked when exposed to active energy rays to form a film. It is estimated that the colorant component is less likely to aggregate and precipitate even if the colorant molecules are fixed and the solvent is removed in the subsequent development step.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, it acts as a colorant-adsorbing group and an alkali-soluble group during development from the viewpoint of dispersibility, penetrability, developability and heat resistance of the pigment. The balance of aliphatic groups and aromatic groups acting as affinity groups for the carboxyl group, colorant carrier and solvent is important for the dispersibility, penetrability, developability, and durability of the pigment, with an acid value of 20-300 mg KOH / G of resin is preferably used. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  Since the binder resin has good film formability and various resistances, it is preferable to use it in an amount of 30 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant, the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500 parts by mass or less.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, cardo resins, and phenol resins.

The thermosetting resin may be, for example, a low-molecular compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts at the time of firing the filter segment, the cross-linking density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. It is done.
Among these, an epoxy resin, a cardo resin, or a melamine resin is preferable.

<Organic solvent>
In the coloring composition of the present invention, a colorant is sufficiently dissolved in a monomer, a resin, and the like, and applied to a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. In order to facilitate this, an organic solvent is included.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  Moreover, since the organic solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, the amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the total mass of the colorant. It is preferable to use in. In one embodiment, the organic solvent is used in an amount of preferably 500 to 2000 parts by mass, more preferably 500 to 1000 parts by mass with respect to 100 parts by mass of the total mass of the colorant.

<Method for producing colored composition>
In the coloring composition of the present invention, a coloring agent containing the phthalocyanine pigment represented by the general formula (1) is preferably dispersed in a coloring agent carrier composed of the resin and, if necessary, a solvent. Along with the auxiliary agent, it can be produced by finely dispersing using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. In addition, when the solubility of the phthalocyanine pigment represented by the general formula (1) is high, specifically, the solubility in an organic solvent to be used is high, and if it is in a state where dissolution and foreign matter are not confirmed by stirring, There is no need to produce such finely dispersed products.

  The colored composition of the present invention can also be produced by mixing pigments, phthalocyanine pigments represented by the general formula (1) and other colorants separately dispersed in a colorant carrier.

[Dispersion aid]
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less with respect to 100 parts by mass of the colorant.

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  In the case of adding a resin-type dispersant and a surfactant, from the viewpoint of the effect on dispersion, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. It is.

  The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator. Furthermore, the coloring composition of the present invention can contain a sensitizer, a polyfunctional thiol, an amine compound, a leveling agent, a curing agent, a curing accelerator, and other additive components.

<Photopolymerization initiator>
The coloring composition of the present invention can contain a photopolymerization initiator. It is preferable that the compounding quantity at the time of using a photoinitiator is 5-200 mass parts with respect to 100 mass parts of phthalocyanine pigments represented with General formula (1), and 10-150 from a photocurable viewpoint. More preferably, it is part by mass.

  As the photopolymerization initiator, a conventionally known polymerization initiator can be used. Specifically, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane , Oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl Acetophenones such as phenyl] -2-methylpropan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as benzoin isopropyl ether and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Examples include glyoxylic methyl ester. More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 Cure 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01, IRGACURE OXE-02 (BASF), Adekaoptomer N1717, Adekaoptomer N1919, Adeka Arcles NCI- 831 (ADEKA), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 61-9621, and Triazine derivatives described in JP-A-60-60104, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, Japanese Patent Publication No. 47-1604 and diazonium compound publications described in US Pat. No. 3,567,453, USP No. 2,848,328, USP No. 2,852,379, and USP No. 2,940,853, organic azide compounds described in Japanese Patent Publication No. Sho 36- Ortho-quinonediazides described in JP-A-22062, JP-B-37-13109, JP-B-38-18015 and JP-B-45-9610, JP-B-55-39162, JP-A-59-140203 And `` MACROMOLECULES '', No. Vol. 0, various onium compounds including iodonium compounds described on page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851 EP-A-126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986), metal allene complexes described in JP-A-61-151197. Transition metals such as ruthenium described in JP-A-2-182701, as well as the titanocenes described in Japanese Patent Publication No. 1993, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) Transition metal complexes, aluminate complexes described in JP-A-3-209477, JP-A-2-1577 No. 60, borate compounds, JP-A Nos. 55-127550 and 60-202437, 2,4,5-triarylimidazole dimers, carbon tetrabromide and JP-A No. Nos. 59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A-54-99185, JP-A-63-264560, and JP-A-10-29977. Aminoketone compounds described in JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, JP-T-2004-534797, JP-A-2006-342166 , JP2008-094770, JP2009-40762, 2010-15025, JP 2010-189279, JP 2010-189280, JP 2010-526946, JP 2010-527338, JP 2010-527339, USP 3558309 (1971), USP 4202697 (1980) And oxime ester compounds described in JP-A No. 61-24558.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

