JP2018013512A - Color filter coloring composition, production method thereof and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition and a color filter that are excellent in color characteristics (lightness) and the contrast ratio and has good temporal stability.SOLUTION: A color filter coloring composition contains at least a colorant, a dispersant, a binder resin and an organic solvent. The colorant contains a phthalocyanine pigment represented by general formula (1) and a halogenated zinc phthalocyanine pigment.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 imaging tube element typified by a C-MOS (ComPlementaRy Metal OXiDe SemiconductorDuctoR: complementary metal oxide semiconductor), a CCD (ChaRge CouPleD Device: 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 (red) 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, pigment compositions containing these aluminum phthalocyanine compounds have problems such as low contrast ratio due to poor dispersibility and poor temporal stability.

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 to provide a coloring composition and a color filter that are excellent in color characteristics (brightness) and contrast ratio, and have good temporal stability.

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 color filter coloring composition comprising at least a colorant, a dispersant, a binder resin, and an organic solvent, wherein the colorant is a phthalocyanine pigment represented by the following general formula (1) and a halogenated compound: The present invention relates to a coloring composition for a color filter comprising a zinc phthalocyanine pigment.

General formula (1)

(In general formula (1), 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, The halogen distribution width is at least 4. Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , R ₁ and R _2. Each independently has a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or a substituent. Represents an optionally substituted alkoxyl group or an aryloxy group which may have a substituent, R ₁ and R ₂ may be combined, and R ₃ may have a hydrogen atom or a substituent; An alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or substituent .R represents a heterocyclic group which may have _4, hydroxyl, optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group Represents.)

  Further, the present invention provides the color filter coloring composition, wherein the color filter coloring composition contains a co-dispersion of the phthalocyanine pigment and the halogenated zinc phthalocyanine pigment represented by the general formula (1). Relates to the composition.

  The present invention also relates to the color composition for a color filter, wherein X is bromine.

  The present invention further relates to the coloring composition for a color filter, further comprising a basic resin type dispersant having an amine value of 10 to 300 mgKOH / g.

  The present invention further relates to the color composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also provides a color filter characterized in that a phthalocyanine pigment and a halogenated zinc phthalocyanine pigment represented by the following general formula (1) are co-dispersed in a pigment carrier using a media-type wet disperser. The present invention relates to a method for producing a colored composition.

General formula (1)

(In general formula (1), 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, The halogen distribution width is at least 4. Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , R ₁ and R _2. Each independently has a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or a substituent. Represents an optionally substituted alkoxyl group or an aryloxy group which may have a substituent, R ₁ and R ₂ may be combined, and R ₃ may have a hydrogen atom or a substituent; An alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or substituent .R represents a heterocyclic group which may have _4, hydroxyl, optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group Represents.)

  The present invention also provides a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one green filter segment is formed of the colored composition. It relates to a color filter.

  The colored composition for a color filter of the present invention can provide a colored composition for a color filter having high brightness and high contrast ratio and good stability over time, and a color filter using the same.

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” in this specification means a color index (CI).

<Colorant>
The coloring composition for a color filter of the present invention is a coloring composition comprising at least a coloring agent, a dispersing agent, a binder resin and an organic solvent, and the coloring agent is represented by the following general formula (1). And a halogenated zinc phthalocyanine pigment.

(Phthalocyanine pigment represented by the general formula (1))
General formula (1)

(In general formula (1), 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, The halogen distribution width is at least 4. Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , R ₁ and R _2. Each independently has a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or a substituent. Represents an optionally substituted alkoxyl group or an aryloxy group which may have a substituent, R ₁ and R ₂ may be combined, and R ₃ may have a hydrogen atom or a substituent; An alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or substituent .R represents a heterocyclic group which may have _4, hydroxyl, optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group Represents.)

  Here, examples of the “halogen” include fluorine, bromine, chlorine, and iodine. Bromine and chlorine are preferable, and bromine is particularly preferable from the viewpoint of lightness. 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. When used in combination, 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.

