JP5568804B2 - ε-type phthalocyanine pigment composition and method for producing the same - Google Patents

Description

  The present invention relates to an ε-type phthalocyanine pigment composition and a method for producing the same, a coloring composition using the composition, and a color filter.

  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. By providing a color filter between the two polarizing plates, color display is possible, and it has come to be used for televisions, personal computer monitors and the like. In recent years, demands for higher brightness, higher contrast, and higher color reproducibility are increasing for color filters from the viewpoint of energy saving.

  The reason why the polarization plane of the light transmitted through the first polarizing plate is disturbed by the color filter is that the light polarized by the first polarizing plate is reflected or scattered by the pigment particles when passing through the color filter. The polarization is disturbed (depolarization).

  In addition, in order to increase the brightness and contrast ratio of a color liquid crystal display, it is necessary to select a pigment having suitable spectral characteristics. In the case of blue, in the transmission spectrum of the color filter, the wavelength from near 500 nm to the shorter wavelength side It is necessary to increase the transmittance and the transmittance from around 400 nm to 450 nm. As one of pigments having spectral characteristics suitable as such a blue color filter, an ε-type phthalocyanine pigment is known.

  However, in order to further increase the brightness and contrast ratio, not only the selection of a suitable pigment, but also to make the primary particles of the pigment as fine as possible in order to improve the transmittance when used in a color filter, A coloring composition having excellent dispersion stability of the finely divided primary pigment particles is required.

  By the way, the primary particles of the pigment are generally refined by mechanically kneading the pigment (see Patent Documents 1 and 2). As can be seen from Patent Documents 3 and 4, this kneading process is known to be capable of producing finer particles by suppressing particle growth by keeping the temperature as low as possible.

  However, in the case of phthalocyanine pigments, it is known that the kneading process is susceptible to crystal transition due to temperature. For example, when kneading (wet kneading) is performed at a low temperature using widely used diethylene glycol, A crystal transition from the ε-type to the α-type has occurred, and it has been a problem that an ε-type phthalocyanine pigment having a desired hue cannot be obtained. Patent document 5 etc. are known as a manufacturing method of an epsilon-type phthalocyanine pigment.

JP 2001-220520 A JP 2005-189672 A JP 2008-285532 A JP 2010-195911 A JP 2007-332317 A

  The problem to be solved by the present invention is that the conventional wet kneading using diethylene glycol has a high contrast ratio when used in a color filter in a temperature range where crystal transition to a crystal structure of α type or β type occurs. It is to provide a ε-type phthalocyanine pigment composition that is fine and that does not substantially contain α-type or β-type, and a method for producing the same.

  As a result of intensive investigations to solve the above problems, the present inventors have found that when wet kneading crude phthalocyanine, by using a styrene-based resin and polyethylene glycol, the α type and β The present inventors have found that a fine ε-type phthalocyanine composition can be obtained without a crystal transition to a type crystal structure.

That is, an embodiment of the present invention is a method for producing an ε-type phthalocyanine pigment composition comprising an ε-type phthalocyanine pigment, a styrene resin, and a phthalocyanine pigment derivative represented by the following general formula (1), ε-type phthalocyanine characterized by wet-grinding an ε-type phthalocyanine pigment, a styrene resin, and a phthalocyanine pigment derivative represented by the general formula (1) in the presence of a water-soluble inorganic salt and polyethylene glycol The present invention relates to a method for producing a pigment composition.

General formula (1)

P-L _m

[In general formula (1),
P is a phthalocyanine pigment residue;
m is an integer of 1 to 4,
L is independently —OH, —SO ₃ H, —COOH , a phthalimidomethyl group which may have a substituent, the following formulas (a), (b), (c), (d) , ( f) a group represented by (1-56) or (1-57) . ]

[In the formulas (a) to (d) and (f),
X ^1, X ^2, X ³ _{are, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y ¹ and Y ² are —NH—, —O—, —S—, or a direct bond,
n is an integer of 1 to 10,
R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted alkenyl group having 2 to 30 carbon atoms. R ¹⁶ and R ¹⁷ may be combined to form a heterocyclic ring containing nitrogen, oxygen and sulfur atoms.
R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , and R ²² may each independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or a substituent. An alkenyl group having 2 to 20 carbon atoms.
R ²³ is a group represented by formula (a) or formula (b).
R ²⁴ is a chlorine atom, —OH, an alkoxyl group, a group represented by the formula (a) or the formula (b).
Z ¹ and Z ³ are —CONH—, —NHCO—, —SO ₂ NH—, or —NHSO ₂ —.
R ²⁵ is a hydrogen atom, —NH ₂ , —NHCOCH ₃ , —NHR ²⁷ , or a group represented by the formula (c), wherein R ²⁷ has 1 to 20 carbon atoms which may have a substituent. Or an alkenyl group having 2 to 20 carbon atoms which may have a substituent . ]

  An embodiment of the present invention also relates to a method for producing the ε-type phthalocyanine pigment composition, wherein the polyethylene glycol has a number average molecular weight of 300 or more and 2000 or less.

