JP2012032833A - Coloring composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter satisfying a high contrast ratio required for the color filter by using more minute organic pigment as compared with a substance manufactured with a conventional kneader, and to provide the color filter having a higher contrast ratio than the conventional color filter.SOLUTION: In a coloring composition for a color filter containing a transparent resin, a pigment carrier comprising precursor of the transparent resin or their mixture and pigment. The pigment is minute organic pigment which is formed by kneading a kneading mixture containing organic pigment, water-soluble inorganic salt and water-soluble organic solvent by a planetary mixer in which a plurality of blades make sun-and-planet motion. The color filter comprises a filter segment formed by using the coloring composition.

Description

  The present invention relates to a color composition for a color filter used for forming a filter segment constituting a color filter used in a color liquid crystal display device and a solid-state imaging device, and a color filter obtained using the color composition for 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 that performs display by the above method is the mainstream, and color display is enabled by providing a color filter between the two polarizing plates. Currently, as a method for producing a color filter, a method called a pigment dispersion method in which a pigment having excellent light resistance and heat resistance is used as a colorant is mainly used. However, a color filter in which an organic pigment is dispersed is generally based on pigment particles. There is a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering or the like. That is, there is a phenomenon in which light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state). The above luminance ratio is called the contrast ratio.

  Generally, it is difficult to obtain a stable dispersion by dispersing fine pigment particles in a pigment carrier such as a varnish, and the dispersion often has a high viscosity due to aggregation of the pigment particles over time and exhibits thixotropic properties. It becomes like this. Such an increase in viscosity and poor fluidity of the dispersion cause various problems in manufacturing work and product value. For example, the filter segment of a color filter is generally formed by applying a colored composition in which a pigment is dispersed in a carrier containing a monomer and a resin on a transparent substrate such as glass. If a coloring composition with poor coating properties is used, a coating film having a uniform film thickness cannot be obtained due to poor coating properties, poor leveling, etc. In addition, since the color filter formed using the dispersion in which pigment particles are aggregated significantly reduces the contrast ratio, the pigment has stable fine particles without agglomeration and is easy to handle. It is hoped that.

A solvent salting method is currently widely used as a method for obtaining such fine pigment particles.
In the solvent salt milling method, coarse pigment particles are mechanically treated by a kneader or the like in the presence of inorganic salts such as sodium chloride and sodium sulfate and highly viscous water-soluble organic solvents such as ethylene glycol, diethylene glycol and polyethylene glycol. It is a method to grind and refine. The solvent salt milling method is an effective method for refining and sizing pigment particles. To achieve higher contrast in color filters, the solvent salt milling method is more effective than the pigment obtained by the conventional salt milling method. There is also a need to use finer and sized pigments.
Japanese Patent Laid-Open No. 7-53889

Although the solvent salt milling method is industrially advantageous, the conventionally used kneader uses a great deal of energy for miniaturization of organic pigments and realizes the high contrast ratio required for color filters. For this purpose, finer pigment particles are required, but it has been difficult to obtain this by the method described above.
The present invention has been made in view of such a situation, and for a color filter that satisfies a high contrast ratio required for a color filter by using a finer organic pigment than that produced by a conventional kneader. It is an object of the present invention to provide a coloring composition and a color filter having a higher contrast ratio than conventional ones.

The color filter coloring composition of the present invention is a color filter coloring composition containing a pigment carrier and a pigment made of a transparent resin, a precursor thereof, or a mixture thereof.
The pigment is a fine organic pigment obtained by grinding and kneading a kneaded mixture containing an organic pigment, a water-soluble inorganic salt, and a water-soluble organic solvent with a planetary mixer in which a plurality of blades move in a planetary motion, and ,
The aspect ratio of the pigment relates to a color filter coloring composition, wherein the aspect ratio is 1.68 or less.

  The present invention also relates to the above color filter coloring composition, wherein the kneaded mixture further contains at least one derivative selected from a pigment derivative, an anthraquinone derivative, an acridone derivative and a triazine derivative.

  In addition, the present invention relates to the coloring composition for a color filter, wherein the planetary mixer has 3 planetary blades.

  The present invention also relates to the above color filter coloring composition, wherein the kneading temperature when kneading the kneaded mixture is controlled to 0 to 150 ° C.

  The kneaded mixture further contains a resin.

  The present invention also relates to a color filter comprising a filter segment formed using the above color filter coloring composition.

  The coloring composition for a color filter according to the present invention includes a kneaded mixture containing an organic pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, and a plurality of blades rotating and revolving by planetary motion between blades and blades and tanks. The fine composition of the color filter according to the present invention includes a fine pigment that is sized and refined by exhibiting a powerful kneading effect with very little dead space (dead center) due to the precise spacing of the inner walls. By using it, it is possible to form a color filter having a higher contrast ratio than the conventional one.

  The colored composition for a color filter of the present invention contains a pigment carrier and a pigment made of a transparent resin, a precursor thereof, or a mixture thereof, and the pigment includes an organic pigment, a water-soluble inorganic salt, and a water-soluble organic salt. The greatest feature is that it is a fine organic pigment obtained by kneading a kneaded mixture containing a solvent with a planetary mixer in which a plurality of blades move in a planetary motion.

  A planetary mixer used in the present invention will be described with reference to the drawings. The planetary mixer main body (1) has a plurality of drive shafts (2) (two examples in the drawing) that perform planetary movement via a suitable transmission mechanism by a drive source (not shown) such as a motor. The drive shaft (2) is attached with a blade (4) so as to be inserted into the tank (3). When the kneaded mixture is put into the tank, the blade is lowered and set in a state as shown in FIG. 1, and a plurality of blades are planetarily moved in the tank, the blade and the inner wall of the tank, between the bottom wall and the plurality of blades A shearing force is applied to the kneaded mixture between the blades.