Examples of the alkyl group in R _{1 to} R ₄ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, and a 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. Examples include an ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group 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 _{1 to} R ₃ include a monocyclic aliphatic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group, and a 4-tert-butylcyclohexyl group, a bornyl group, and an adamantyl group. And condensed aliphatic hydrocarbon groups such as a group. 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. It is preferable that 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. Also, R ₃ and R ₄ is preferably a heterocyclic group which may have an aryl group or a substituted group 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). As the representative examples of the general formula (1), [AlPc (Y)] BRn (4 ≦ n ≦ 16), [AlPc (Y)] Cln (4 ≦ n) ≦ 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.

Y is preferably a structure represented by —OP (═O) R ₁ R ₂ .

(Halogenated zinc phthalocyanine pigment)
The coloring composition for a color filter of the present invention is characterized by containing a zinc halide phthalocyanine pigment together with the phthalocyanine pigment represented by the general formula (1). “Halogen” includes fluorine, bromine, chlorine and iodine, with bromine and chlorine being preferred. Examples of the halogenated zinc phthalocyanine pigment include C.I. I. Examples include zinc phthalocyanine pigments described in CI Pigment Green 58 and 59, JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and International Publication No. 2015/118720 pamphlet. However, it is not particularly limited to these.

(Other colorants)
The coloring composition for a color filter of the present invention may contain other colorants for the purpose of adjusting the chromaticity and the like as long as the effects of the present invention are not impaired. Other colorants are not particularly limited, but include green pigments and yellow pigments.

Examples of green pigments include green pigments and green dyes.
Examples of the green pigment include C.I. I. And CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55. It is not limited to.

  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. Although a modern dye etc. are mentioned, it is not specifically limited to these.

Examples of yellow pigments include yellow pigments and yellow dyes.
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 yellow pigments 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.

(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 pigment 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).

<Method for Producing Color Filter Coloring Composition (Pigment Dispersion)>
The coloring composition of the present invention comprises a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, and a colorant in a pigment carrier composed of a binder resin and / or an organic solvent, preferably together with a dispersion aid. It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a vertical sand mill, an annular bead mill, or an attritor. At this time, the specific aluminum phthalocyanine pigment represented by the general formula (1), the halogenated zinc phthalocyanine pigment, and other colorants may be simultaneously dispersed in the pigment carrier, or separately dispersed in the pigment carrier. However, it is possible to use a co-dispersion in which the specific aluminum phthalocyanine pigment represented by the general formula (1) and the halogenated zinc phthalocyanine pigment are simultaneously dispersed in the pigment carrier. More preferable from the viewpoint.

(Covariance)
As a method for producing a colored composition in the present invention, it is preferable to co-disperse a phthalocyanine pigment represented by the general formula (1) and a zinc halide phthalocyanine pigment in a pigment carrier using a media type wet disperser. . Co-dispersion means that two or more pigments are mixed and dispersed together under the same conditions. By co-dispersing, it is possible to finely and finely disperse the pigment fine particles, and it is possible to produce a coloring composition for a color filter having excellent dispersion stability after dispersion.

  The co-dispersing method is, for example, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical type, in which at least two pigments are mixed with a dispersant and pre-dispersed with a homogenizer or the like. It can be carried out by dispersing by various dispersing means such as a sand mill, an annular bead mill, or an attritor. Especially, it is preferable to perform co-dispersion using a media-type wet disperser.

  In the present invention, when co-dispersion is performed, it is more preferable to include at least one dispersant because the dispersibility of the pigment can be improved.

<Dispersant>
When dispersing the colorant in the pigment carrier, a dispersant such as a dye derivative, a resin-type dispersant, and a surfactant may be appropriately contained. Since the dispersant has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the pigment carrier using the dispersant has good brightness and viscosity stability. .

The resin-type dispersant has a colorant affinity part that has the property of adsorbing to the colorant and a part that is compatible with the pigment carrier, and adsorbs to the colorant to stabilize the dispersion of the colorant into the pigment carrier. It works to make it. 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 addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, 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 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-TeRRa- U, 203, 204, or BYK-P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 11200, 130 made by Lubrizol Japan, Lactimon, Lactimon-WS, or Bykumen, etc. 0, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 3300, 33500, 32600, 34750, 35100, 35200, 36600, 37500, 38500, 39000, 41000, 41090, 53095, 56000, 55000, 7100, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060 manufactured by BASF , 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450 351, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. , PB822, PB824, etc.

  The content of the resin-type dispersant is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the content of the resin-type dispersant is less than 0.1 parts by weight, it is difficult to obtain the added effect, and when the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. is there.

