JP2010195911A - Polyhalogenated phthalocyanine pigment composition and coloring composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyhalogenated phthalocyanine pigment composition which, when used for a color filter used in a color liquid crystal display device and a solid-state image sensor, can make the color filter excellent in display quality and high in contrast and lightness. <P>SOLUTION: A polyhalogenated phthalocyanine pigment composition obtained by wet-grinding a polyhalogenated phthalocyanine, an azoic pigment derivative and a styrene acrylic resin in the presence of an inorganic salt and an organic solvent is provided. A color filter containing the polyhalogenated phthalocyanine pigment composition in its green pixel area is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyhalogenated phthalocyanine pigment composition, and more specifically, it is finely sized to a uniform particle size, has a very good dispersibility, has excellent viscosity characteristics, a color liquid crystal display device and a solid When used in a color filter used in an image sensor, the present invention relates to the above pigment that can form a uniform colored film with higher contrast and brightness and provide a color filter with excellent display quality.

Halogenated phthalocyanine pigments have hues ranging from blue to green depending on the number of halogen groups. In particular, polyhalogenated copper phthalocyanine pigments have been used as paints, printing inks, and colorants for plastics as green pigments. In recent years, it has also been used as a color filter colorant for liquid crystal displays and an ink colorant for inkjet ink recording. C. a polyhalogenated copper phthalocyanine pigment. I. Pigment Green 7 and 36 are used as green pigments for forming the green pixel portion of the colored pixel portions of the color filter, and a yellow pigment is used in combination for color matching as necessary. .
As the liquid crystal display expands from a monitor application to a large color television application, a high contrast ratio and a high brightness of the color filter for the liquid crystal display are required. As a result, in order to realize a high contrast ratio of the color filter, the pigment is further refined and sized so as to be higher than the level normally used in printing ink, gravure ink and colorant.

  The method for producing a green pigment comprises the production of a crude polyhalogenated phthalocyanine pigment by halogenation of phthalocyanine, and the pigmentation to make the crude pigment a product pigment having a clear and high coloring power. Crude polyhalogenated phthalocyanine pigments can be produced by co-molten salts of aluminum chloride and sodium chloride, halogenated with titanium tetrachloride as a solvent, solid phase method with inorganic salt powder as a carrier, halogenated phthalimide, etc. A method using a cyclocondensation reaction is known.

  The crude polyhalogenated phthalocyanine pigment synthesized by any method has an amorphous crystal form, an extremely fine particle size, and an agglomerated state. Therefore, as it is, it cannot be sufficiently dispersed in the varnish and is not suitable as a coloring material. Therefore, it is necessary to perform crystallization and pigmentization to a pigment having an optimum particle size and particle size distribution.

  For example, Patent Document 1 discloses a method in which crude polyhalogenated phthalocyanine is crystallized with an organic solvent to form a pigment, and a method in which crystal is grown by heating while adding a share by wet grinding to form a pigment. However, since these methods grow the particles to form pigments, the only way to obtain fine particles is to complete the pigmentation at a lower temperature and in a shorter time in order to prevent particle growth. However, since polyhalogenated phthalocyanine pigments are difficult to crystallize unlike other pigments, when trying to obtain fine particles, some pigments remain without being pigmented, resulting in poor dispersion and reduced contrast and the like. There was a problem.

Therefore, Patent Document 2 discloses a method in which particles are first grown by solvent treatment or wet pulverization, the particles are enlarged to form a pigment, and then wet pulverization is performed at a low temperature to obtain a fine pigment. Yes. However, this method has to be pigmented twice and is very inefficient. Moreover, miniaturization is incomplete by this method, and the high contrast and brightness required by the market for color filters could not be obtained.
Regarding the refinement of pigments, generally, as shown in Patent Document 3, if the pigment derivative has the base skeleton of the pigment to be refined or a similar skeleton, the adsorption to the pigment is stronger and the crystal growth The effect which suppresses is high. In addition, it is known that the kneading state at the time of wet pulverization is good and is effective in miniaturization. However, although polyhalogenated phthalocyanine has a pigment derivative having a base skeleton of a pigment as shown in Patent Document 4, no significant effect is seen in miniaturization, and the azo dye derivative having no host skeleton used this time It became clear that the method has an effect on miniaturization.