  An embodiment of the present invention also relates to a method for producing the ε-type phthalocyanine pigment composition, wherein the wet milling temperature is 20 ° C. or higher and 55 ° C. or lower.

  An embodiment of the present invention also relates to an ε-type phthalocyanine pigment composition obtained by the above production method.

  In addition, an embodiment of the present invention relates to a coloring composition comprising the ε-type phthalocyanine pigment composition and a binder resin and an organic solvent.

  An embodiment of the present invention also relates to a color filter comprising a filter segment formed from the above-described colored composition on a substrate.

  According to the present invention, a fine ε-type phthalocyanine pigment composition suitable for a color filter can be efficiently produced in a temperature range where crystal transition occurs in wet kneading using conventional diethylene glycol. As a result, it is possible to provide color filters that give high brightness and contrast ratios, and are used in various display fields such as liquid crystal display panels, plasma display panels, organic EL display panels, and other fields where color filters are required. I was able to do that.

  Hereinafter, the present invention will be described in detail. Note that “CI” described below means a color index (CI). In the present specification, unless otherwise specified, “ε-type phthalocyanine pigment” is “pigment”, “phthalocyanine pigment derivative represented by the general formula (1)” is “pigment derivative”, and “ε-type phthalocyanine pigment” “Composition” may be abbreviated as “pigment composition”.

<Ε-type phthalocyanine pigment>
The ε-type phthalocyanine pigment used in the present invention is not particularly limited, but a commercially available ε-type phthalocyanine pigment having a large particle diameter can be used. In addition, the manufacturing method described in JP-A-57-141453, PIGMENT HANDBOOK, Volume 1, page 667 (1988), and “Phthalocyanine-Chemistry and Function” written by Yasuyoshi Shirai and Nagao Kobayashi, pages 55-62. After synthesizing phthalocyanine by a known production method described in (1997), if necessary, an α-type phthalocyanine pigment is produced by an acid pasting method as disclosed in JP-A-48-76925, Next, the α-type phthalocyanine pigment and the crystal stabilizer can be crystallized by milling. The ε-type phthalocyanine pigment can be qualitatively and quantitatively determined by X-ray diffraction. The ε-type copper phthalocyanine pigment has the strongest diffraction peak at a Bragg angle 2θ (allowable range ± 0.2 degrees) = 9.2 degrees according to the X-ray diffraction diagram (CuKα ray). The ε-type phthalocyanine pigment used in the present invention is not only a case where the content of the ε-type phthalocyanine pigment is 100% by weight, but also an ε-type phthalocyanine pigment partially containing α-type or β-type is also an ε-type phthalocyanine It is called a pigment. Specifically, the content of the ε-type phthalocyanine pigment as the crude ε-type phthalocyanine pigment is preferably 80% by weight or more, and more preferably 90% by weight or more.

<Phthalocyanine pigment derivative>
The method for producing the pigment derivative of the present invention is not particularly limited, but “Mother and Thomas“ Phthalocyanine Compounds ”(1983) by Moser and Thomas,“ Yoshio Shirai and Nagao Kobayashi “Phthalocyanine-Chemistry and Function” ” (1997) and the like and other suitable methods are used.

  The pigment derivative used in the present invention is a phthalocyanine pigment derivative represented by the general formula (1).

In the general formula (1), examples of the metal in the monovalent to trivalent metal salt of the acidic group (—OH, —SO ₃ H, —COOH) include sodium, potassium, magnesium, calcium, iron, and aluminum. It is done. In addition, as an alkyl ammonium salt of an acidic group (—OH, —SO ₃ H, —COOH), an ammonium salt of a long-chain monoalkylamine such as octylamine, laurylamine, or stearylamine, or palmityltrimethylammonium salt And quaternary alkyl ammonium salts such as dilauryl dimethyl ammonium salt and distearyl dimethyl ammonium salt.

  Examples of the phthalimidomethyl group which may have a substituent include the following structures.

  Examples of the alkyl group having 1 to 30 carbon atoms which may have a substituent include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and pentyl. Group, sec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, isononyl group, decyl group, undecyl group, dodecyl group, tridecyl group Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like.

  As a C2-C30 alkenyl group which may have a substituent, a vinyl group, a propenyl group, a butenyl group, a hexenyl group, an oleyl group etc. are mentioned, for example. It may be either linear or branched, and the position of the double bond is not particularly limited.