(Basic resin type dispersant)
It is preferable that the coloring composition for color filters of this invention contains the basic resin type dispersing agent whose amine value is 10-300 mgKOH / g among resin type dispersing agents. More preferably, it is 50-300 mgKOH / g. When a basic resin type dispersant having an amine value within this range is used, the pigment is sufficiently adsorbed by the adsorption or reaction with respect to the acidic component in the pigment carrier, whereby the dispersion becomes good and the dispersion stability is excellent. Since the zinc halide phthalocyanine pigment, which is an acidic pigment, is adsorbed to the surface of the specific aluminum phthalocyanine pigment, which is a neutral pigment, the basic resin-type dispersant having a high amine value is used as the resin-type dispersant used during dispersion. By using this, it is possible to obtain a coloring composition for a color filter having excellent dispersibility and dispersion stability.

  As a number average molecular weight of the basic resin type dispersing agent used by this invention, 500-50000 are preferable normally, and 3000-30000 are especially more preferable. When the number average molecular weight is less than 500, the effect of steric repulsion due to the pigment affinity group, the effect of compatibility with the pigment carrier, and the effect of compatibility with the pigment carrier and solvent when using a solvent are small, It may be difficult to prevent aggregation of the pigment, and the viscosity of the dispersion may increase. On the other hand, if the number average molecular weight is 50000 or more, the amount of resin added for dispersion increases, and the pigment concentration in the coating film may be lowered.

  As the basic resin type dispersant having an amine value of 10 to 300 mgKOH / g, various types of resin systems such as vinyl, urethane, polyester, polyether, or polyamide can be used. A vinyl monomer copolymer type that is easy and excellent in various resistances is preferable. Specifically, N, N-disubstituted amino group-containing vinyl monomer units, alkyl (meth) acrylate monomer units, and other vinyl monomers Copolymer resins with units are preferred.

  As N, N-disubstituted amino group-containing vinyl monomer units, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, Examples thereof include N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, and N, N-diethylaminoethyl (meth) acrylamide, but are not necessarily limited thereto. These monomer units are adsorbed to the pigment as basic group-containing monomer units.

  As alkyl (meth) acrylate monomer units, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, It is obtained by the reaction of unsaturated monocarboxylic acid such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, or lauryl (meth) acrylate with alkyl alcohol having 1 to 18 carbon atoms (meta ) Acrylic esters and the like, but are not necessarily limited thereto. These monomer units act as pigment carrier affinity groups.

  Other vinyl monomer units include nitro group-containing vinyl monomers such as (meth) acrylonitrile, vinyl aromatic monomers such as styrene, α-methylstyrene, or benzyl (meth) acrylate, 2-hydroxyethyl ( Hydroxyl group-containing vinyl monomers such as (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol (meth) acrylate, (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, etc. Amide group-containing vinyl monomers, vinyl monomers such as N-methylol (meth) acrylamide or dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, or N-butoxime Alkoxymethyl group-containing vinyl monomers such as ru (meth) acrylamide, olefins such as ethylene, propylene or isoprene, dienes such as chloroprene or butadiene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, Examples thereof include vinyl ethers such as n-butyl vinyl ether or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate, which are appropriately used according to the purpose, but are not necessarily limited thereto.

  Polymers having primary amino group-containing monomer units such as allylamine, or polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, or poly (aminomethylated) epoxy resin, polyester resin, acrylic resin Alternatively, a comb-shaped basic resin dispersant modified with a polyether resin or the like can also be used.

  As a commercially available product of such a preferable basic resin type dispersant, for example, DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2050, manufactured by Big Chemie Japan, 2150, 2163, 2164, BYK-LPN6919, Nippon Lubrizol Corporation SOLPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000 , 53095, 56000, 7100, EFKA4300, 4330, 4046, 4060, 4080 from BASF.

(Dye derivative)
In the coloring composition for a color filter of the present invention, a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine as a pigment derivative. Compounds can be included. Examples of such a pigment derivative include, for example, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5-9469. JP 2001-335717 A, JP 2003-128669 A, JP 2004-091497 A, JP 2007-156395 A, JP 2008-094773 A, JP 2008-094986 A, Those described in Japanese Unexamined Patent Application Publication No. 2008-095007, Japanese Patent Application Laid-Open No. 2008-195916, Japanese Patent No. 45855781, and the like can be used, and these can be used alone or in combination of two or more. When a pigment derivative is used, one having a quinophthalone skeleton is preferable from the viewpoint of brightness.