  Specific examples of the planetary mixer of the present invention include, for example, a planetary mixer, a spiral mixer, and a trimix (manufactured by Inoue Seisakusho). Among them, the trimix having three blades that move in a planetary motion can give a large shearing force, and has the effect of refining the organic pigment and having a large particle size, which is the object of the present invention. It is preferable for achieving contrast.

Next, the kneaded composition subjected to the kneading and dispersing treatment by such a kneader will be described in detail.
The kneaded composition contains an organic pigment, a water-soluble inorganic salt, a water-soluble organic solvent, and at least one derivative selected from resins and / or pigment derivatives, anthraquinone derivatives, acridone derivatives, or triazine derivatives as necessary. To do.

  The organic pigment used in the present invention is a known organic pigment used in color filters, and can be used alone or in combination of two or more. When an organic pigment having an average primary particle size of 0.1 to 0.5 μm is used as the organic pigment, the organic pigment can be refined to a very fine state with an average primary particle size of 0.01 to 0.1 μm. This is preferable because a particularly high contrast is exhibited. As organic pigments, crude organic pigments, that is, as obtained by synthesis, (a) large particles having an average primary particle diameter of about 10 to 200 μm, and (b) very large particles having an average primary particle diameter of 0.01 μm or less. It is also possible to use particles (aggregates) in which fine particles are aggregated very strongly. Moreover, you may contain a dye within the range which does not reduce heat resistance for color matching.

Hereinafter, specific examples of usable organic pigments are shown by color index numbers.
Red pigmented compositions for forming red filter segments include CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, Red pigments such as 226, 227, 228, 240, 246, 254, 255, 264, and 272 can be used. In the red coloring composition, yellow pigments exemplified later and orange pigments such as CI Pigment orange 36, 43, 51, 55, 59, 61, 71, 73 can be used in combination.

As the green coloring composition for forming the green filter segment, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green coloring composition.
Examples of blue coloring compositions for forming blue filter segments include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. Blue pigments can be used. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the blue coloring composition.

The yellow coloring composition for forming yellow filter segments includes CI Pig
ment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177 It can be used yellow pigments such 179,180,181,182,185,187,188,193,194,199.

For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used as a cyan coloring composition for forming a cyan filter segment. Can do.
For the magenta coloring composition for forming the magenta color filter segment, for example, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81 can be used. A yellow pigment can be used in combination with the magenta composition.

The water-soluble inorganic salt used in the kneaded composition is not particularly limited, and examples thereof include sodium chloride (sodium chloride), potassium chloride, sodium sulfate, zinc chloride, calcium chloride, and mixtures thereof.
The amount of the water-soluble inorganic salt in the kneaded composition is not particularly limited. However, if the amount is too small, it is difficult to refine and size the organic pigment, and if the amount is too large, the amount of pigment processed decreases. This is industrially disadvantageous due to a decrease in properties. Therefore, the water-soluble inorganic salt is preferably in the range of 100 to 3000 parts by weight with respect to 100 parts by weight of the organic pigment, and can be selected according to the target particle size.

The water-soluble organic solvent used in the kneaded composition is an organic pigment and a water-soluble inorganic salt that are added so as to form a uniform mass. It has a solubility that can be removed by washing with water, and is not particularly limited as long as the pigment particles grow.However, since the temperature rises during kneading and the solvent easily evaporates, it has a high boiling point from the viewpoint of safety. Solvents are preferred.
The amount of the water-soluble organic solvent in the kneaded composition is not particularly limited, but if it is too small, the kneaded composition becomes too hard and difficult to operate stably, and if it is too much, the kneaded composition becomes too soft and fine. The level of crystallization and sizing decreases. For this reason, the range of 10-700 weight part of a water-soluble organic solvent with respect to 100 weight part of organic pigments is preferable, and it can select according to the quantity of water-soluble inorganic salt, and the hardness of a kneading composition.

  Examples of the water-soluble organic solvent include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Low molecular weight polypropylene glycol, aniline, pyridine, tetrahydrofuran, dioxane, methanol , Ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Can be mentioned. Two or more organic solvents may be mixed and used as necessary.

A resin may be added to the kneaded composition.
The resin is preferably poorly water-soluble and partially soluble in a water-soluble organic solvent. The resin itself can be used as the pigment carrier constituting the color filter coloring composition, or the resin can be used as a pigment carrier. Those with little difference in properties are used. In particular, rosin resins such as rosin, disproportionated rosin, polymerized rosin, hydrogenated rosin, rosin ester, rosinamine, maleated rosin, fumarated rosin, rosin metal salts, rosin modified phenolic resin and rosin modified maleic resin And it is preferable from the aspect of price.
By adding such a resin to the kneaded mixture, aggregation of the fine organic pigment can be prevented and it can be easily dispersed in the subsequent pigment carrier.
Although there is no restriction | limiting in particular as the usage-amount of resin in a kneaded mixture, it is 0.01-100 weight part with respect to 100 weight part of pigments, More preferably, it is 0.5-50 weight part. When the amount of the resin is less than 0.01 part by weight, the effect on dispersibility is reduced, and when it exceeds 100 parts by weight, the added dispersion effect cannot be obtained.