JP 2002-250812 A JP 2008-285532 A JP 2001-220520 A JP 2006-309171 A

  An object of the present invention is to provide a polyhalogenated phthalocyanine pigment composition capable of obtaining a color filter having a particularly high contrast and brightness with excellent display quality when used in a color filter used in a color liquid crystal display device and a solid-state imaging device. To do.

As a result of diligent research to achieve the above-mentioned object, the present inventors have succeeded in making the pigment finer and easier to disperse by using an azo dye derivative and a styrene acrylic resin during wet pulverization, thereby completing the present invention. I came to let you.
That is, the present invention relates to a polyhalogenated phthalocyanine pigment composition characterized by wet pulverizing a polyhalogenated phthalocyanine and an azo dye derivative represented by the general formula (1) in the presence of an inorganic salt and an organic solvent.
General formula (1)

In general formula (1),
A and B represent a hydroxyl group or a basic substituent represented by the following general formulas (2) to (3).

General formula (2)

General formula (3)

In general formulas (2) and (3),
R ₁ and R ₂ each independently represents a saturated or unsaturated alkyl group which may be substituted, or a heterocyclic ring which may be substituted containing a nitrogen, oxygen or sulfur atom in R ₁ or R _2. . However, n represents the integer of 1-10.

Furthermore, the present invention is a polyhalogenated phthalocyanine characterized by wet-pulverizing a polyhalogenated phthalocyanine, an azo dye derivative represented by the above general formula (1), and a styrene acrylic resin in the presence of an inorganic salt and an organic solvent. The present invention relates to a pigment composition.
Furthermore, the present invention provides that the polyhalogenated phthalocyanine is C.I. I. Pigment green 7, C.I. I. The present invention relates to the pigment composition which is CI Pigment Green 36.

  Furthermore, this invention relates to the coloring composition characterized by including the said pigment composition and a pigment carrier.

Furthermore, this invention relates to the coloring composition characterized by including the said pigment and a yellow pigment.
Furthermore, this invention relates to the color filter formed by containing the said pigment composition in a green pixel part.

The polyhalogenated phthalocyanine pigment composition obtained in the present invention has preferable absorption wavelength characteristics for use in color filters used in color liquid crystal display devices and solid-state imaging devices, and when used in color filters. A colored film having particularly high contrast and brightness, which is important as its characteristics, can be obtained.

  Next, the present invention will be described in more detail with reference to embodiments of the invention.

  The polyhalogenated phthalocyanine used in the present invention has at least four or more halogen atoms, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. The central metal of the polyhalogenated phthalocyanine is Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, or Sn, and more preferably Cu. Depending on the valence of the central metal, a halogen atom or a hydroxyl group is bonded to the axis. Further, the polyhalogenation method of phthalocyanine can be selected from conventionally known methods and is not particularly limited. Examples of the polyhalogenated phthalocyanine include C.I. I. Pigment green 7, C.I. I. Pigment Green 36 is more preferable.

Examples of the azo dye derivative used in the present invention include compounds represented by the following general formula (1).
General formula (1)

In general formula (1),
A and B represent a hydroxyl group or a basic substituent represented by the following general formulas (2) to (3).

General formula (2)

General formula (3)

In general formulas (2) and (3),
R _1, R ₂ are, each independently represent a optionally substituted saturated or unsaturated alkyl group, or R _1, R _2, nitrogen, oxygen or sulfur atom, the heterocyclic ring which may be substituted . However, n represents the integer of 1-10.
As the azo dye derivative used in the present invention, the following compounds can be used, but are not limited thereto.

  The styrene acrylic resin used in the present invention is a copolymer of a monomer A having a styrene group and a monomer B which is an unsaturated carboxylic acid. Specific examples of the monomer A include styrene, α-methylstyrene, ortho, meta, and para-alkyl derivatives of styrene. These may be used alone or in combination of two or more. . Specific examples of the monomer B include acrylic acid, acrylic acid ester, maleic acid, maleic acid ester, fumaric acid, fumaric acid ester, itaconic acid, itaconic acid ester, etc. May be used in combination. The polymerization method of monomer A and monomer B can be selected from conventionally known methods and is not particularly limited.