<Photopolymerizable monomer>
The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce transparent resins include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and epoxy (meth). Acrylate, EO-modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, di Various acrylic esters such as enterythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate And methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile The effects of the present invention are not limited to these.

  Moreover, the photopolymerizable monomer may contain an acid group. For example, esterified product of poly (meth) acrylates containing free hydroxyl group of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; esterified product of polycarboxylic acid and monohydroxyalkyl (meth) acrylates, etc. Can be mentioned. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And a monoesterified product of free carboxyl group with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. However, the effects of the present invention are not limited to these.

  The content of the photopolymerizable monomer is preferably 10 to 300 parts by mass and more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the colorant from the viewpoint of photocurability and developability. It is particularly preferable to use it in an amount of 20 to 100 parts by mass.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, teto Benzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran Examples thereof include, but are not limited to, derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organoruthenium complexes.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, the dyes and sensitizers described in “Functional Materials” (1986, CMC), and other dyes and sensitizers that absorb light from the ultraviolet to the near infrared region. There may be mentioned sensitizers, and these may be used in an arbitrary ratio as required. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). Raised Although it is Rukoto, but is not limited thereto.

  Two or more kinds of sensitizers may be used in any ratio as required. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 mass parts with respect to 100 mass parts of total mass of the photoinitiator (E) contained in a coloring photosensitive composition, and photocuring. It is more preferable that it is 5-50 mass parts from a viewpoint of property.

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (5-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the mass (100% by mass) of the total solid content of the colored composition. When the polyfunctional thiol content is less than 0.1% by mass, the effect of adding the polyfunctional thiol is insufficient, and when it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass in a total of 100% by mass of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. A storage stabilizer can be used in the quantity of 0.1-10 mass parts with respect to 100 mass parts of whole quantity of a coloring agent.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (5, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (5,4-epoxycyclohexyl) methyltrimethoxysilane, β- (5,4-epoxycyclohexyl) ethyltriethoxysilane, β- (5,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the colorant in the coloring composition.

<Removal of coarse particles>
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment.
The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  As a base material such as a transparent substrate constituting the color filter, a glass plate such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. Used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “part” and “%” represent “part by mass” and “% by mass”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

(Resin polymerization average molecular weight (Mw))
Polymerization average molecular weight (Mw) of the resin is TSKgel column (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and measured in terms of polystyrene measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Halogen substitution number)
The number of halogen substitutions in the pigment is determined by analyzing the liquid obtained by burning the pigment by the oxygen combustion flask method and absorbing the combustion product in water by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX). It was obtained by quantifying the amount of halogen and converting it to the number of halogen substitutions.

(Halogen distribution width)
The halogen distribution width in the pigment was determined using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics).
In the mass spectrum obtained by mass spectrometry of the pigment powder, the halogen content is the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value obtained by integrating each peak value (total peak value) Was calculated from the ratio of each peak value to the total peak value.
The halogen distribution width was defined as the halogen distribution width by counting the number of peaks in which the ratio of each peak value to the total peak value was 1% or more.

(Volume average primary particle size (MV))
The volume average primary particle size (MV) of the phthalocyanine pigment and the yellow colorant was determined by a transmission electron microscope (TEM) “H-7650” manufactured by Hitachi High-Technologies Corporation and the following calculation formula. First, colorant particles were photographed by TEM. In the obtained image, select 100 arbitrary colorant particles, the average value of the minor axis diameter and major axis diameter of the primary particles is the particle diameter (d) of the colorant particles, and then the individual colorants are selected. The volume (V) of each particle was determined by considering it as a sphere having the determined particle size (d), and this operation was performed on 100 colorant particles, and the calculation was performed using the following equation (1).