  The kneaded composition contains at least one selected from a pigment derivative, an anthraquinone derivative, an acridone derivative or a triazine derivative in order to prevent crystal growth and crystal transition of the organic pigment and to efficiently produce a fine organic pigment. It is preferable to contain a derivative. Each of the derivatives is a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group into an organic pigment, anthraquinone, acridone, or triazine. The phthalimidomethyl group may have a substituent. Among these, pigment derivatives, particularly pigment derivatives having the same structure as the organic pigment to be refined as a base skeleton are preferable because they have a particularly high effect of suppressing the crystal growth of the pigment.

The pigment derivative is a compound represented by the following general formula (1).
AB Formula (1)
A: Organic pigment residue B: Basic substituent, acidic substituent or phthalimidomethyl group In the formula (1), as the organic pigment constituting the organic pigment residue of A, diketopyrrolopyrrole pigments, azo, disazo , Azo pigments such as polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, etc. Pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, etc. .

In the formula (1), examples of the basic substituent of B include substituents represented by the following formula (2), formula (3), formula (4), and formula (5). , Formula (6), formula (7), and substituents represented by formula (8).

In the above formulas (2) to (5),
X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, Alternatively, R ₁ and R ₂ together represent an optionally substituted heterocyclic ring containing a further nitrogen, oxygen or sulfur atom.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or Represents an optionally substituted phenyl group.

Y represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents a group.
Z represents an alkylene group having 1 to 36 carbon atoms which may be substituted, an alkenylene group having 2 to 36 carbon atoms which may be substituted, or a phenylene group which may be substituted.
P represents a substituent represented by the formula (9) or a substituent represented by the formula (10).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (9) or a substituent represented by the formula (10). In formula (9) and formula (10), R _{1 to} R ₇ and n are as defined above.

In the above formulas (6) to (8),
M represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom.
i represents the valence of M.
R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, It represents an optionally substituted phenyl group or polyoxyalkylene group.

  Examples of the amine component used for forming the substituent represented by the formulas (2) to (5), (9), and (10) include dimethylamine, diethylamine, N, N-ethylisopropyl, and the like. Amine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine N, N-methyloctadecylamine, didecyla , 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-diisobutylaminopentylamine, N, N- Tyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3 -Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinemethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Ethyl isonicopetic acid, 2-Piperidinethanol, Pyrrolidine 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, 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-cyclopentylpiperazine and the like.

The amine component used to form the sulfonic acid amine salt of formula (8) may be any of primary, secondary, tertiary and quaternary amines. For example, as the primary amine, hexylamine, heptylamine, octylamine, which may have a side chain, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexa Examples thereof include saturated amines such as decylamine, heptadecylamine, octadecylamine, nonadecylamine, eocosylamine, and unsaturated amines corresponding to the respective carbon numbers.
Examples of secondary amines include dioleylamine and distearylamine.
Examples of the tertiary amine include dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, and trioctylamine.

Quaternary amines include dimethyl didodecyl ammonium chloride, dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride. , Trimethyloctadecylammonium chloride, dimethyldodecyltetradecylammonium chloride, dimethylhexadecyloctadecylammonium chloride, and the like.
Moreover, when any of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in formula (8) represents a polyoxyalkylene group, examples thereof include a polyoxyethylene group and a polyoxypropylene group.

Specific examples of pigment derivatives are shown below with compound numbers, but are not limited thereto.

The compounding amount of the derivative in the kneaded composition is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the organic pigment. When the compounding amount of the derivative is less than 1 part by weight, it is difficult to obtain the added effect, and when it exceeds 30 parts by weight, the dispersion may be affected by an excess of the derivative.
In addition, since the derivative also has an effect as a dispersant, it is preferable to select a derivative having good dispersibility in the pigment carrier. However, a derivative having a high crystal growth preventing effect and a resin-type pigment that is a dispersion aid other than the derivative You may combine a dispersing agent, surfactant, etc. These derivatives and dispersion aids can be used not only when kneading with the kneader in the present invention but also when dispersing the pigment on the pigment carrier.

  The resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Salt or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are used. These can be used alone or in admixture of two or more.

  Examples of the surfactant 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 surfactants such as sodium acid, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, poly Oxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene Nonionic surfactants such as glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines Is mentioned. These can be used alone or in admixture of two or more.

  The operating conditions of the kneader in the present invention are not particularly limited, but the amount of organic pigment processed and the quality of the fine organic pigment obtained are controlled by the mixing ratio of the kneaded mixture, the kneading temperature, the mechanical energy input amount, and the rotational speed. This can be achieved by adjusting the supply amount of the raw material, the main shaft power load, and the like. However, the kneading temperature is preferably from 0 to 150 ° C., particularly from 40 to 130 ° C., in order to effectively promote both the grinding of the organic pigment particles and the particle growth by contact with the water-soluble organic solvent. By increasing the temperature, it is possible to promote the growth rate of the pigment particles. Conversely, when the kneading temperature is low, the crystal growth of the organic pigment is controlled, and the finer and sized effect is enhanced. However, if the kneading temperature is higher than 150 ° C., the crystal growth of the organic pigment is large, so that the kneading time needs to be short, the pigment sizing effect becomes insufficient, and this is not preferable in terms of quality.

If necessary, adjust the temperature of the kneader to two or more stages over time, knead the initial stage at a high temperature and the subsequent stage at a low temperature, and more efficiently control crystal growth, refinement, and sizing It is also possible. In addition, before or after kneading with the kneader, preliminary kneading or additional kneading is performed in another type of kneader and the temperature is changed each time, and the pigment particles are more effectively refined and sized. good.
It is not necessary to add the entire amount of the kneaded composition in the initial stage, and appropriately add a water-soluble organic solvent and a water-soluble inorganic salt according to the hardness condition of the kneaded composition or after the start of kneading, depending on the refinement and particle size of the kneaded composition. May be.