  Examples of the alkoxyl group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, octyloxy group, 2-ethylhexyloxy group and the like.

  Pigment derivatives are sulfonated by heating in sulfuric acid or fuming sulfuric acid, phthalimide methylation reaction by dehydration condensation with N-hydroxymethylphthalimide in sulfuric acid, chlorosulfonated using chlorosulfonic acid and thionyl chloride. And can be synthesized by a known production method such as sulfonamidation reaction with an amine component such as dimethylaminopropylamine.

  Examples of the amine component used to form the substituent represented by the above formula (a), formula (b), and formula (c) include dimethylamine, diethylamine, methylethylamine, N, N-ethyl. Isopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N , N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) ) Amine, dioctylamine, N, N Methyl octadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N- Dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-di Butylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearyl Aminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, Ethyl isonipecotate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl 2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1 -Cyclopentyl piperazine etc. are mentioned, However, It is not limited to these.

  In addition to the method of mixing the pigment derivative when dispersing the pigment, a method of mixing in water or an organic solvent at the time of manufacturing the pigment composition, or a method of adding at the time of the salt milling process may be mentioned. It is preferable that the compounding quantity of a pigment derivative is the range of 0.5-40 mass parts with respect to 100 mass parts of pigment compositions. More preferably, it is the range of 1-35 mass parts.

Hereinafter, although the specific example of the pigment derivative used for this invention is described, this invention is not limited to these. C ₃ H ₇ and n-C ₃ H ₇ are propyl groups, i-C ₃ H ₇ is isopropyl groups, C ₄ H ₉ is butyl groups, C ₃ H ₆ is propylene groups, and C ₄ H ₈ is butylene groups. Represents.

<Wet kneading>
In order to make the pigment composition fine, wet kneading is performed, and a salt milling process that is wet kneading and mixing is preferable. Salt milling is a process of heating a mixture of pigment, pigment derivative, water-soluble inorganic salt, and water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. In the present invention, a styrene resin and polyethylene glycol are further added to the above mixture, and wet kneading is performed. The water-soluble inorganic salt works as a crushing aid, and it is considered that the pigment composition is crushed using the high hardness of the inorganic salt during salt milling, resulting in an active surface and crystal growth. It has been. Therefore, the crushing and crystal growth of the pigment composition occur simultaneously during kneading, and the primary particle size of the pigment composition obtained varies depending on the kneading conditions.

  The kneading temperature is preferably −35 ° C. or higher from the melting point of polyethylene glycol, more preferably −10 ° C. to 70 ° C., and further preferably 20 ° C. to 55 ° C. When the kneading temperature is less than −10 ° C., crystal growth does not occur sufficiently, and the shape of the pigment composition particles becomes close to amorphous, and the crystal transition to α-type may occur. On the other hand, when the kneading temperature exceeds 70 ° C., there is a possibility that crystal transition to β type may occur, which is not preferable.

  The kneading time is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the pigment composition subjected to the salt milling treatment and the cost required for the salt milling treatment.

  By optimizing the conditions for salt milling the pigment composition, the primary particle size is very fine and the range of particle size distribution is not accompanied by crystal transition to α-type or β-type crystal structure. A narrow pigment composition can be obtained.

<Water-soluble inorganic salt>
As the water-soluble inorganic salt used in the salt milling treatment, 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 parts by mass, more preferably 300 to 1500 parts by mass with respect to 100 parts by mass of the pigment composition, from the viewpoint of both processing efficiency and production efficiency.

<Polyethylene glycol>
The polyethylene glycol used in the present invention preferably has a number average molecular weight of 200 or more and 4000 or less, and more preferably 300 or more and 2000 or less. When the number average molecular weight is less than 200, there is a possibility that sufficient miniaturization is difficult to occur. On the other hand, when the number average molecular weight exceeds 4000, the solubility in water is lowered, and it may remain in the pigment composition and cause a reduction in coloring power.

  The number average molecular weight is a value obtained from a hydroxyl group in polyethylene glycol. Specifically, by performing neutralization titration with sodium hydroxide, the number of existing polymers is obtained, and the mass per one polymer (number average molecular weight) is calculated from the total mass and the molecular weight of the monomer. To do.

  The polyethylene glycol used in the present invention is preferably used in an amount of 5 to 1000 parts by weight, more preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment composition.

<Styrene resin>
The styrenic resin used in the pigment composition of the present invention is a polymer obtained by polymerizing a monomer comprising 50 to 90% by weight of styrene and 10 to 50% by weight of another monomer copolymerizable therewith, As the other monomer, at least one kind of radical polymerizable monomer is preferable.

  Examples of the radical polymerizable monomer include esters of acrylic acid or methacrylic acid and vinyl aromatic compounds.