Formula (1)
MV = Σ (V · d) / Σ (V)

<Binder resin production method>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Acrylic resin solution 1 was prepared by adding ether acetate.

<Phthalocyanine pigment and pigment production method>
[Production Example 1]
(Method for producing phthalocyanine pigment PC-1)
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of hydroxyaluminum phthalocyanine (P-1) and 99.1 parts of N-bromosuccinimide (NBS) were added and stirred, and reacted at 20 ° C. for 3 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was filtered, washed with water, and dried to obtain a phthalocyanine pigment (PC-1). The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 2]
(Method for producing phthalocyanine pigment PC-2)
Reaction of 50 parts of hydroxyaluminum phthalocyanine (P-1) with 50 parts of chloroaluminum phthalocyanine (P-2) and 99.1 parts of NBS with 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) Except having changed time from 3 hours to 4 hours, operation similar to manufacture example 1 was performed and the phthalocyanine compound (PC-2) was obtained. The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 3]
(Method for producing phthalocyanine pigment PC-3)
A phthalocyanine compound (PC-3) was obtained in the same manner as in Production Example 2, except that the amount of DBDMH and the reaction time were changed to the conditions described in Table 1, respectively. The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 4]
(Method for producing phthalocyanine pigment PC-4)
203 parts of aluminum bromide, 47 parts of sodium bromide and 5 parts of ferric bromide were heated and melted, and 50 parts of chloroaluminum phthalocyanine (P-2) was added at 140 ° C. The temperature was raised to 160 ° C., and the reaction was carried out at 160 ° C. for 6 hours while blowing 173.7 parts of bromine. The above reaction mixture was poured into 2500 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. The residue was washed with 1% hydrochloric acid aqueous solution, warm water, 1% sodium hydroxide aqueous solution and warm water in this order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Thereafter, the sulfuric acid solution was poured into 9800 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried. Next, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added to the beaker, and the mixture was stirred at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water and dried to obtain a phthalocyanine pigment (PC-4). The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Examples 5 and 6]
(Method for producing phthalocyanine pigment PC-5, 6)
A phthalocyanine pigment (PC-5, PC-6) was obtained in the same manner as in Production Example 4 except that the amount of bromine and the reaction time were changed to the conditions described in Table 1, respectively. The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 7]
(Method for producing phthalocyanine pigment PC-7)
Except that 99.1 parts of NBS was changed to 74.4 parts of N-chlorosuccinimide (NCS) and the reaction time was changed from 3 hours to 4 hours, the same operation as in Production Example 1 was carried out to obtain a phthalocyanine pigment (PC-7). Obtained. The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 8]
(Method for producing phthalocyanine pigment PC-8)
In a three-necked flask, 250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added and stirred at 150 ° C. for 30 minutes. Thereto, 50 parts of hydroxyaluminum phthalocyanine (P1) was added and stirred at 155 ° C. for 30 minutes to dissolve. Further, 58.5 parts of trichloroisocyanuric acid was added and stirred at 190 ° C. for 5 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a phthalocyanine pigment (PC-8). The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Examples 9 to 12]
(Method for producing phthalocyanine pigment PC-9 to 12)
Except for changing the amount of trichloroisocyanuric acid and the reaction time to the conditions described in Table 1, the same operations as in Production Example 8 were performed to obtain phthalocyanine pigments (PC-9 to PC-12), respectively. The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 13]
(Method for producing phthalocyanine pigment PC-13)
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-2) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 45.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 210.0 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the formed precipitate is treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, followed by drying, 165.7 parts. Phthalocyanine pigment (PC-13) was obtained. The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 14]
(Method for producing phthalocyanine pigment PC-14)
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-2) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 125.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 155.0 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, and the mixture was stirred at 25 ° C. for 5 hours. Subsequently, the sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, and then dried to 157.1 parts. Phthalocyanine pigment (PC-14) was obtained. The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 15]
(Method for producing phthalocyanine pigment PC-15)
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-2) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 45.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 205.0 parts of 1,3-diiodo-5,5-dimethylhydantoin (DIDMH) was gradually added, followed by stirring at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the produced precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, and dried to obtain 145.3 parts. Phthalocyanine pigment (PC-15) was obtained. The yield, the yield, the average value of the number of substitutions of halogen atoms represented by X, and the halogen distribution width were as shown in Table 2.