The kneaded composition after kneading is processed by a conventional method. That is, the kneaded composition is treated with water or a mineral acid aqueous solution, the water-soluble inorganic salt and the water-soluble organic solvent are removed by filtration and water washing, and the fine organic pigment is isolated. The fine organic pigment can be used in a wet state as it is, or in a powder state by drying and pulverization. If necessary, a resin, a resin-type pigment dispersant, a surfactant, and other additives may be added after kneading.
The average primary particle size of the fine organic pigment varies depending on the conditions of the refinement treatment and the type of organic pigment, but can be controlled to an arbitrary primary particle size within a range of about 10 to 500 nm by appropriately setting the conditions. Can do.

Next, the coloring composition for color filters containing the fine organic pigment obtained as described above and a pigment carrier made of a transparent resin, a precursor thereof or a mixture thereof will be described.
The pigment carrier constituting the coloring composition for a color filter in the present invention is made of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Examples of the transparent resin include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and active energy ray curable resins are particularly preferable. Moreover, as the precursor, the monomer or oligomer which hardens | cures by active energy ray irradiation and produces | generates transparent resin is mentioned, These can be used individually or in mixture of 2 or more types.

  The pigment carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, based on 100 parts by weight of the pigment in the color filter coloring composition. When a mixture of a transparent resin and its precursor is used as a pigment carrier, the transparent resin is 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the pigment in the coloring composition. Can be used. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

  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, 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 (meth) acrylic having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group on a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a compound or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  Monomers and oligomers that are precursors of transparent resins include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (me Acrylate), neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy ( Various acrylic esters and methacrylic esters such as (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy Examples include methyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

In addition, in the coloring composition for a color filter of the present invention, a pigment is sufficiently dispersed in a pigment carrier, and applied to a transparent substrate such as glass so that the dry film thickness is 0.2 to 5 μm. In order to make it easier to form, a solvent can be included. 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, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These can be used alone or in combination.
The solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, based on 100 parts by weight of the pigment in the color filter coloring composition.

When the colored composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition for a color filter of the present invention.
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 (trick (Romethyl) -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 amount of 5-200 weight part with respect to 100 weight part of pigments in the blue coloring composition for color filters, Preferably it is 10-150 weight part.

  These photopolymerization initiators are used alone or in admixture 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. A sensitizer can be used in the quantity of 0.1-60 weight part with respect to 100 weight part of photoinitiators in the coloring composition for color filters.

  In addition, the coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the coloring composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment in the color filter coloring composition.

The color filter coloring composition can be prepared as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent developing type or alkali developing type colored resist material. The solvent development type or alkali development type colored resist material is generally contained in a composition containing a thermoplastic resin, a thermosetting resin or an active energy ray curable resin, a monomer, a photopolymerization initiator, and a solvent. A pigment is dispersed in the mixture. The coloring composition for a color filter of the present invention can be produced by finely dispersing a pigment in a pigment carrier using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. . The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.
The colored composition for a color filter of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

When dispersing the pigment in the pigment carrier, a dispersion aid such as at least one derivative selected from the above-mentioned pigment derivatives, anthraquinone derivatives, acridone derivatives, and triazine derivatives, a resin-type pigment dispersant, a surfactant, and the like is appropriately added. Can be used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.
Among them, at least one derivative selected from pigment derivatives, anthraquinone derivatives, acridone derivatives, and triazine derivatives is excellent in preventing the aggregation of fine organic pigments and maintaining the finely dispersed state of organic pigments. By using the coloring composition to be contained, a color filter having a high contrast ratio and high color purity can be produced, which is preferable as a dispersion aid.
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust.

Next, the color filter of the present invention will be described.
The color filter of this invention is a color filter which comprises the filter segment formed using the coloring composition for color filters of this invention. The color filter includes an additive color mixture comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one magenta filter segment, at least one cyan filter segment, And a subtractive color type with at least one yellow filter segment.
The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the coloring composition of this invention and the coloring composition of said each color by the printing method or the photolithographic method.

As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. 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 is not dried and solidified 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 each color filter segment is formed by photolithography, the colored composition prepared as the solvent development type or alkali development type color resist is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. 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, 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, or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.
Prior to the examples, the measurement methods of the average primary particle diameter, aspect ratio, specific surface area and contrast ratio of the pigment, the preparation of the acrylic resin solutions used in the examples and comparative examples, and the production of fine organic pigments will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

  The average primary particle diameter of the pigment was measured by a general method for directly measuring the size of primary particles from a transmission electron microscope (TEM) photograph. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size was defined as the average primary particle size. The same result can be obtained by using either a transmission type (TEM) or a scanning type (SEM).

The aspect ratio of the pigment was calculated by the following formula by measuring the short axis diameter and the long axis diameter of the primary particles of each pigment from an electron microscope. The closer the aspect ratio is to 1, the more preferable the crystal state of the particles approaches a square.
(Aspect ratio) = (Long axis diameter) / (Short axis diameter)
The specific surface area of the pigment particles was determined by the BET method using nitrogen adsorption. For the measurement, an automatic vapor adsorption amount measuring device (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) was used.