  A pigment derivative having a copper phthalocyanine structure as a base skeleton is also preferable because the dispersibility of the colorant is improved and the heat resistance and light resistance of the colored composition are improved. The pigment derivative having a copper phthalocyanine structure as a base skeleton is preferably added in an amount of 10 to 40 parts by weight with respect to 100 parts by weight of the aluminum phthalocyanine pigment in the colorant.

  Moreover, the coloring composition for a color filter in the present invention can be obtained by using both a basic resin type dispersant having an amine value of 10 to 300 mgKOH / g and a pigment derivative having a basic substituent or an acidic substituent. It has excellent stability.

  The content of the pigment derivative is preferably 1.0 part by weight or more, more preferably 3 parts by weight or more, and most preferably 5 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 30 parts by weight or less, more preferably 25 parts by weight or less.

(Surfactant)
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.

  The content of the surfactant is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the content of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<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.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

  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 carboxyl groups, aliphatic groups and aromatic groups that act as affinity groups for the pigment carrier and solvent is important for the dispersibility, penetrability, developability, and durability of the pigment, with an acid value of 20-300 mg KOH / It is preferable to use g resin. 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 preferably used in an amount of 30 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant, and has a high colorant concentration and good color characteristics. 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 to 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.

<Production of photosensitive coloring composition (resist material) for color filter>
When the coloring composition for color filter of the present invention is used as a photosensitive coloring composition (resist material), it can be prepared as a solvent developing type or alkali developing type coloring composition. The solvent development type or alkali development type coloring composition is a mixture of the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, a dispersion aid, and an additive. Can be adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and other acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, ru (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (P-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (P-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like. These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  Among these, it is preferable to contain an acetophenone compound or an oxime ester compound as a photopolymerization initiator in order to produce a color filter having a good pattern shape and linearity.

  The oxime ester-based compound absorbs ultraviolet rays to cleave the N—O bond of the oxime to generate an iminyl radical and a benzoyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. As oxime ester photoinitiators, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 1,2- Octadione-1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is preferred.

  An acetophenone compound is cleaved to generate a radical having an amino group that becomes an active hydrogen donor, so that it is possible to reduce the influence of oxygen inhibition, which is a problem in UV curing, and to cure the surface of the coating film. . Examples of the acetophenone compound include α-aminoalkylacetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone is preferred.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, 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, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone. These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-teRt-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -P-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-diteRt-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate-based antioxidant include phenyl salicylate, P-octylphenyl salicylate, and P-teRt butylphenyl salicylate. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition because the brightness and sensitivity are good.

<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 leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  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 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with 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. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-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 weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Removal of coarse particles>
The colored 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, “parts” and “%” represent “parts by mass” and “mass%”, respectively. “PGMAc” means propylene glycol monomethyl ether acetate.

  Moreover, the weight average molecular weight (Mw) of the resin, the average molecular weight of the basic resin type dispersant and the amine value of the basic resin type dispersant, the number of halogen substitutions in the pigment, and the calculation method of the halogen distribution width in the pigment Is as follows.

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

(Average molecular weight of basic resin type dispersant)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the basic resin type dispersant are HLC-8320GPC (manufactured by Tosoh Corporation) as a device, SUPER-AW3000 as a column, and 30 mM triethylamine as an eluent. And polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using an N, N-dimethylformamide solution of 10 mM LiBR.

(Amine value of basic resin type dispersant)
The amine value of the basic resin type dispersant is a value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 into a solid content.

(Number of halogen substitutions in the pigment)
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 in pigment)
The halogen distribution width in the pigment was determined using a time-of-flight mass spectrometer (autoful XIII (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.

<Method for producing refined pigment>
(Fine refined pigment (P-1))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the formula (50), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out for 6 hours at ° C. 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 pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 10.1 bromine atoms substituted on the resulting phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain a phthalocyanine pigment (P-1) represented by the following formula (51). The halogen distribution width was 9.