  In the copolymer obtained by copolymerizing the monomer A and the monomer B in the present invention, the copolymer weight fraction when the total amount of each monomer is 100% by weight is preferably in the following range.

Monomer A; 10 to 95% by weight, more preferably 20 to 85% by weight
Monomer B; 5-90% by weight, more preferably 15-80% by weight
The glass transition point (Tg) of the styrene acrylic resin used in the present invention is preferably 200 ° C. or less, and more preferably 50 to 150 ° C., which is the same as the temperature at which wet pulverization is performed.

  The mixing ratio of the polyhalogenated phthalocyanine, the azo dye derivative, and the styrene acrylic resin in the wet pulverization according to the present invention is preferably such that the added weight separation when the total amount of each added amount is 100% by weight is in the following range. .

Polyhalogenated phthalocyanine; 60-99 wt%, more preferably 70-96 wt%
Azo dye derivative; 1 to 20% by weight, more preferably 2 to 15% by weight
Styrene acrylic resin; 0 to 20% by weight, more preferably 2 to 15% by weight
The wet pulverization of the present invention is a step of pulverizing crude polyhalogenated phthalocyanine as a viscous liquid composition together with a water-soluble inorganic salt as a grinding agent and an organic solvent as a wetting agent.

Examples of the water-soluble inorganic salt that is a grinding agent used in the present invention include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The higher the amount of water-soluble inorganic salt used, the higher the pigment grinding effect, but it is preferably 1 to 50 times the weight of the crude polyhalogenated phthalocyanine, and 1 to 20 times the weight in terms of productivity. It is more preferable that Furthermore, the water content in the water-soluble inorganic salt is preferably 1% or less.

  The amount of the water-soluble organic solvent used is preferably 0.5 to 3 times the weight, more preferably 1 to 2 times the weight of the crude polyhalogenated phthalocyanine.

  The wetting agent used in the present invention is not particularly limited as long as it is brought into contact with the crude polyhalogenated phthalocyanine so that the crude polyhalogenated phthalocyanine is moistened to increase the grinding effect and promote miniaturization. A water-soluble organic solvent is preferred.

  Water-soluble organic solvents include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene Examples include goricol monomethyl ether acetate, acetone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like. These may be used as a mixture of two or more if necessary.

  Further, the amount of the water-soluble organic solvent used is preferably 0.1 to 10 times the weight, more preferably 1 to 4 times the weight of the crude polyhalogenated phthalocyanine.

  For wet milling, if it is used in a small amount and adsorbs to the crude polyhalogenated phthalocyanine and does not run away in the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate , Isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. in combination with the above water-soluble organic solvent May be. These may be used as a mixture of two or more if necessary.

Although there is no restriction | limiting in particular about the wet crushing apparatus used in this invention, It is using apparatus, such as a trimix (made by Inoue Seisakusho), a supermix (made by Shinei Machine), and a kneader (made by Inoue Seisakusho) with a high grinding effect. it can.
Although there is no restriction | limiting in particular about the operating conditions of the wet grinding apparatus in this invention, In order to advance grinding | pulverization by a grinding | pulverization media effectively, the following operating conditions are preferable when an apparatus is a kneader. That is, the rotation speed of the blade in the apparatus is preferably 10 to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 24 hours, and the internal temperature of the apparatus is preferably 50 to 150 ° C. The water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

  In the present invention, a surfactant and a higher fatty acid may be added as necessary during wet pulverization. The surfactant is not particularly limited, and any anionic, neutral or cationic surfactant may be used.