The contrast ratio of the coating film was measured by the following method using the measuring apparatus shown in FIG. The light emitted from the backlight unit (7) for liquid crystal display passes through the polarizing plate (6), is polarized, and passes through the dried coating film (4) of the colored composition applied on the glass substrate (5). To the polarizing plate (3). If the polarization planes of the polarizing plate (6) and the polarizing plate (3) are parallel, light is transmitted through the polarizing plate (3), but if the polarization plane is perpendicular, the light is transmitted by the polarizing plate (3). Blocked. However, when light polarized by the polarizing plate (6) passes through the dried coating film (4) of the colored composition, scattering by pigment particles or the like occurs, and a part of the polarization plane is displaced. Is parallel, the amount of light transmitted through the polarizing plate (3) is reduced. When the deflecting plate is perpendicular, a part of the light is transmitted through the polarizing plate (3). This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)

Accordingly, when scattering occurs due to the pigment of the dried coating film (4) of the coloring composition, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.
A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter (1), and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask (2) having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

(Preparation of acrylic resin solution)
Place 800 parts of cyclohexanone in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 100 ° C. while injecting nitrogen gas into the vessel. A mixture of 60.0 parts of styrene, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate, and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to polymerize the reaction. Went.
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 and 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.

(Production of fine organic pigment 1)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6, “Lionol Blue E” manufactured by Toyo Ink Mfg. Co., Ltd.) 500 parts, sodium chloride 5000 parts, diethylene glycol 700 parts, 15000 capacity parts planetary mixer (Inoue And the mixture was ground to produce a fine copper phthalocyanine pigment. As operating conditions, the mixture was kneaded for 10 hours while maintaining a dense lump at a revolution of 18 rpm, a rotation of 54 rpm and a grinding temperature of 110 ° C. After grinding, the mixture was poured into warm water and stirred with a high speed mixer for 1 hour while heating to about 80 ° C. to form a slurry, which was filtered, washed with water and dried to obtain fine organic pigment 1.
The specific surface area of the obtained fine organic pigment 1 was 100 m ² / g, the average primary particle diameter was 45 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 1 was 1.67.

(Production of fine organic pigment 2)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6, “Lionol Blue E” manufactured by Toyo Ink Mfg. Co., Ltd.), copper phthalocyanine pigment derivative having phthalimidomethyl group (Compound 3), 50 parts, sodium chloride 5000 650 parts of diethylene glycol was charged into a 15000 volume part planetary mixer (Inoue Seisakusho), and the mixture was ground to produce a fine copper phthalocyanine pigment. As operating conditions, the mixture was kneaded for 14 hours while maintaining a dense lump at a revolution of 18 rpm, a rotation of 54 rpm and a grinding temperature of 70 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water and dried to obtain fine organic pigment 2.
The obtained fine organic pigment 2 had a specific surface area of 104 m ² / g, an average primary particle size of 42 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 2 was 1.67.

(Production of fine organic pigment 3)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6, “Lionol Blue E” manufactured by Toyo Ink Manufacturing Co., Ltd.) 455 parts, copper phthalocyanine pigment derivative having a basic group (compound 2) 45 parts, sodium chloride 5000 And 700 parts of diethylene glycol were put into a 15000 volume part trimix (Inoue Seisakusho), and the mixture was ground to produce a fine copper phthalocyanine pigment. As operating conditions, the mixture was kneaded for 10 hours while maintaining a dense lump at a revolution of 18 rpm, a rotation of 54 rpm and a grinding temperature of 70 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain fine organic pigment 3.
The obtained fine organic pigment 3 had a specific surface area of 111 m ² / g, an average primary particle size of 39 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 3 was 1.58.

(Production of fine organic pigment 4)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6, “Lionol Blue E” manufactured by Toyo Ink Mfg. Co., Ltd.), copper phthalocyanine pigment derivative having phthalimidomethyl group (Compound 3), 50 parts, sodium chloride 5000 Part, 750 parts of diethylene glycol was added to 15,000 parts by volume of Trimix (Inoue Seisakusho), and the mixture was ground to produce a fine copper phthalocyanine pigment. The operating conditions were: revolution 36 rpm, autorotation 108 rpm, grinding temperature 50 ° C. and kneading for 16 hours while maintaining a dense lump. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain fine organic pigment 4.
The specific surface area of the obtained fine organic pigment 4 was 122 m ² / g, the average primary particle diameter was 32 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 4 was 1.50.

(Production of fine organic pigment 5)
450 parts of ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6, “Lionol Blue E” manufactured by Toyo Ink Co., Ltd.), copper phthalocyanine pigment derivative (compound 3) having a phthalimidomethyl group, rosin as a resin 20 parts of ester, 5000 parts of sodium chloride and 750 parts of diethylene glycol were charged into 15000 parts by volume of Trimix (Inoue Seisakusho), and the mixture was ground to produce a fine copper phthalocyanine pigment. The operating conditions were: revolution 36 rpm, autorotation 108 rpm, grinding temperature 50 ° C. and kneading for 16 hours while maintaining a dense lump. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water and dried to obtain fine organic pigment 5.
The specific surface area of the obtained fine organic pigment 5 was 124 m ² / g, the average primary particle size was 30 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 5 was 1.51.

(Production of fine organic pigment 6)
550 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254, “Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals), 5000 parts of sodium chloride, 700 parts of diethylene glycol, 15000 parts by volume of planetary The mixture was put into a mixer (Inoue Seisakusho) and the mixture was ground to produce a fine diketopyrrolopyrrole pigment. As operating conditions, the mixture was kneaded for 10 hours while maintaining a dense lump at a revolution of 18 rpm, a rotation of 54 rpm and a grinding temperature of 110 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain fine organic pigment 6.
The obtained fine organic pigment 6 had a specific surface area of 90 m ² / g, an average primary particle size of 41 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 6 was 1.67.