  Examples of esters of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylic acid Acrylic acid such as ethyl, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate or the like, alkyl ester having 1 to 18 carbon atoms of methacrylic acid, methoxybutyl acrylate, methoxy methacrylate Acrylic acid such as butyl, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, or methacrylic acid having 2 to 18 carbon atoms C2-C8 alkenyl ester of acrylic acid or methacrylic acid such as alkoxyalkyl ester, allyl acrylate, allyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate Acrylic acid such as methacrylic acid, acrylic acid such as allyloxyethyl acrylate and allyloxyethyl methacrylate, or alkenyloxyalkyl ester of methacrylic acid having 3 to 18 carbon atoms. .

  Examples of the vinyl aromatic compound include α-methylstyrene, vinyltoluene, and p-chlorostyrene.

  The styrene resin has an acid value in the range of 50 to 300 mgKOH / g, a softening point in the range of 50 to 160 ° C., and a weight average molecular weight of 1500 to 20000, preferably in the range of 7000 to 13000. It is better to use one.

  For this reason, if the acid value of the styrenic resin is less than 50, there is a possibility of adversely affecting the miniaturization and dispersibility. If the acid value exceeds 300, the compatibility with the dispersion solvent may be poor. When the softening point exceeds 160 ° C., there is a possibility that sufficient kneading cannot be performed during wet kneading. On the other hand, when the softening point is lower than 50 ° C., the coating film of the color filter exhibits adhesiveness and may not be suitable as a color filter. Further, if the weight average molecular weight is less than 1000, the effect of refining the pigment may be reduced. When the weight average molecular weight exceeds 20000, the viscosity of the coloring composition is increased, and the contrast and the lightness may be decreased.

  Styrene-based resins can be obtained from commercial products, and examples thereof include John Crill 67, John Crill 586, and John Crill 611 (manufactured by Johnson Polymer Co., Ltd.). In addition, several kinds of styrenic resins can be used in combination as required.

  Although the manufacturing method of the styrenic resin used for this invention is not specifically limited, What was obtained by the well-known method and the other suitable method can also be used.

  The blending amount of the styrene resin is preferably 0.5% to 35% by weight of the pigment composition, more preferably 1 to 15% by weight as the styrene resin solid content. If it exceeds 35% by weight, kneading may be difficult, and in that case, there is a concern that coloring power may be reduced. If it is less than 0.5% by weight, there is a possibility that a sufficient fine effect cannot be obtained.

  Moreover, when performing a salt milling process, you may add resin other than a styrene resin as needed. 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 organic solvent. It is preferable that the usage-amount of these resin is the range of 5-200 mass parts with respect to 100 mass parts of pigment compositions.

<Coloring composition>
The pigment composition can be used as a coloring composition together with a binder resin and an organic solvent. At that time, in addition to the pigment composition of the present invention, other colorants may be used in combination.

<Other colorants>
In order to adjust the chromaticity, the pigment composition may be used in combination with the following pigments or dyes as other colorants in addition to the above-described pigment composition as long as the effects of the present invention are not impaired.

  Other pigments that can be used in the colorant include, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 280, 281, 282, 283, 284, 285, 286 or 287. Other red dyes that can be used in the colorant include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, anthraquinone series, and the like. Specifically, C.I. I. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, C.I. I. Pigment Orange 43, 71, or 73, and / or 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 , 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination. Examples of the orange dye and / or yellow dye include quinoline series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and methine series.

  Other preferred colorants that can be used in combination are C.I. I. And CI Pigment Violet 23.

  The colorant for adjusting the chromaticity is preferably in the range of 0.1 to 75 parts by mass with respect to 100 parts by mass of the pigment composition, although depending on the backlight and the target hue.

<Binder resin>
Examples of the binder resin contained in the colored composition of the present invention include conventionally known thermoplastic resins and thermosetting resins.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  When used as a coloring composition for a color filter, the spectral transmittance is 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, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the alkali-soluble resin obtained by copolymerizing 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 these alkali-soluble resins include acrylic resins having acidic groups, α-olefin / (anhydrous) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, and ethylene / (meth) acrylic acid copolymers. Examples thereof include a polymer, an isobutylene / (anhydrous) maleic acid copolymer, and the like. 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.

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, formyl groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as the photosensitive coloring composition for color filters.

  The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly (Meth) acrylates such as tylene glycol (meth) acrylate, or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye (Meth) acrylamides such as acetone (meth) acrylamide or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether Examples thereof include vinyl ethers, vinyl acetate, and fatty acid vinyls such as vinyl propionate.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  On the other hand, examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, 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) were determined by connecting four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene-equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by Corporation and using tetrahydrofuran as the mobile phase.