Formula (50)

Formula (51)

(Fine refined pigment (P-2))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the above formula (50), 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 20 ° C. for 4 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 pigment in which 8.0 average bromine atoms were substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring, and 15.8 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (P-2) represented by the following formula (52). The halogen distribution width was 9.

Formula (52)

(Fine refined pigment (P-3))
203 parts of aluminum bromide, 47 parts of sodium bromide and 5 parts of ferric bromide were heated and melted, and 50 parts of a phthalocyanine pigment represented by the formula (50) was added at 140 ° C. The temperature was raised to 160 ° C., and reaction was carried out at 160 ° C. for 7 hours while blowing 215.4 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, this mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 15.0 bromine atoms were substituted on the phthalocyanine ring on average. Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having 15.0 bromine atoms substituted on the phthalocyanine ring and 10.8 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain a phthalocyanine pigment (P-3) represented by the following formula (53). The halogen distribution width was 4.

Formula (53)

(Refinement pigment (P-4))
To a three-necked flask, add 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring prepared in (P-2), and 13.8 parts of diphenylphosphinic acid. The mixture was heated to 90 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain a phthalocyanine pigment (P-4) represented by the following formula (54). The halogen distribution width was 9.

Formula (54)

(Fine refined pigment (P-5))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicclo [5.4.0] unDec-7-ene) was added, and the temperature was raised and refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (55).

Formula (55)

  Next, 250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added to the three-necked flask and stirred at 150 ° C. for 30 minutes. Thereto was added 50 parts of an aluminum phthalocyanine pigment represented by the formula (55), and the mixture was stirred at 155 ° C. for 30 minutes to be dissolved. 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 pigment in which 8.1 average chlorine atoms were substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 8.1 bromine atoms substituted on the resulting phthalocyanine ring, and 22.6 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (P-5) represented by the following formula (56). The halogen distribution width was 8.

Formula (56)

(Fine refined pigment (P-6))
In a reaction vessel, 100 parts of aluminum phthalocyanine pigment represented by the formula (55) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following formula (57).

Formula (57)

  Subsequently, 100 parts of the aluminum phthalocyanine pigment represented by the formula (57), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. . This kneaded product is put into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. Pigmented pigment (P-6) was obtained.

(Refinement pigment (P-7))
Phthalocyanine green pigment C.I. I. 100 parts of Pigment Green 58 (“FASTGENGREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product is put into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 97 parts of a modified pigment (P-7) were obtained.

(Fine refined pigment (P-8))
A 300 mL flask was charged with 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 52 parts of bromine. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of crushed sodium chloride, 32 parts of diethylene glycol and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a refined pigment (P-8). The obtained finely divided pigment (P-8) has an average number of halogen atoms of 12.69 in one molecule based on fluorescent X-ray analysis, of which the average number of bromine atoms is 8.54 and the number of chlorine atoms. The average was 4.16 zinc halide phthalocyanine pigments.

(Refinement pigment (P-9))
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride. This 1-chloronaphthalene solution had light absorption at 600 to 700 nm. Halogenation was performed by mixing 2.9 parts of sulfuryl chloride, 3.5 parts of anhydrous aluminum chloride, 0.43 parts of sodium chloride, and 1.0 part of zinc phthalocyanine at 40 ° C. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a partially chlorinated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts of a purified partially chlorinated zinc phthalocyanine crude pigment. 1.0 part of this partially chlorinated zinc phthalocyanine crude pigment, 7.0 parts of pulverized sodium chloride, 1.6 parts of diethylene glycol, and 0.09 part of xylene were charged into a double arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out into 100 parts of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a finer pigment (P-9). The obtained refined pigment (P-9) has an average composition of ZnPcCl ₁₃ H ₃ (Pc: phthalocyanine) from a halogen content analysis by a mass spectrometer (device name: BRUKER REFLEXII Bruker Daltonics Co., Ltd.). The average chlorine ratio in the molecule was 81.3%.

(Fine refined pigment (P-10))
C. I. 100 parts of Pigment Yellow 138 (PY138) ("Pariotol Yellow K0960-HD" manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts fine. Pigmented pigment (P-10) was obtained.