[Production Example 16]
(Method for producing phthalocyanine pigment PCY-1)
To a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of PC-1 and 18.2 parts of diphenyl phosphate were added, heated to 90 ° C., and reacted for 8 hours. After cooling this to room temperature, this reaction solution was poured into 4000 parts of water. The product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PCY-1). Table 4 shows the yield, yield, average value of the number of substitution of halogen atoms represented by X, halogen distribution width, and volume average primary particle size.

[Production Examples 17 to 38]
(Method for producing phthalocyanine pigments PCY-2 to 23)
A phthalocyanine pigment (PCY-2 to PCY23) is obtained in the same manner as in Production Example 16 except that the phthalocyanine pigment (PC-2 to PC-15) and the acidic compound are changed to the conditions described in Table 3, respectively. It was. Table 4 shows the yield, yield, average value of the number of substitution of halogen atoms represented by X, halogen distribution width, and volume average primary particle size.

  The structural formulas of the phthalocyanine pigments (PCY-1 to 23) obtained in Production Examples 16 to 38 are shown below. However, in the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of the number of halogen atoms substituted.

[Comparative Production Example 1]
A phthalocyanine pigment (PCY-24) was obtained in the same manner as in Production Example 16 except that the phthalocyanine pigment (PC-1) was changed to hydroxyaluminum phthalocyanine (P-1). The yield was 98%. The volume average primary particle diameter was 31 nm.

[Comparative Production Example 2]
To a three-necked flask, 50 parts of 4-bromophthalimide, 66 parts of urea, 1.2 parts of ammonium molybdate, 0.4 part of sodium sulfate, and 100 parts of 1-chloronaphthalene were added and stirred. After heating to 150 ° C., 8.3 parts of aluminum chloride and 10.6 parts of urea were added and reacted at 250 ° C. for 7 hours. After cooling to room temperature, the product was filtered, washed with methanol and dried. Next, 500 parts of 98% sulfuric acid was added to the Erlenmeyer flask. The dried product was added and dissolved therein, followed by stirring at room temperature for 1 hour. Thereafter, sulfuric acid was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried. A phthalocyanine pigment (PC−) having an average number of bromine atoms of 4 and a bromine distribution width of 1 was obtained. 16) 35.2 parts were obtained. The yield was 73%.
Subsequently, except having changed the phthalocyanine pigment (PC-1) into (PC-16), operation similar to manufacture example 16 was performed and 39.7 parts of phthalocyanine pigments (PCY-25) were obtained. The yield was 89%. The number of halogen substitutions and the halogen distribution width were the same as PC-16. The volume average primary particle size was 53 nm.

[Comparative Production Example 3]
A phthalocyanine having an average value of the number of bromine atom substitutions of 8 and a bromine distribution width of 1 in the same manner as in Comparative Production Example 2, except that 50 parts of 4,5-dibromophthalic acid was used instead of 4-bromophthalimide. 29.3 parts of pigment (PC-17) were obtained. The yield was 64%. Subsequently, except having changed the phthalocyanine pigment (PC-1) into (PC-17), operation similar to manufacture example 16 was performed and the phthalocyanine pigment (PCY-26) 31.9 parts was obtained. The yield was 91%. The number of halogen substitutions and the halogen distribution width were the same as PC-17. The volume average primary particle diameter of the phthalocyanine pigment was 51 nm.

[Comparative Production Example 4]
Phthalocyanine having an average number of substitutions of chlorine atoms of 8 and a chlorine distribution width of 1 in the same manner as in Comparative Production Example 2, except that 50 parts of 4,5-dichlorophthalic acid is used instead of 4-bromophthalimide. 31.8 parts of pigment (PC-18) were obtained. The yield was 72%. Subsequently, except having changed the phthalocyanine pigment (PC-1) into (PC-18), operation similar to manufacture example 16 was performed and the phthalocyanine pigment (PCY-27) 36.7 parts was obtained. The yield was 90%. The number of halogen substitutions and the halogen distribution width were the same as PC-18. The volume average primary particle size was 53 nm.