Higher fatty acids are fatty acids that react with glycerin and react with glycerin, and are widely soluble in animal fats and vegetable oils. They are sparingly soluble in highly lipophilic water, such as palmitic acid and linoleic acid. , Stearic acid, linolenic acid, oleic acid and the like. As the higher fatty acid, a fatty acid having 10 or more carbon atoms is preferable, and an unsaturated higher fatty acid which is liquid at 20 ° C. to 30 ° C. is more preferable. In contrast, fatty acids with a small number of carbons include acetic acid, valeric acid, and lactic acid, which are free acid and hydrophilic. Higher fatty acids with strong lipophilicity are suitable as the fatty acid that wets the pigment to increase the grinding effect and promotes refinement. In addition, water-soluble inorganic salts and water-soluble organic solvents used in wet grinding are separated from the pigment by washing with water, but hydrophilic fatty acids with a small number of carbons are dissolved in water, resulting in BOD and COD. This is not preferable because it causes an increase. Two or more types of higher fatty acids may be used as needed.
When the polyhalogenated phthalocyanine pigment of the present invention is contained in a pigment carrier, the offset printing ink, gravure printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type coloring resist agent It can be set as a coloring composition.

The colored composition obtained by uniformly dispersing the polyhalogenated phthalocyanine pigment of the present invention in a pigment carrier exhibits stable viscosity characteristics, and by using the colored composition, a color having high contrast, brightness, and sharpness. A filter can be manufactured.
The pigment carrier is composed of a resin, its precursor, or a mixture thereof. Resins include thermosetting resins, thermoplastic resins, and active energy ray curable resins, and precursors of resins include monomers and oligomers that form a coating film similar to the resin by being cured by irradiation with active energy rays. These can be used alone or in combination of two or more. The pigment carrier can be used in an amount of preferably 50 to 700 parts by weight, more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the polyhalogenated phthalocyanine pigment.

  In the case of producing a color filter using a colored composition, the resin is preferably a transparent resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. . In addition, since a high-temperature heating process is performed in a later process in manufacturing the color filter, it is necessary to use a resin having good heat resistance.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Active energy ray curable resins include polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, (meth) acrylic compounds, cinnamic acid via isocyanate groups, aldehyde groups, epoxy groups, etc. A resin having a photocrosslinkable group introduced therein is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified polymers can also be used.

  Resin precursor monomers and oligomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Various acrylic and methacrylic acid esters such as dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, hexa (meth) acrylate of caprolactone adduct of dipentaerythritol hexa (meth) acrylate, acrylic acid, Methacrylic acid, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, styrene, vinyl acetate, acrylonitrile, melamine (meth) acrylate, epoxy Examples include cis (meth) acrylate prepolymers.

  When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition. 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-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p -Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (Trichloromethyl) -s-triazine, 2,4-bis (tri (Loromethyl) -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, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used. A photoinitiator can be used in the quantity of 5-150 weight part with respect to 100 weight part of polyhalogenated phthalocyanine pigments.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenance are used. Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination. The sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  In the coloring composition, a solvent can be used in order to sufficiently disperse the pigment in the pigment carrier and uniformly apply it to the substrate. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination. The solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the polyhalogenated phthalocyanine pigment.

  Various dispersion means such as a three-roll mill, a two-roll mill, a sand mill, and a kneader can be used for dispersing the polyhalogenated phthalocyanine pigment composition of the present invention in a pigment carrier. Moreover, in order to make these dispersion | distribution favorable, dispersion | distribution adjuvants, such as various surfactant and a pigment derivative, can be added suitably. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing reaggregation of the pigment after dispersion. These coloring compositions such as printing ink and coloring resist agent are coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove the coarse particles and the mixed dust.

  Since the coloring composition of this invention adjusts to desired chromaticity, a yellow pigment can be used together as needed. These yellow pigments are preferably added in a range that does not impair the color characteristics. In addition, these yellow pigments may use surface-treated pigments in which the surface of pigment particles is coated with surface treatment agents such as known and commonly used pigment derivatives, dispersants, surfactants and resins, if necessary. . As a method for adding the yellow pigment, there are a method of adding at the time of wet pulverization, a method of adding at the time of dispersion, and a method of adding the respective dispersions by mixing.

When used in a color filter, the yellow pigment that can be used in combination with the present invention can be used for picking up a desired emission line of a backlight light source having a wavelength (Tmax) that maximizes the transmittance of the spectral transmission spectrum.
Examples of toning yellow pigments that can be used in the present invention include C.I. I. Pigment yellow 83, 128, 138, 139, 150, 154, 180, 185 and the like.