  When the binder resin is used as a coloring composition for a color filter, a pigment adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that serves as an affinity group for the coloring composition carrier and solvent, and an aromatic group The balance of groups is important for pigment dispersibility, developability, and durability, and it is preferable to use a binder resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it is difficult to form a fine pattern. On the contrary, if the acid value exceeds 300 mgKOH / g, a fine pattern does not remain by development, which is not preferable.

  The binder resin is preferably used in an amount of 20 to 500 parts by mass with respect to 100 parts by mass of the pigment composition.

<Organic solvent>
In the colored composition of the present invention, it is easy to form a filter segment by sufficiently dispersing the pigment composition and applying it onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Therefore, an organic solvent is included. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

  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.

  Among them, since the solubility of each component in the coloring composition and the coating property of the coloring composition are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol It is preferable to use glycol acetates such as monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. The organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the colored composition in order to adjust the colored composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness. Is preferred.

<Dispersion of coloring composition>
In the coloring composition of the present invention, the pigment composition is a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular type in a colored composition carrier composed of the binder resin and an organic solvent. It can be produced by finely dispersing using various dispersing means such as a bead mill or an attritor. In the colored composition of the present invention, the pigment composition and other colorants may be simultaneously dispersed in the colored composition carrier, or those separately dispersed in the colored composition carrier may be mixed. The carrier means a composition comprising a binder resin and an organic solvent.

  Further, when the pigment composition is dispersed in the colored composition carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition using the dispersion aid can be expected to improve contrast and viscosity stability.

<Resin type dispersant and surfactant>
The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colored composition and a part compatible with the colored composition carrier, and adsorbs to the pigment composition to disperse in the colored composition. It works to stabilize. Specific examples of the resin-type dispersant 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 alkyls. Amine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) and polyesters having free carboxyl groups, Oil-based dispersants such as salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified Li acrylate, 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 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

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

  When adding a resin-type dispersant and a surfactant, the amount 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 pigment composition.

  The colored composition of the present invention can be used as a photosensitive colored composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays or heat to form a transparent resin. These may be used alone or in combination of two or more. Can be used. It is preferable that the compounding quantity of a monomer is 5-400 mass parts with respect to 100 mass parts of coloring compositions, and it is more preferable that it is 10-300 mass parts from a photocurable and developable viewpoint.

  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) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate 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, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
When the colored composition of the present invention is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator is added to form a photosensitive colored composition. Or it can adjust with the form of an alkali image development type colored resist material.

  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 benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ' Benzophenone compounds such as 1,4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethyl Thioxanthone compounds such as thioxanthone; 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 (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-benzoyl) Oxime)], 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; A carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment composition in the coloring composition, and 3 to 150 parts by mass from the viewpoint of photocurability and developability. It is more preferable.

<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.

  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.

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

<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 parts by mass with respect to 100 parts by mass of the colored composition.

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

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

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

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

<Curing agent, curing accelerator>
In order to assist the curing of the thermosetting resin, the coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as necessary. 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- Til-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, it is preferable to use 0.01-15 mass parts with respect to 100 mass parts 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% by mass as a colored composition (100% by mass).

  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% by mass, preferably 0.05 to 5% by mass, based on the total amount of the colorant in the coloring composition (100% by mass).

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. It is preferable to remove the mixed 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 a red filter segment, a green filter segment, and a blue filter segment, and the red filter segment therein is formed from a coloring composition containing the disazo coloring composition of the present invention. The

  The green filter segment can be formed using a normal green coloring composition containing a green pigment and a coloring composition carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.

  A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination 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, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or it can be given a yellow pigment 221, and the like. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition including a blue pigment and a coloring composition carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When using a dye, a xanthene dye is preferable in terms of heat resistance and lightness.

<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 the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. 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. Control of ink fluidity on a printing press is also important, and ink viscosity 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, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. 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. Further, 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.

  Hereinafter, the present invention will be described in detail with reference to examples and comparative examples according to conventional methods. However, the present invention is not limited to the scope of these examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

(Average primary particle diameter of pigment composition)
The average primary particle diameter of the produced pigment composition was measured (calculated) by the following method.
Propylene glycol monomethyl ether acetate was added to the powder of the pigment composition, a small amount of Disperbyk-161 was added as a resin-type dispersant, and the mixture was treated with ultrasonic waves for 1 minute to prepare a measurement sample. This sample was taken with a transmission electron microscope (TEM), and three photographs (for three fields of view) in which 100 or more primary particles of the pigment composition could be confirmed were taken, and the size of 100 primary particles in order from the upper left. Was measured. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment composition are measured in nm units, and the average is defined as the primary particle diameter of the pigment composition, with a total of 300 distributions in 5 nm increments. Create a number average particle size by approximating the median value in 5 nm increments (for example, 8 nm for 6 nm or more and 10 nm or less) as the particle size of those particles, and calculating based on each particle size and its number did.