<Others / Manufacturing method of fine pigment>
(Production of refined green pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG58-1) was obtained.

(Production of fine green pigment (PG7-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 7 (“GreenGNX” manufactured by CLARIANT), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG7-1) was obtained.

(Production of fine green pigment (PG36-1))
Phthalocyanine green pigment C.I. I. 200 parts of CI Pigment Green 36 (“Green 8G” manufactured by CLARIANT), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG36-1) was obtained.

(Production of refined yellow pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY150-1) was obtained.

(Production of refined yellow pigment (PY138-1))
Quinophthalone yellow pigment C.I. I. 200 parts of Pigment Yellow 138 (“Paliotol Yellow L 0962HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY138-1) was obtained.

(Production of refined yellow pigment (PY 139-1))
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 139 (“Paliotol Yellow L 2146HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY139-1) was obtained.

(Production of refined yellow pigment (PY185-1))
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 185 (BASF “Pariotol Yellow L 1155”), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY185-1) was obtained.

(Production of fine red pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. 200 parts of Pigment Red 254 (“B-CF” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a refined diketopyrrolopyrrole pigment (PR254-1) was obtained.

(Production of refined red pigment (PR177-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Anthraquinone-based fine red pigment (PR177-1) was obtained.

(Production of refined blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor “LIONOL BLUE ES”, specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). It knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine blue pigment (PB15: 6-1) was obtained.

(Production of refined purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A purple refined purple pigment (PV23-1) was obtained.

<Manufacture of pigment dispersion>
About the pigment created above, the pigment dispersion which is one aspect | mode of a coloring composition was manufactured.
(Preparation of resin-type dispersant solution)
A commercially available resin type dispersant EFKA4300 manufactured by BASF and propylene glycol monomethyl ether acetate were mixed to prepare a solution having a nonvolatile content of 40% by mass to obtain a resin type dispersant solution 1.

[Example 1]
(Phthalocyanine pigment dispersion (GP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (GP-1) having a non-volatile component of 20% by mass.
Phthalocyanine pigment (PCY-1): 11.0 parts Acrylic resin solution 1: 17.5 parts Propylene glycol monomethyl ether acetate (PGMAC): 66.5 parts Resin-type dispersant solution 1: 5.0 parts

[Examples 2 to 23, Comparative Examples 1 to 4]
(Phthalocyanine pigment dispersion (GP-2 to 27))
A phthalocyanine / pigment dispersion (GP-2 to 27) was prepared in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to phthalocyanine pigments (PCY-2) to (PCY-27). Each was produced.

<Manufacture of other pigment dispersions>
(PG58 pigment dispersion (GP-28))
A PG58 / pigment dispersion (GP-28) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to (PG58-1).

(PG7 pigment dispersion (GP-29))
A PG7 / pigment dispersion (GP-29) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to (PG7-1).

(PG36 / Pigment dispersion (GP-30))
A PG36 / pigment dispersion (GP-30) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to (PG36-1).

(PY150 / pigment dispersion (YP-1))
A PY150 / pigment dispersion (YP-1) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to PY150-1.

(PY138, pigment dispersion (YP-2))
A PY138 pigment dispersion (YP-2) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to PY138-1.

(PY139 / pigment dispersion (YP-3))
A PY139 • pigment dispersion (YP-3) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to PY139-1.

(PY185 / pigment dispersion (YP-4))
A PY185 / pigment dispersion (YP-4) was prepared in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to PY185-1.

(PR254 / Pigment dispersion (RP-1))
A PR254 / pigment dispersion (RP-1) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to PR254-1.

(PR177 / Pigment dispersion (RP-2))
A PR177 / pigment dispersion (RP-2) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to PR177-1.

(PB15: 6, pigment dispersion (BP-1))
A PB15: 6 • pigment dispersion (BP-1) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to PB15: 6-1.

(PV23 / Pigment Dispersion (VP-1))
A PV23 / pigment dispersion (VP-1) was produced in the same manner as in Example 1 except that the phthalocyanine pigment (PCY-1) was changed to PV23-1.