<Method for producing basic resin-type dispersant>
(Basic resin type dispersant solution 1)
A reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 4.0 parts of AIBN (2,2′-azobisisobutyronitrile) and 133 parts of propylene glycol monomethyl ether acetate, and then ethyl. 7.8 parts acrylate, 39.0 parts methyl methacrylate, 31.2 parts n-butyl methacrylate, and 5.0 parts 2,2,6,6, -tetramethyl-1-piperidinyloxy radical (TEMPO) Was replaced with nitrogen for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 12 hours to perform living radical polymerization. Next, 22.0 parts of N, N-dimethylaminoethyl methacrylate was dissolved in this reaction solution, followed by replacement with nitrogen for 30 minutes, and living radical polymerization was performed at 80 ° C. for 12 hours. 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 monomethyl ether so that the nonvolatile content was 50% by weight in the previously synthesized dispersant. Acetate was added to prepare a basic resin type dispersant solution 1. It was Mw8100 of the polymer as a result of GPC measurement. In this way, a basic resin type dispersant solution 1 having an amine value per solid content of 79 mgKOH / g was obtained.

(Basic resin type dispersant solutions 2 to 4)
Basic resin type dispersant solutions 2 to 4 were obtained in the same manner as the basic resin type dispersant solution 1 except that the composition was changed to the composition shown in Table 1.

<Binder resin production method>
(Adjustment of acrylic resin solution 1)
233 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 30 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 19 parts of benzyl methacrylate, 16 parts of methyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, and 2, A mixture of 1.33 parts of 2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further heated and stirred at 80 ° C. for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of acrylic resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 50% by weight. Acrylic resin solution 1 was prepared by adding ether acetate. As a result of GPC measurement, this acrylic resin solution 1 had a weight average molecular weight (Mw) of 16000.

<Manufacture of pigment dispersion>
[Example 1]
(Preparation of pigment dispersion (D-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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (D-1) was obtained. The pigment dispersion was adjusted with PGMAc (propylene glycol monomethyl ether acetate) to a solid content of 20% by weight.
Fine pigment (P-1): 9.6 parts Fine pigment (P-7): 2.4 parts Basic dispersant solution 1: 6.0 parts Acrylic resin solution 1: 25.0 parts PGMAc: 57. 0 copies

[Examples 2 to 12, Comparative Examples 1 to 3]
(Preparation of pigment dispersions (D-2 to 12) and (D-14 to 16))
Except having changed into the composition shown in Table 2, it carried out similarly to the pigment dispersion (D-1), and obtained the pigment dispersion (D-2-12) and (D-14-16).

[Example 13]
(Preparation of pigment dispersion (D-13))
The following mixture was stirred and mixed to be uniform and then filtered through a 5.0 μm filter to obtain a pigment dispersion (D-13).
Pigment dispersion (D-15): 80.0 parts Pigment dispersion (D-16): 20.0 parts

(Preparation of yellow pigment dispersion (D-17))
A yellow pigment dispersion (D-17) was obtained in the same manner as the pigment dispersion (D-1) except that the composition was changed to the composition shown below.
Refined pigment (P-10): 12.0 parts Basic dispersant solution 1: 6.0 parts Acrylic resin solution 1: 25.0 parts PGMAc: 57.0 parts

<Evaluation of pigment dispersion>
The obtained pigment dispersions (D-1 to 16) were evaluated for brightness, contrast ratio, and viscosity stability by the following methods. In the brightness evaluation and contrast ratio evaluation, when the pigment dispersion (D-1 to 16) is used as a coated substrate, x (c) = 0.280 and y (c) = 0.600 with a C light source. It was used by mixing with a yellow pigment dispersion (D-17). The evaluation results are shown in Table 3.

(Brightness evaluation of pigment dispersion)
The obtained pigment dispersions (D-1 to 16) were mixed with the yellow pigment dispersion (D-17) as described above, and y-cooked on a 100 mm × 100 mm, 1.1 mm thick glass substrate with a C light source. (C) = 0.600 was applied using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain a coated substrate. Then, after heating and cooling at 230 ° C. for 20 minutes, the chromaticity of the obtained coating film was measured for brightness Y (C) using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).
The brightness was evaluated according to the following criteria.
A: Y (C) is 58.7 or more. O: Y (C) is 58.3 or more and less than 58.7. Δ: Y (C) is 57.9 or more and less than 58.3. X: Y (C) is 57. Less than 9