(Content of α-type and ε-type copper phthalocyanine pigment in the pigment composition)
The contents of α-type and ε-type copper phthalocyanine pigment in the pigment composition were calculated according to the method described in JP-A-2007-332317. That is, the diffraction intensity of the pigment composition is measured in the range of 2θ = 3.5 to 15 using an X-ray diffractometer (RINTKU manufactured by Rigaku Co.), and the Bragg angle 2θ is 5 ° and 12 °. , The diffraction intensity at 6.8 ° is A, the maximum diffraction intensity at 9.1 ° ± 0.2 ° is B, and the minimum diffraction intensity at 8.2 ° ± 0.2 ° is C. In some cases, the contents of α-type and ε-type copper phthalocyanine were estimated from the index values calculated according to the formula (AC) / (AC−B). The closer the index value is to “0” (zero), the smaller the content of α-type copper phthalocyanine pigment in the pigment composition, and the higher the content of ε-type copper phthalocyanine pigment. The index value is “0”. In this case, it means that the content of α-type copper phthalocyanine pigment in the pigment composition is substantially 0% by weight.

[Example 1]
98 parts of ε-type copper phthalocyanine pigment (LIONOL BLUE E average particle size 70 nm, manufactured by Toyo Ink Manufacturing Co., Ltd.) and 2 parts of a pigment derivative of the following formula (2), 5 parts of BASF's Jonkrill 586 as a styrene resin, 1000 parts of sodium chloride and 150 parts of polyethylene glycol having a number average molecular weight of 300 were charged into a 1500-volume part double-arm kneader and kneaded at 20 ° C. for 10 hours. After kneading, the mixture was taken out into 3500 parts of 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour, filtered, washed with water, and dried to obtain a fine ε-type phthalocyanine pigment composition. The obtained pigment composition was measured for diffraction intensity in the range of 2θ = 3.5 to 15 with an X-ray diffractometer (RINTKU manufactured by Rigaku), and Bragg angle 2θ was 5 ° and 12 °. From a diffraction intensity A of 6.8 °, a maximum diffraction intensity B of 9.1 ° ± 0.2 °, and a minimum diffraction intensity C of 8.2 ° ± 0.2 °, the α-type copper The index value (AC) / (AC + B) of the phthalocyanine content was calculated to be 0.001, and no crystal transition to α-type copper phthalocyanine was observed. The average primary particle size was 25 nm.

[Example 2]
Kneading was performed in the same manner as in Example 1 except that the kneading temperature was changed to 55 ° C. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 30 nm.

[Example 3]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to 15 parts. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 20 nm.

[Example 4]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to 35 parts. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 15 nm.

[Example 5]
Kneading was carried out in the same manner as in Example 1 except that polyethylene glycol was changed to polyethylene glycol having a number average molecular weight of 1000. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 6]
Kneading was carried out in the same manner as in Example 1 except that polyethylene glycol was changed to polyethylene glycol having a number average molecular weight of 1000. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 7]
The kneading was carried out in the same manner as in Example 1 except that the styrene resin was changed to Joncrill 611 manufactured by BASF. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 8]
Kneading was carried out in the same manner as in Example 1 except that the styrenic resin was changed to Joncrill 67 manufactured by BASF. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 9]
700 parts of cyclohexanone was added to a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device, and heated to 80 ° C. After purging the inside of the reaction vessel with nitrogen, a mixture of 195 parts of styrene, 62 parts of α-methylstyrene, 39 parts of methyl methacrylate, and 4.0 parts of 2,2′-azobisisobutyronitrile was added for 2 hours from the dropping tube. It was dripped over. After completion of the dropping, the reaction was continued for 3 hours to obtain a styrene resin solution. After cooling to room temperature, the resin solution was dried by heating at 180 ° C. for 20 minutes to obtain a styrene resin.

Subsequently, it knead | mixed similarly to Example 1 except having changed into the said styrene resin. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value of the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. . The average primary particle size was 25 nm.

[Example 10]
700 parts of cyclohexanone was added to a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and heated to 80 ° C. After substituting the inside of the reaction vessel with nitrogen, a mixture of 124 parts of styrene, 24 parts of α-methylstyrene, 148 parts of methyl methacrylate, and 4.0 parts of 2,2′-azobisisobutyronitrile was added over 2 hours from the dropping tube. And dripped. After completion of the dropping, the reaction was continued for 3 hours to obtain a styrene resin solution. After cooling to room temperature, the resin solution was dried by heating at 180 ° C. for 20 minutes to obtain a styrene resin.