These yellow pigments can be used alone or in combination of two or more. Among the yellow pigments, C.I. I. Pigment Yellow 138, 139, and 150 are more preferable in terms of excellent color purity and transparency.
The mixing ratio of the yellow pigment can be appropriately selected according to the use.Generally, when used in a color filter, the total amount of the green pigment composition of the present invention and the yellow pigment is based on the mass, It is preferable to set it as 10 to 60% of range, and it is more preferable to set it as 30 to 50% of range especially.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to a following example. In the examples, “parts” and “%” are by weight unless otherwise specified.

[Example 1]
Crude polyhalogenated copper phthalocyanine (bromine number: 13.1, chlorine number: 2.2) 150 parts, azo dye derivative (compound 1) 5 parts, and styrene acrylic resin (Johncrill 611: manufactured by BASF Japan Ltd.) 5 parts Was added to a kneader together with 1500 parts of crushed and dried sodium chloride having an average particle size of 20 μm. The temperature was controlled at 70 ° C., 220 parts of diethylene glycol was added, and after forming a good dough state, wet grinding was performed for 6 hours. After wet pulverization, the mixture was added to 10 times the content of water and stirred to dissolve sodium chloride and diethylene glycol, followed by filtration and purification to separate the pigment. The wet cake was dried with a dryer until the water content was less than 1%, and then pulverized with a hammer mill type pulverizer to obtain a polyhalogenated copper phthalocyanine pigment through a 5 mm screen.
(Compound 1)

[Example 2]
The same operation as in Example 1 was carried out except that Compound 1 in Example 1 was changed to Compound 2.
(Compound 2)

[Example 3]
The same operation as in Example 1 was carried out except that Compound 1 in Example 1 was changed to Compound 3.
(Compound 3)

[Example 4]
The same operation as in Example 1 was carried out except that Compound 1 in Example 1 was changed to Compound 4.
(Compound 4)

[Example 5]
The same operation as in Example 1 was performed except that the styrene acrylic resin of Example 1 was changed to Joncrill 586 (BASF Japan Ltd.).
[Example 6]
The same operation as in Example 1 was performed except that the styrene acrylic resin of Example 1 was changed to Joncrill 819 (manufactured by BASF Japan Ltd.).
[Example 7]
The same operation as in Example 1 was performed except that the styrene acrylic resin in Example 1 was changed to Joncrill 61J (manufactured by BASF Japan Ltd.). Joncrill 61J was added in an amount of 5 parts by solid content calculation.
[Example 8]
150 parts of the crude polyhalogenated copper phthalocyanine of Example 1 and 5 parts of an azo dye derivative (Compound 1) were added to a kneader together with 1500 parts of pulverized and dried sodium chloride having an average particle diameter of 20 μm. Wet grinding was performed in the same manner as in Example 1 to obtain a polyhalogenated copper phthalocyanine pigment.
(Compound 1)

[Comparative Example 1]
150 parts of the crude polyhalogenated copper phthalocyanine of Example 1 was added to a kneader together with 1500 parts of crushed and dried sodium chloride having an average particle size of 20 μm. Wet grinding was performed in the same manner as in Example 1 to obtain a polyhalogenated copper phthalocyanine pigment.
[Comparative Example 2]
150 parts of crude polyhalogenated copper phthalocyanine of Example 1 and 5 parts of styrene acrylic resin (Johncrill 611: manufactured by BASF Japan Ltd.) were added to a kneader together with 1500 parts of crushed and dried sodium chloride having an average particle diameter of 20 μm. Wet grinding was performed in the same manner as in Example 1 to obtain a polyhalogenated copper phthalocyanine pigment.
[Comparative Example 3]
150 parts of the crude polyhalogenated copper phthalocyanine of Example 1 and 5 parts of a polyhalogenated copper phthalocyanine dye derivative (Compound 5) were added to a kneader together with 1500 parts of pulverized and dried sodium chloride having an average particle size of 20 μm. Wet grinding was performed in the same manner as in Example 1 to obtain a polyhalogenated copper phthalocyanine pigment.
(Compound 5)

(Evaluation of color filter characteristics of pigments obtained in Examples and Comparative Examples)
The chromaticity and lightness of the pigments obtained in Examples and Comparative Examples were measured. In these evaluations, a photosensitive coloring composition was prepared, the photosensitive coloring composition was applied to a glass substrate using a spin coater, and the chromaticity, brightness, and contrast of the coated substrate after exposure and heating were measured. The evaluation method will be described in detail below.