(Production of fine organic pigment 7)
500 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254, “Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals), 50 diketopyrrolopyrrole pigment derivative having a basic group (Compound 5) Parts, 5000 parts of sodium chloride and 700 parts of diethylene glycol were put into a 15000 volume part trimix (Inoue Seisakusho), and the mixture was ground to produce a fine diketopyrrolopyrrole pigment. As operating conditions, the mixture was kneaded for 14 hours while maintaining a dense lump at a revolution of 18 rpm, a rotation of 54 rpm and a grinding temperature of 70 ° C. After grinding, the mixture was poured into warm water and stirred with a high-speed mixer for 1 hour while heating to about 80 ° C. to form a slurry, which was filtered, washed with water and dried to obtain fine organic pigment 7.
The specific surface area of the obtained fine organic pigment 7 was 112 m ² / g, the average primary particle diameter was 34 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 7 was 1.61.

(Production of fine organic pigment 8)
500 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254, “Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals), 50 parts of a quinacridone derivative having an acidic group (Compound 7), sodium chloride 5000 parts and 700 parts of diethylene glycol were added to 15000 parts by volume of Trimix (Inoue Seisakusho), and the mixture was ground to produce a fine diketopyrrolopyrrole pigment. As operating conditions, the mixture was kneaded for 10 hours while maintaining a dense lump at a revolution of 18 rpm, a rotation of 54 rpm and a grinding temperature of 70 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain fine organic pigment 8.
The specific surface area of the obtained fine organic pigment 8 was 104 m ² / g, the average primary particle diameter was 36 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 8 was 1.61.

(Production of fine organic pigment 9)
500 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254, “Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals), 50 diketopyrrolopyrrole pigment derivative having a basic group (Compound 5) Part, 20 parts of rosin ester as resin, 5000 parts of sodium chloride and 800 parts of diethylene glycol were charged into 15000 parts by volume of Trimix (Inoue Seisakusho), and the mixture was ground to produce a fine diketopyrrolopyrrole pigment. The operating conditions were: revolution 36 rpm, autorotation 108 rpm, grinding temperature 50 ° C. and kneading for 16 hours while maintaining a dense lump. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain fine organic pigment 9.
The specific surface area of the obtained fine organic pigment 9 was 121 m ² / g, the average primary particle diameter was 32 nm, and all the pigment particles were refined, and no coarse particles were observed. Moreover, the aspect ratio of the obtained fine organic pigment 9 was 1.59.

(Production of fine organic pigment 10)
2250 parts of halogenated copper phthalocyanine pigment (CI Pigment Green 36, “Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 250 parts of quinacridone pigment derivative having a basic group (Compound 4), 2250 parts of sodium chloride, diethylene glycol 2000 parts were put into a 15000 capacity part planetary mixer (Inoue Seisakusho), and the mixture was ground to produce a fine halogenated copper phthalocyanine pigment. The operating conditions were: revolution 18 rpm, rotation 54 rpm, grinding temperature 120 ° C., and kneading for 10 hours while maintaining a dense lump. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water and dried to obtain fine organic pigment 10.
The specific surface area of the obtained fine organic pigment 10 was 92 m ² / g, the average primary particle diameter was 54 nm, and all the pigment particles were refined, and no coarse particles were observed. Moreover, the aspect ratio of the obtained fine organic pigment 10 was 1.72.

(Production of fine organic pigment 11)
2250 parts of halogenated copper phthalocyanine pigment (CI Pigment Green 36, “Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 250 parts of quinacridone pigment derivative having a basic group (Compound 4), 2250 parts of sodium chloride, diethylene glycol 2000 parts were charged into 15000 parts by volume of Trimix (Inoue Seisakusho), and the mixture was ground to produce a fine halogenated copper phthalocyanine pigment. As operating conditions, the mixture was kneaded for 14 hours while maintaining a dense lump at a revolution of 18 rpm, a rotation of 54 rpm and a grinding temperature of 60 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain fine organic pigment 11.
The specific surface area of the obtained fine organic pigment 11 was 95 m ² / g, the average primary particle diameter was 48 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 11 was 1.68.

(Production of fine organic pigment 12)
Add quinophthalone pigment (CI Pigment Yellow 138, 500 parts of “Pariotol Yellow K0961HD” manufactured by BASF, 6000 parts of sodium chloride, and 700 parts of diethylene glycol into 15,000 volume parts of Trimix (Inoue Seisakusho) and polish the mixture. The quinophthalone pigment was crushed to produce a fine quinophthalone pigment that was kneaded for 10 hours while maintaining a dense lump at a revolution of 18 rpm and a rotation of 54 rpm at 70 ° C. The mixture was stirred for 1 hour with a high-speed mixer while being heated to about 80 ° C. to form a slurry, which was filtered, washed with water and dried to obtain a fine organic pigment 12.
The obtained fine organic pigment 12 had a specific surface area of 95 m ² / g, an average primary particle size of 44 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 12 was 1.74.

(Production of fine organic pigment 13)
460 parts of quinophthalone pigment (CI Pigment Yellow 138, “Pariotol Yellow K0961HD” manufactured by BASF), 40 parts of an azo pigment derivative having a basic group (Compound 12), 6000 parts of sodium chloride, 800 parts of diethylene glycol, 15000 The mixture was put into a trimix (Inoue Seisakusho Co., Ltd.) in a volume and the mixture was ground to produce a fine quinophthalone pigment. The operating conditions were: revolution 36 rpm, autorotation 108 rpm, grinding temperature 50 ° C. and kneading for 16 hours while maintaining a dense lump. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain fine organic pigment 13.
The obtained fine organic pigment 13 had a specific surface area of 104 m ² / g, an average primary particle size of 40 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 13 was 1.68.