Subsequently, it knead | mixed similarly to Example 1 except having changed into the said styrene resin. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 11]
Kneading was carried out in the same manner as in Example 1 except that the amount of styrene-based resin Joncrill 586 manufactured by BASF was changed to 0.5 parts. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 12]
Kneading was carried out in the same manner as in Example 1 except that the amount of styrene-based resin Joncrill 586 manufactured by BASF was changed to 15 parts. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 13]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of formula (3). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 14]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the formula (4). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 15]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the following formula (5). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 16]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the formula (6). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 17]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the following formula (7). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 18]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the following formula (8). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 19]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the following formula (9). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value of the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. . The average primary particle size was 25 nm.

[Example 20]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the following formula (10). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 21]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the following formula (11). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 22]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the following formula (12). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 23]
Kneading was carried out in the same manner as in Example 1 except that the pigment derivative was changed to the pigment derivative of the following formula (13). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 25 nm.

[Example 24]
The epsilon-type copper phthalocyanine pigment was kneaded in the same manner as in Example 1 except that the product name was changed to BASF AG's trade name Heliogen Blue L6700F (average particle size 300 nm). The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value for the content of α-type copper phthalocyanine was calculated to be 0.000, and no crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 30 nm.

[Comparative Example 1]
Except for changing polyethylene glycol to diethylene glycol. Kneading was carried out in the same manner as in Example 1. The obtained kneaded composition was post-treated in the same manner as in Example 1 to obtain a pigment composition. The obtained pigment composition was measured for X-ray diffraction intensity, and the index value of the content of α-type copper phthalocyanine was calculated to be 0.310, and some crystal transition to α-type copper phthalocyanine was observed. It was. The average primary particle size was 40 nm.

<Preparation of acrylic resin solution>
700 parts of cyclohexanone was added to a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device, and heated to 80 ° C. After replacing the inside of the reaction vessel with nitrogen, 133 parts of n-butyl methacrylate, 46 parts of 2-hydroxyethyl methacrylate, 43 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 74 A mixture of 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 parts of the resin solution was heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added so that the nonvolatile content of the resin solution was 20% to obtain an acrylic resin solution.

<Preparation of salt-forming compound (A)>
In the following procedure, C.I. I. A salt-forming compound (A-1) composed of Acid Red 289 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety was 550) was produced. In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 289 was dissolved, thoroughly mixed and stirred, heated to 70 to 90 ° C., and then Cotamine D86P (manufactured by Kao Corporation) was added dropwise little by little. Next, the reaction was sufficiently carried out by stirring at 70 to 90 ° C. for 60 minutes. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of Acid Red 289 and distearyldimethylammonium chloride, a salt-forming compound (A-1) was obtained.

<Preparation of dye solution>
The following mixture was stirred and mixed to be uniform and then filtered through a 5.0 μm filter to prepare a dye solution.

Salt-forming compound (A-1): 11.0 parts Acrylic resin solution: 40.0 parts Dye dilution solvent (cyclohexanol acetate): 49.0 parts

<Preparation of photosensitive coloring composition>
A mixture having the following composition was stirred and mixed uniformly, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 1 mm to prepare a colored composition. After filtering this colored composition through a 5 μm filter, 12 parts of a dye solution, 14 parts of an acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate as a monomer, a photoinitiator (“Irgacure 907 manufactured by Ciba Japan Co., Ltd.) "] 1.2 parts, 0.4 parts of sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) and 23.2 parts of cyclohexanone as a solvent were stirred and mixed uniformly, and then 1.0 .mu.m. The photosensitive coloring composition was produced by filtering with a filter.

ε-type copper phthalocyanine pigment composition: 10.8 parts (pigment compositions obtained in Examples 1 to 24 and Comparative Example 1)
Pigment derivative of the above formula (2): 0.5 part Acrylic resin solution: 8.0 parts

(Creation of color filter and evaluation of coloring composition)
A coating film (color filter) was prepared using the obtained colored composition, and each evaluation result of brightness and contrast was performed by the following methods.

(Create color filter)
The coloring composition produced using the pigment composition obtained in Examples 1 to 24 and Comparative Example 1 was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm on a glass substrate using a spin coater. The film was applied to a film thickness such that y = 0.098 with a C light source, then dried at 70 ° C. for 20 minutes, exposed to ultraviolet light with an integrated light amount of 150 mJ using an ultra-high pressure mercury lamp, and alkali developed at 23 ° C. Liquid (a liquid composed of 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of anionic surfactant ("PERILEX NBL" manufactured by Kao Corporation), and 90% by weight of water) Development was performed to obtain a coated substrate. Then, after heating and cooling at 230 ° C. for 1 hour, a coating film substrate (color filter) was prepared.