(Evaluation of contrast ratio of pigment dispersion)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered. 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, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.
A substrate for contrast ratio measurement was prepared and measured in the same manner as the substrate for brightness evaluation. The contrast ratio was evaluated according to the following criteria.
◎: 16500 or more ○: 14000 or more and less than 16500 ×: less than 14000

(Evaluation of viscosity stability of pigment dispersion)
The viscosity at 25 ° C. immediately after dispersion of the obtained pigment dispersion (D-1 to 16) and the viscosity after storage for 7 days in a constant temperature room at 40 ° C. were measured using an E-type viscometer (TUE-20L type manufactured by TOKI SANKGYO) ) At a rotation speed of 20 RPm. The viscosity on the day of preparation of the colored composition is the initial viscosity (η0: mPa · s) and the viscosity after storage for 7 days in a constant temperature room at 40 ° C (η7: mPa · s). It was evaluated with.
◎: η7 / η0 is 1.05 or less ○: η7 / η0 is larger than 1.05 and 1.20 or less △: η7 / η0 is larger than 1.20 and 1.50 or less ×: η7 / η0 is 1.50 or less large

  As shown in Examples 1 to 13, each pigment dispersion showed high brightness and contrast ratio, and viscosity stability was also good. Further, comparing Example 1 using a co-dispersion with Example 13 using a monodisperse mixture, Example 1 using a co-dispersion is particularly excellent in terms of contrast ratio and viscosity stability. It was shown that In Comparative Examples 1 and 3, since the colorant was not the phthalocyanine compound represented by the general formula (1), the lightness was very low. In Comparative Example 2, since no zinc halide phthalocyanine pigment was contained, the contrast ratio was low and the viscosity stability was poor.

<Production of photosensitive coloring composition>
[Example 14]
(Preparation of photosensitive coloring composition (R-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare a photosensitive green coloring composition (R-1).
Pigment dispersion (D-1): 15.0 parts Yellow pigment dispersion (D-17): 22.5 parts Acrylic resin solution 1: 8.2 parts Photopolymerizable monomer (“Aronix M, manufactured by Toagosei Co., Ltd.) -402 "): 3.0 parts Photopolymerization initiator (" OXE-02 "manufactured by BASF): 0.4 parts PGMAc: 50.9 parts

[Examples 15 to 26, Comparative Examples 4 to 6]
(Preparation of photosensitive coloring composition (R-2 to 16))
A photosensitive colored composition (R-2 to 16) was obtained in the same manner as the photosensitive colored composition (R-1) except that the pigment dispersion (D-1) was changed to the pigment dispersion shown in Table 4. It was. The ratio of the pigment dispersion (D-1 to 16) and the yellow pigment dispersion (D-17) matches the chromaticity of x = 0.280 and y = 0.600 with the C light source during coating film evaluation. As described above, the ratio was appropriately changed and adjusted.

<Evaluation of photosensitive coloring composition>
About the obtained photosensitive coloring composition (R-1 to 16), brightness evaluation, contrast ratio evaluation, and viscosity stability evaluation were performed by the following methods. The evaluation results are shown in Table 4.

(Lightness evaluation of photosensitive coloring composition)
The brightness was measured in the same manner as in the evaluation of the pigment dispersion. The prepared photosensitive coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the film thickness of the dried coating film was about 2.5 μm, and a predetermined pattern was formed. After performing ultraviolet exposure through the mask which has, the alkali developing solution was sprayed with the spray and the uncured part was removed, and the desired pattern was formed. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. The brightness was measured using the obtained coated substrate.
The brightness was evaluated according to the following criteria.
◎: Y (C) is 58.4 or more ○: Y (C) is 58.1 or more and less than 58.4 Δ: Y (C) is 57.8 or more and less than 58.1 ×: Y (C) is Less than 57.8

(Contrast ratio evaluation of photosensitive coloring composition)
The contrast ratio was measured in the same manner as the evaluation of the pigment dispersion. The prepared photosensitive coloring composition was applied to a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the film thickness of the dried coating film was about 2.5 μm. After the ultraviolet exposure, an alkali developer was sprayed by spraying to wash the coating film to obtain a measurement substrate. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. The contrast ratio was measured using the obtained coated substrate.
The contrast ratio was evaluated according to the following criteria.
◎: 16000 or more ○: 14000 or more and less than 16000 ×: less than 14,000