(Production of fine organic pigment 14)
500 parts of dioxazine violet pigment (CI Pigment Violet 23, “Sumiton First Violet RL Base” manufactured by Sumitomo Chemical Co., Ltd.), 5000 parts of sodium chloride and 700 parts of diethylene glycol are added to a 15,000 volume part trimix (Inoue Seisakusho). The mixture was ground and the fine diketopyrrolopyrrole pigment was produced. As operating conditions, the mixture was kneaded for 10 hours while maintaining a dense lump at a revolution of 18 rpm, a rotation of 54 rpm and a grinding temperature of 70 ° C. After grinding, the mixture was poured into warm water and stirred with a high-speed mixer for 1 hour while being heated to about 80 ° C. to form a slurry, which was filtered, washed with water and dried to obtain a fine organic pigment 14.
The specific surface area of the obtained fine organic pigment 14 was 96 m ² / g, the average primary particle diameter was 52 nm, and all the pigment particles were refined, and no coarse particles were observed. Moreover, the aspect ratio of the obtained fine organic pigment 14 was 1.72.

(Manufacture of fine organic pigment 15)
450 parts of dioxazine violet pigment (CI Pigment Violet 23, “Sumiton First Violet RL Base” manufactured by Sumitomo Chemical Co., Ltd.), 50 parts of dioxazine violet pigment derivative (compound 6) having a basic group, 5000 parts of sodium chloride Then, 800 parts of diethylene glycol was added to 15,000 parts by volume of Trimix (Inoue Seisakusho), and the mixture was ground to produce a fine dioxazine violet pigment. The operating conditions were: revolution 36 rpm, autorotation 108 rpm, grinding temperature 50 ° C. and kneading for 16 hours while maintaining a dense lump. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water and dried to obtain fine organic pigment 15.
The specific surface area of the obtained fine organic pigment 15 was 108 m ² / g, the average primary particle diameter was 41 nm, and all the pigment particles were refined, and no coarse particles were observed. Further, the aspect ratio of the obtained fine organic pigment 15 was 1.62.

(Comparative pigment 1)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6, “Lionol Blue E” manufactured by Toyo Ink Manufacturing Co., Ltd.) 500 parts, 5000 parts of sodium chloride and 550 parts of diethylene glycol are charged into a 15000 capacity part double arm type kneader. The mixture was kneaded for 12 hours at 80 ° C. while maintaining a dense lump (dough). After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain Comparative Pigment 1. The comparative pigment 1 obtained had a specific surface area of 90 m ² / g and was observed with a TEM photograph. As a result, all the pigment particles were refined and no coarse particles were observed, but the average primary particle diameter was 60 nm. The aspect ratio was 1.75.

(Comparative pigment 2)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6, “Lionol Blue E” manufactured by Toyo Ink Mfg. Co., Ltd.), copper phthalocyanine pigment derivative having phthalimidomethyl group (Compound 3), 50 parts, sodium chloride 5000 Part and 550 parts of diethylene glycol were charged in a 15000 volume part double-arm kneader and kneaded for 10 hours while maintaining a dense lump at 70 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain comparative pigment 2.
The comparative pigment 2 obtained had a specific surface area of 95 m ² / g and was observed with a TEM photograph. As a result, all the pigment particles were fine and coarse particles were not observed, but the average primary particle size was 56 nm. The aspect ratio was 1.70.

(Comparative pigment 3)
550 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254, "Irgafore Red B-CF" manufactured by Ciba Specialty Chemicals), 5000 parts of sodium chloride, 600 parts of diethylene glycol, 15000 parts by volume The kneader was charged and kneaded for 12 hours while maintaining a dense lump at 80 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high-speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water and dried to obtain comparative pigment 3.
The specific surface area of the obtained comparative pigment 3 was 76 m ² / g, and when observed with a TEM photograph, all the pigment particles were refined and no coarse particles were observed, but the average primary particle diameter was 52 nm. The aspect ratio was 1.76.

(Comparative pigment 4)
500 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254, “Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals), 50 diketopyrrolopyrrole pigment derivative having a basic group (Compound 5) Parts, 5000 parts of sodium chloride and 600 parts of diethylene glycol were charged into a 15000 volume part double-arm kneader and kneaded for 10 hours while maintaining a dense lump at 70 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while being heated to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain comparative pigment 4.
The specific surface area of the obtained comparative pigment 4 was 82 m ² / g, and when observed with a TEM photograph, all the pigment particles were refined and no coarse particles were observed, but the average primary particle diameter was 43 nm. The aspect ratio was 1.72.

(Comparative pigment 5)
First, 2500 parts of a halogenated copper phthalocyanine pigment (CI Pigment Green 36, “Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 2500 parts of sodium chloride, and 1250 parts of diethylene glycol were charged into a 15000 capacity part double-arm kneader. The mixture was kneaded for 10 hours while maintaining a dense lump (dough) at 0 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain comparative pigment 5.
The specific surface area of the obtained comparative pigment 5 was 74 m ² / g, and when observed with a TEM photograph, all the pigment particles were fine and coarse particles were not observed, but the average primary particle diameter was 72 nm. The aspect ratio was 1.81.