<Evaluation of pigment dispersion>
(Evaluation of contrast ratio (CR) of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

A phthalocyanine / pigment dispersion (GP-1 to 27) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then 230 ° C. The coated substrate was prepared by heating and cooling for 60 minutes. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C.
The contrast ratio was determined according to the following criteria. The results are shown in Table 5.
A: 9000 or more: extremely good B: 6000 or more but less than 9000: good Δ: 3000 or more but less than 6000: practical use ×: less than 3000: poor

(Evaluation of heat resistance of coating film)
A phthalocyanine / pigment dispersion (GP-1 to 27) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then 230 ° C. The coated substrate was prepared by heating and cooling for 60 minutes. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. [L * (1), a * (1), b * (1)] was measured for the chromaticity of the obtained coating film using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Further, the chromaticity [L * (2), a * (2), b * (2)] after heat treatment at 250 ° C. for 60 minutes is measured, and the color difference ΔE * ab is obtained by the following equation (1). It was.
Formula (1)
ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

The heat resistance was determined according to the following criteria. The results are shown in Table 5.
A: ΔE * ab = 1 or less: Extremely good ○: ΔE * ab = 1-3: Good Δ: ΔE * ab = 3-5: Practical use ×: ΔE * ab = 5 or more: Bad

(Light resistance evaluation of coating film)
A phthalocyanine / pigment dispersion (GP-1 to 27) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then 230 ° C. The coated substrate was prepared by heating and cooling for 60 minutes. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. An ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) was applied on the substrate, and the color before and after irradiation with ultraviolet light for 150 hours using a 470 W / m ² xenon lamp was measured. Thus, the color difference ΔE * ab was obtained. The judgment criteria are the same as in the heat resistance evaluation. The results are shown in Table 5.

(Foreign substance evaluation)
Evaluation of the generation of foreign matter was performed by applying a colored composition on a transparent substrate so that the dried coating film was about 2.0 μm, and heating and cooling in an oven at 250 ° C. for 60 minutes. The number of foreign objects in the inside was counted. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification was 500 times, and the number of foreign matters observable in arbitrary 5 fields of view through transmission was measured. The results are shown in Table 5.
◎: The number of foreign matters is less than 3: Extremely good ○: The number of foreign matters is 3 or more and less than 20: Good Δ: The number of foreign matters is 21 or more and less than 100: Practical use ×: The number of foreign matters is 100 More than: bad

  As in Comparative Example 1, when the phthalocyanine ring was not substituted with halogen, both the contrast ratio and the fastness were low. Further, in Comparative Example 2 in which the number of bromine substitutions was 4 and the halogen distribution width was 1, both the contrast ratio and heat resistance were low, and the light resistance was improved as compared with Comparative Example 1, but foreign matters increased. Although the number of halogen substitutions was 8 as in Comparative Examples 3 and 4 and the halogen distribution was less than 4, the heat resistance was improved as compared with Comparative Example 3, but the number of foreign matters tended to increase further. In the coloring composition containing a phthalocyanine compound having a halogen substitution number of 6 to 15 and a halogen distribution width of 4 or more in Examples 1 to 23 of the present invention, it has a high contrast ratio and excellent fastness (heat resistance and light resistance). In addition, almost no foreign matter was found. In particular, when the halogen substitution number is 8 or more and the halogen distribution is 4 or more, the fastness tends to be higher. From these results, it can be seen that the combination of those having a halogen substitution number of 6 or more and a halogen distribution of 4 or more is the best for achieving both contrast ratio and fastness.

<Production and evaluation of photosensitive coloring composition>
Using the pigment dispersion, a photosensitive coloring composition which is an embodiment of the coloring composition of the present invention was prepared and evaluated.

[Example 24]
(Green photosensitive coloring composition (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a green photosensitive coloring composition (GR-1).
Phthalocyanine / pigment dispersion (GP-1): 22.2 parts PY138 / pigment dispersion (YP-2): 27.8 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd.) "Aronix M-402"): 2.0 parts Dipentaerythritol hexaacrylate photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) ]): 0.3 part Cyclohexanone: 39.0 parts

[Examples 25-49, Comparative Examples 5-8]
The green photosensitive coloring compositions (GR-2 to 33) were respectively obtained in the same manner as in Example 24 except that the total of 50 parts of the pigment dispersion was changed to the types and parts by mass shown in Table 6. Obtained.