<Evaluation of brightness>
The brightness (Y) of the color filter obtained above was measured using a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The prepared substrate was made to have the chromaticity with the C light source shown in Table 5 after heat treatment at 230 ° C. The lightness was evaluated by the relative value in the following five steps based on the lightness of the color filter obtained using the coloring composition prepared using the pigment of Example 2.

◎◎: + 5% or more (very good)
A: Less than + 5% to + 2% or more (good)
○: Less than + 2% to -5% or more (equivalent to standard)
X: Less than -5% (inferior to standard)
XX: -5% or less (remarkably inferior to standard)

<Evaluation of contrast>
Using a color luminance meter BM-5A manufactured by Topcon Corporation and a polarizing film LLC2-92-18 manufactured by Sanritsu Co., Ltd. as a polarizing plate, the luminance of the color filter prepared above was measured. When the color filter is sandwiched between two polarizing plates, the luminance at y = 0.098 when the polarizing plate is made parallel and perpendicular is measured, and the luminance when it is made orthogonal to the luminance when made parallel is measured. The ratio was contrast.

Contrast = (Brightness when polarizing plates are parallel) / (Brightness when polarizing plates are perpendicular)

In the measurement, in order to block scattered light, the measurement was performed by applying a black mask having a 1 cm square hole in the measurement portion. The lightness was evaluated by the relative value in the following five steps on the basis of the contrast of the color filter obtained using the coloring composition prepared using the pigment composition obtained in Example 2.

◎◎: + 10% or more (very good)
A: Less than + 10% to + 5% or more (good)
○: Less than + 5% to -10% or more (equivalent to standard)
X: Less than -10% to -30% or more (inferior to standard)
XX: -30% or less (remarkably inferior to standard)

From the above results, when crude copper phthalocyanine is wet-kneaded at low temperature using styrene resin and polyethylene glycol, a fine ε-type copper phthalocyanine composition can be obtained without crystal transition to α-type or β-type crystal structure. It was confirmed.
Also, in Example 24 using coarser ε-type copper phthalocyanine, it was confirmed that it showed higher brightness and contrast than Comparative Example 1.

Claims (6)

A method for producing an ε-type phthalocyanine pigment composition comprising an ε-type phthalocyanine pigment, a styrene resin, and a phthalocyanine pigment derivative represented by the following general formula (1), the crude ε-type phthalocyanine pigment, and a styrene resin And a phthalocyanine pigment derivative represented by the general formula (1) in the presence of a water-soluble inorganic salt and polyethylene glycol by wet milling.

General formula (1)

P-L _m

[In general formula (1),
P is a phthalocyanine pigment residue;
m is an integer of 1 to 4,
L is each independently —OH, —SO ₃ H, —COOH, an optionally substituted phthalimidomethyl group, the following formulas (a), (b), (c), (d) , (f ) , (1-56), or (1-57) . ]

[In the formulas (a) to (d) and (f),
X ^1, X ^2, X ³ _{are, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y ¹ and Y ² are —NH—, —O—, —S—, or a direct bond,
n is an integer of 1 to 10,
R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted alkenyl group having 2 to 30 carbon atoms. R ¹⁶ and R ¹⁷ may be combined to form a heterocyclic ring containing nitrogen, oxygen and sulfur atoms.
R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , and R ²² may each independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or a substituent. An alkenyl group having 2 to 20 carbon atoms.
R ²³ is a group represented by formula (a) or formula (b).
R ²⁴ is a chlorine atom, —OH, an alkoxyl group, a group represented by the formula (a) or the formula (b).
Z ¹ and Z ³ are —CONH—, —NHCO—, —SO ₂ NH—, or —NHSO ₂ —.
R ²⁵ is a hydrogen atom, —NH ₂ , —NHCOCH ₃ , —NHR ²⁷ , or a group represented by the formula (c), wherein R ²⁷ has 1 to 20 carbon atoms which may have a substituent. Or an alkenyl group having 2 to 20 carbon atoms which may have a substituent . ]

The method for producing an ε-type phthalocyanine pigment composition according to claim 1, wherein the polyethylene glycol has a number average molecular weight of 300 or more and 2000 or less. The method for producing an ε-type phthalocyanine pigment composition according to any one of claims 1 to 2, wherein the wet milling temperature is 20 ° C or higher and 55 ° C or lower. An ε-type phthalocyanine pigment composition obtained by the production method according to claim 1. A coloring composition comprising the ε-type phthalocyanine pigment composition according to claim 4 and further comprising a binder resin and an organic solvent. A color filter comprising a filter segment formed from the colored composition according to claim 5 on a substrate.