(Evaluation of viscosity stability of photosensitive coloring composition)
Viscosity stability was measured in the same manner as the pigment dispersion, and evaluated according to the following criteria.
◎: η7 / η0 is 1.02 or less ○: η7 / η0 is greater than 1.02 and 1.15 or less △: η7 / η0 is greater than 1.15 and 1.30 or less ×: η7 / η0 is 1.30 or less large

  The photosensitive coloring composition also showed the same results as the pigment dispersion. As shown in Examples 14 to 26, each pigment dispersion exhibited high brightness and contrast ratio, and viscosity stability was also good. In addition, when Example 14 using a co-dispersion and Example 26 using a monodispersed mixture are compared, Example 14 using a co-dispersion, in particular the contrast result of the pigment dispersion, is particularly contrast. It was shown that the ratio and viscosity stability were excellent. In Comparative Examples 4 and 6, since the colorant was not the phthalocyanine compound represented by the general formula (1), the lightness was very low. In Comparative Example 5, since no halogenated zinc phthalocyanine pigment was contained, the contrast ratio was low and the viscosity stability was poor.

<Manufacture of color filters>
Next, a black matrix is patterned on a glass substrate, and the colorant used in the photosensitive coloring composition (R-1) is formed on the substrate by a spin coater. I. Pigment ReD 254 / C.I. I. Pigment ReD 177 = 5.1 parts / 0.9 parts except that the photosensitive red coloring composition prepared in the same manner as in Example 14 was used in a C light source (hereinafter also used for green and blue) x = 0 .645, y = 0.330 was applied to form a colored film. Next, the film was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed.

  Similarly, the photosensitive green coloring composition (R-1) obtained in Example 14 was applied so that x = 0.280 and y = 0.600, and a green filter segment was obtained. In addition, the colorant used in the photosensitive coloring composition (R-1) is C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 3.6 parts / 2.4 parts were used, except that x = 0.149 and y = 0.0.05 using a photosensitive blue coloring composition prepared in the same manner as in Example 14 The color filter was obtained by applying a thin film to form a blue filter segment.

  When the colored composition in the present invention is used, it is possible to produce a color filter having excellent brightness in a wide chromaticity range.

Claims (7)

A color filter coloring composition comprising at least a colorant, a dispersant, a binder resin and an organic solvent, wherein the colorant comprises a phthalocyanine pigment represented by the following general formula (1) and a halogenated zinc phthalocyanine pigment: A coloring composition for a color filter, comprising:
General formula (1)


(In general formula (1), 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, The halogen distribution width is at least 4. Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , R ₁ and R _2. Each independently has a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or a substituent. Represents an optionally substituted alkoxyl group or an aryloxy group which may have a substituent, R ₁ and R ₂ may be combined, and R ₃ may have a hydrogen atom or a substituent; An alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or substituent .R represents a heterocyclic group which may have _4, hydroxyl, optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group Represents.)   The coloring composition for a color filter according to claim 1, wherein the coloring composition for a color filter contains a co-dispersion of a phthalocyanine pigment represented by the general formula (1) and a zinc halide phthalocyanine pigment. object.   The coloring composition for a color filter according to claim 1 or 2, wherein X is bromine.   Furthermore, the coloring composition for color filters as described in any one of Claims 1-3 containing the basic resin type dispersing agent whose amine value is 10-300 mgKOH / g.   Furthermore, the coloring composition for color filters as described in any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator. A method for producing a coloring composition for a color filter, comprising co-dispersing a phthalocyanine pigment represented by the following general formula (1) and a zinc halide phthalocyanine pigment in a pigment carrier using a media-type wet disperser .
General formula (1)

(In general formula (1), 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, The halogen distribution width is at least 4. Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , R ₁ and R _2. Each independently has a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or a substituent. Represents an optionally substituted alkoxyl group or an aryloxy group which may have a substituent, R ₁ and R ₂ may be combined, and R ₃ may have a hydrogen atom or a substituent; An alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or substituent .R represents a heterocyclic group which may have _4, hydroxyl, optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group Represents.)   6. A color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein at least one green filter segment is colored according to any one of claims 1-5. A color filter formed from the composition.