(Comparative pigment 6)
500 parts of quinophthalone pigment (CI Pigment Yellow 138, “Pariol Yellow K0961HD” manufactured by BASF), 6000 parts of sodium chloride, and 600 parts of diethylene glycol are charged into a 15000 capacity part double-arm kneader, and a dense lump at 50 ° C. The mixture was kneaded for 14 hours while being held at (dough). After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain comparative pigment 6.
The specific surface area of the obtained comparative pigment 6 was 84 m ² / g, and when observed with a TEM photograph, all the pigment particles were refined and no coarse particles were observed, but the average primary particle diameter was 64 nm. The aspect ratio was 1.83.

(Comparative pigment 7)
450 parts of dioxazine violet pigment (CI Pigment Violet 23, “Sumiton First Violet RL Base” manufactured by Sumitomo Chemical Co., Ltd.), 50 parts of dioxazine violet pigment derivative (compound 6) having a basic group, 5000 parts of sodium chloride Then, 500 parts of diethylene glycol was charged into a 15000 volume part double-arm kneader and kneaded for 10 hours while maintaining a dense lump at 110 ° C. After grinding, the mixture was poured into warm water, stirred for 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered, washed with water, and dried to obtain comparative pigment 7.
The specific surface area of the obtained comparative pigment 7 was 87 m ² / g, and when observed with a TEM photograph, all the pigment particles were refined and no coarse particles were observed, but the average primary particle diameter was 64 nm. The aspect ratio was 1.88.

[Example 1]
After the resulting mixture having the following composition containing the fine organic pigment 1 is uniformly stirred, the mixture is dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm. The mixture was filtered through a 5 μm filter to prepare a pigment dispersion.
Fine organic pigment 1 10.0 parts Derivative (Compound 1) 1.0 part Phosphoric ester pigment dispersant ("BYK111" manufactured by Big Chemie) 1.0 part Acrylic resin solution 40.0 parts Cyclohexanone 48.0 parts

Furthermore, the mixture of the following composition containing the obtained pigment dispersion was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare an alkali developing resist material.
Pigment dispersion 45.0 parts Acrylic resin solution 15.0 parts Trimethylolpropane triacrylate 9.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator 2.0 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part Cyclohexanone 28.8 parts

[Examples 2 to 9, 11, 13, and 15, Reference Examples 10, 12, and 14, Comparative Examples 1 to 7]

An alkali developing resist material was prepared in the same manner as in Example 1 except that the fine organic pigment 1 of Example 1 was changed to a mixture of 10.0 parts of the fine organic pigment or comparative pigment shown in Table 1 and 1.0 part of the derivative. Obtained.
[Contrast ratio]
Three types of coated substrates having different film thicknesses were obtained from the alkali developing resist materials obtained in Examples and Comparative Examples using a spin coater on a 100 mm × 100 mm, 1.1 mm thick glass substrate.
The coated substrate is 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, heated at 230 ° C. for 1 hour, allowed to cool, and then a color luminance meter (manufactured by Topcon Corporation). The contrast ratio was measured using a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) as the polarizing plate (“BM-5A”). For the resist material-coated substrate, the contrast ratio at a film thickness of 2 μm was determined by an approximation method from the three sets of film thickness and contrast ratio data. The results are shown in Table 1. In addition, Table 1 shows the measurement results of the specific surface area, average primary particle diameter, and aspect ratio of the fine organic pigments used in Examples and Comparative Examples.

The resist material obtained in the examples was prepared by mixing a kneaded mixture containing an organic pigment, a water-soluble inorganic salt, and a water-soluble organic solvent between the blades and the inner wall of the tank by a planetary motion in which a plurality of blades rotate and revolve. Due to the fact that the dead space (dead point) is very small due to its precise spacing, and it has a powerful kneading effect, it contains fine pigments that have been sized together with miniaturization, so it has a higher contrast ratio than before .
In particular, Examples 3 to 5, 7 to 9, 11, 13, and 15 had a small average primary particle diameter, and the aspect ratio was adjusted to be closer to 1, and the contrast ratio was high.

It is a front view which shows an example of the kneading machine used by this invention. It is a conceptual diagram of the apparatus which measures the contrast ratio of a coating film.

(Figure 1)
1 Planetary type mixer body 2 Drive shaft 3 Tank 4 Blade (Fig. 2)
DESCRIPTION OF SYMBOLS 1 Luminometer 2 Mask 3 Polarizing plate 4 Colored composition dry coating film 5 Glass substrate 6 Polarizing plate 7 Backlight unit

Claims (6)

In a coloring composition for a color filter containing a pigment carrier and a pigment composed of a transparent resin, a precursor thereof or a mixture thereof,
The pigment is a fine organic pigment obtained by grinding and kneading a kneaded mixture containing an organic pigment, a water-soluble inorganic salt, and a water-soluble organic solvent with a planetary mixer in which a plurality of blades move in a planetary motion, and ,
A coloring composition for a color filter, wherein the aspect ratio of the pigment is 1.68 or less.   The colored composition for a color filter according to claim 1, wherein the kneaded mixture further contains at least one derivative selected from a pigment derivative, an anthraquinone derivative, an acridone derivative, and a triazine derivative.   The coloring composition for a color filter according to claim 1 or 2, wherein the planetary mixer has 3 planetary blades.   The coloring composition for a color filter according to any one of claims 1 to 3, wherein a kneading temperature when kneading the kneaded mixture is controlled to 0 to 150 ° C.   The colored composition for a color filter according to any one of claims 1 to 4, wherein the kneaded mixture further contains a resin.   A color filter comprising a filter segment formed using the color filter coloring composition according to claim 1.

Images