(Evaluation of brightness)
The green photosensitive coloring composition (GR-1 to 33) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and then further heated to 230 ° C. for 60 minutes. A coated substrate was obtained in which the chromaticity of the substrate obtained by partial heating was such that x = 0.297 and y = 0.570 in a C light source. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows. The results are shown in Table 6.
A: 66.5 or more: Extremely good ○: 65.9 or more and less than 66.5: Good Δ: 65.3 or more and less than 65.9: Practical use ×: Less than 65.3: Bad

(Evaluation of solvent resistance)
The green photosensitive coloring composition (GR-1 to 33) was applied to a glass substrate on which a black matrix had been formed in advance by spin coating, and then dried at 70 ° C. for 20 minutes in a clean oven. Subsequently, after cooling this board | substrate to room temperature, it exposed to the ultraviolet light through the photomask using the ultrahigh pressure mercury lamp.
Thereafter, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, a heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
The obtained striped green pixel was immersed in N-methyl-2-pyrrolidone (NMP) and methanol (MeOH) for 15 minutes, and the color difference of the green pixel part before and after immersion was measured. The color difference measurement method, calculation method, and evaluation criteria were the same as those in the heat resistance and light resistance evaluation. The results are shown in Table 6.

  The coloring composition using the phthalocyanine compound of the present invention was excellent in lightness and solvent resistance. Moreover, even when the phthalocyanine compound of the present invention was used in combination with another green pigment or yellow pigment, good results were obtained. On the other hand, Comparative Examples 5 to 8 which did not satisfy both the halogen substitution number of 6 to 15 and the halogen distribution width of 4 or more both had low brightness and solvent resistance. From this result, it can be seen that the combination of those having a halogen substitution number of 6 or more and a halogen distribution of 4 or more is the best for achieving both brightness and solvent resistance.

<Production of color filter>
(Red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore diameter of 1 μm to prepare a red photosensitive coloring composition (RR-1).
PR254 / Pigment dispersion (RP-1) / Pigment dispersion: 30.0 parts PR177 / Pigment dispersion (RP-2) / Pigment dispersion: 20.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerization Monomer (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator (“Irgacure 907” manufactured by BASF): 1.2 parts Sensitizer (manufactured by Hodogaya Chemical Co., Ltd. “ EAB-F "): 0.3 part Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a blue photosensitive coloring composition (BR-1).
PB15: 6 • Pigment dispersion (BP-1): 45.0 parts PV23 • Pigment dispersion (VP-1): 5.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M-402"): 2.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.3 part cyclohexanone: 39.0 parts

The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix had been formed in advance by spin coating, and then dried at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp.
Thereafter, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, a heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (GR-2) of the present invention is used to form a green coloring pixel layer in the same manner as the red coloring pixel layer, and the blue photosensitive coloring composition (BR-1) is further formed. A blue colored pixel layer was formed using it to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

  The color filter using the green coloring composition of the present invention has high brightness and excellent contrast ratio, and the effect of the present invention was proved.

Claims (5)

A coloring composition comprising at least a coloring agent, a binder resin and an organic solvent, wherein the coloring agent comprises a phthalocyanine pigment represented by the following general formula (1): .
(In the formula, X represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X is 6 to 15, and the halogen distribution width is Y is 4 or more, Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , wherein R ₁ and R ₂ are each independently In addition, a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or an aryloxy which may have a substituent R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Represents a heterocyclic group which may have a reel group or a substituent.)   Furthermore, the coloring composition of Claim 1 containing a green pigment | dye and / or a yellow pigment | dye.   The green pigment is C.I. I. Pigment Green 7, 36 and 58, which is at least one selected from the group consisting of C.I. I. The coloring composition according to claim 2, wherein the coloring composition is at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150 and 185.   The colored composition according to claim 1, further comprising a photopolymerizable monomer and / or a photopolymerization initiator. A color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one green filter segment is formed by the coloring composition according to any one of claims 1 to 4. A formed color filter.