(Preparation of acrylic resin solution)
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Styrene 60.0 parts Methacrylic acid 60.0 parts Methyl methacrylate 65.0 parts Butyl methacrylate 65.0 parts Azobisisobutyronitrile 10.0 parts

  After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a weight average molecular weight. A solution of about 40,000 acrylic resin was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

(Preparation of photosensitive coloring composition)
A mixture having the following composition was uniformly dispersed, stirred and mixed, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition.
Polyhalogenated phthalocyanine pigment 4.5 parts
(Examples 1-8 and Comparative Examples 1-3)
Acrylic resin solution 24.0 parts
5.4 parts of trimethylolpropane triacrylate
(Shin Nakamura Chemical "NK Ester ATMPT")
Photoinitiator ("Irgacure 907" manufactured by Ciba Geigy) 0.3 parts
Sensitizer (Hoabaya Chemical "EAB-F") 0.2 parts
65.1 parts cyclohexanone

  The photosensitive coloring composition produced using the pigments obtained in Examples 1 to 8 and Comparative Examples 1 to 3 was placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at 500 rpm and 1000 rpm. The coating was performed at a rotational speed of 2000 rpm to obtain three types of coated substrates having different film thicknesses. Next, after drying at 70 ° C. for 20 minutes, ultraviolet exposure was performed with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp. The coated substrate was heated at 220 ° C. for 20 minutes and then allowed to cool to produce a colored film. Then, the spectrum of the obtained colored film was measured with a spectrophotometer (“U-3500” manufactured by Hitachi, Ltd.), and each chromaticity (Y, x, y) with a C light source was calculated, and y = 0. Each Y and x at 500 was further calculated. Further, the contrast was measured by measuring the obtained colored film with a contrast tester (“CT-1BF” manufactured by Aisaka Electric Co., Ltd.) and calculating the contrast when y = 0.500. The viscosity was measured with an EL type viscometer (TV-20, manufactured by Toki Sangyo, 50 rpm, the unit being mPa · S). The results are shown in Table 1.

  When Example 1 of Table 1 and Comparative Examples 1 and 2 are compared, the crude polyhalogenated phthalocyanine, the azo dye derivative, and the styrene acrylic resin are simultaneously wet pulverized without adding each of them, or only the styrene acrylic resin It became possible to obtain a colored film having a higher contrast and brightness and a dispersion having a lower viscosity than by wet pulverization. Moreover, the other Examples 2-7 were the same results. Comparing Example 8 and Comparative Example 3, it is clear that the azo dye derivative is more effective in contrast and viscosity than the polyhalogenated copper phthalocyanine dye derivative.

Claims (6)

A polyhalogenated phthalocyanine pigment composition characterized by wet-pulverizing a polyhalogenated phthalocyanine and an azo dye derivative represented by the general formula (1) in the presence of an inorganic salt and an organic solvent.
General formula (1)

In general formula (1),
A and B represent a hydroxyl group or a basic substituent represented by the following general formulas (2) to (3).
General formula (2)

General formula (3)

In general formulas (2) and (3),
R ₁ and R ₂ each independently represents a saturated or unsaturated alkyl group which may be substituted, or a heterocyclic ring which may be substituted containing a nitrogen, oxygen or sulfur atom in R ₁ or R _2. . However, n represents the integer of 1-10.
  A polyhalogenated phthalocyanine pigment composition characterized by wet-pulverizing a polyhalogenated phthalocyanine, an azo dye derivative represented by the general formula (1), and a styrene acrylic resin in the presence of an inorganic salt and an organic solvent. Polyhalogenated phthalocyanines are C.I. I. Pigment green 7, C.I. I. The pigment composition according to claim 1 or 2, which is CI Pigment Green 36. A colored composition comprising the polyhalogenated phthalocyanine pigment according to any one of claims 1 to 3 and a pigment carrier. Furthermore, the coloring composition of Claim 4 containing a yellow pigment. A color filter comprising the polyhalogenated phthalocyanine pigment composition according to claim 1 in a green pixel portion.