WO2005064366A1

WO2005064366A1 - Coloring composition for color filter and color filter

Info

Publication number: WO2005064366A1
Application number: PCT/JP2004/019422
Authority: WO
Inventors: Kenichi Fujita; Kunisuke Nakamura; Takeshi Sato; Takeshi Itoi
Original assignee: Toyo Ink Mfg. Co., Ltd.; Toppan Printing Co., Ltd.
Priority date: 2003-12-26
Filing date: 2004-12-24
Publication date: 2005-07-14
Also published as: TWI246607B; JP4469600B2; CN100416308C; JP2005189672A; KR20060132623A; KR101087546B1; CN1898582A; TW200528772A

Abstract

A coloring composition for a color filter comprising a treated pigment which is produced by preparing a mixture of a crude organic pigment having an average particle diameter of more than 100 nm or a pre-pigment being formed by the dry pulverization of said crude organic pigment and having an average primary particle diameter of 10 to 100 nm with a small amount of an organic solvent exhibiting a crystal growth function for the above crude organic pigment or pre-pigment, and then subjecting the above mixture to dry pulverization, and has a particle size distribution wherein pigment particles having a primary particle diameter of 100 nm or more account for 20 wt % or less of the total pigment particles and pigment particles having a primary particle diameter in the range of 20 to 100 nm account for 60 wt % or more of the total pigment particles; and a color filter which has a filter segment comprising the above coloring composition for a color filter.

Description

Specification

Coloring composition for color filter and color filter

Technical field

The present invention relates to a coloring composition used for manufacturing an optical color filter constituting a liquid crystal color display, a video camera, and the like, and a color filter using the coloring composition. More specifically, the present invention relates to a color filter coloring composition for forming a filter segment of a color filter generally called a stripe filter or a matrix filter.

Background art

[0002] A color filter is formed by arranging two or more types of fine band (stripe) filter segments in parallel or intersecting on the surface of a transparent substrate such as glass, or a fine filter segment. It consists of a fixed arrangement of vertical and horizontal directions. The filter segments are as fine as several microns to several hundred microns, and are arranged in a predetermined arrangement for each hue.

[0003] In general, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is generally necessary to form them at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

[0004] For this reason, a method called a pigment dispersion method in which a pigment having excellent light resistance and heat resistance is used as a coloring material is currently the mainstream method for producing a color filter.

[0005] In the case of the pigment dispersion method, a photosensitive colored composition in which a pigment is dispersed in a photosensitive transparent resin solution

(Pigment resist) is applied to a transparent substrate such as glass, the solvent is removed by drying, pattern exposure of one filter color is performed, and the unexposed part is removed by a development process to form a first color pattern. After applying a process such as heating as required, a color filter can be manufactured by sequentially repeating the same operation for all the filter colors.

[0006] In a liquid crystal display, a liquid crystal layer sandwiched between two polarizers passes through the first polarizer. The type using twisted nematic (TN) type liquid crystal, which performs display by controlling the amount of light passing through a second polarizing plate by controlling the degree of polarization of the polarized light, has become mainstream. Color display is enabled by providing a color filter between the two polarizing plates.However, in general, a color filter in which an organic pigment is dispersed disturbs the degree of polarization controlled by the liquid crystal due to scattering of light by pigment particles. Problem. That is, there is a phenomenon in which light leaks when light must be cut off (OFF state) and transmitted light attenuates when light must be transmitted (ON state). The power to call the ratio of the brightness on the display between the ON state and the OFF state the contrast ratio In general, it is known that the smaller the pigment particle diameter in the color filter, the higher the contrast ratio! /

[0007] In ordinary paints and inks, the transparency generally increases as the degree of dispersion of the pigment is increased. However, in ordinary dispersing machines such as a sand mill, a three-roll mill, and a ball mill, the pigment is dispersed to primary particles. Then, the transparency cannot be improved any more. The dispersing process in a usual dispersing machine is a process of loosening secondary particles, which are mainly aggregates of the primary particles of the pigment, to obtain a dispersion in a state close to the primary particles and further improving the transparency. To do this, the primary particles need to be further finely focused.

[0008] A high-speed sand mill is excellent in atomizing pigments, and is a force capable of reducing primary particles depending on pigments. In this case, a very large amount of energy is required.

[0009] As a means for finely examining the primary particles of the pigment, a method is known in which a pigment dissolved in a strong acid such as concentrated sulfuric acid or polyphosphoric acid is poured into cold water or ice water to precipitate the pigment as fine particles. (See, for example, JP-A-8-179111). However, in this method, the pigments that can be used are significantly limited in terms of solubility and stability of the pigments in strong acids. In addition, since pigments fined by this method cause strong secondary aggregation when dried, it is generally very difficult to re-disperse them into primary particles.

[0010] Further, as other means for reducing the primary particles of the pigment, a dry pulverization method, a solvent salt milling method and the like are widely known.

[0011] The dry pulverization method is a method in which the primary particles of the pigment are finely pulverized by dry pulverization using a ball mill, an attritor, a vibration mill, or the like. Compared to the solvent salt milling method, the production per unit energy is reduced. Efficiency is high. No industrial waste is generated, which has an impact on the environment. This is a preferable method in terms of the point. If dry pulverization is simply applied to the coarse pigment particles while applying force, the primary particles of the pigment can be finely dispersed, but the particle diameter varies greatly and the cohesive force between the particles is extremely strong. Therefore, in many cases, only large aggregates in which a large number of finely divided pigment primary particles are strongly and strongly bonded are obtained, and it is very difficult to disperse the pigment particles.

[0012] The solvent salt milling method uses a kneader or the like in the presence of an inorganic salt such as sodium chloride and sodium sulfate and a highly viscous water-soluble organic solvent such as ethylene glycol, diethylene glycol and polyethylene glycol. This is a method in which the primary particles of the pigment are finely ground by mechanically milling. However, the solvent salt milling method consumes a large amount of electric power and therefore has low productivity per unit energy. In addition, since the organic solvent is used in an amount equal to or more than several times the amount of the inorganic salts with respect to the pigment, water washing and filtration steps for separating the inorganic salts and the organic solvent from the pigment are required. is necessary. In addition, the drying process performed after washing and filtration causes the pigment to form aggregates.In particular, as the primary particles of the pigment are refined to obtain a high-contrast color filter, the pigments become extremely strong aggregates as compared with the dry pulverization method. Is very difficult to disperse. For this reason, even if a pigment whose primary particles are made finer by this method is used, it is difficult to further improve the contrast.o

[0013] The thickness of the filter segment of the color filter is about 1 μm, and the variation in the film thickness is suppressed to 10 Onm or less. Since the photosensitive coloring composition is usually applied with a spin coater or the like, in order to achieve this accuracy, the photosensitive coloring composition is required to have an extremely low viscosity. In general, the more the pigment is dispersed, the higher the viscosity of the photosensitive coloring composition becomes, and the viscosity tends to increase with time.

Disclosure of the invention

An object of the present invention is to provide a coloring composition in which fine pigment particles are stably dispersed and which has a very low viscosity, and which can produce a color filter having a high contrast ratio. Is to provide a high color filter.

According to a first aspect of the present invention, the organic pigment includes a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof, and an organic pigment, wherein the organic pigment has an average particle diameter of greater than 100 nm. A small amount of an organic solvent having a crystal growth effect on the pre-pigment is added to a pre-pigment having an average primary particle diameter of 10 lOOnm obtained by dry-pulverizing a crude organic pigment, followed by dry-pulverization. The pigment particles having a primary particle diameter of lOOnm or more account for 20% by weight or less of all the pigment particles, and the pigment particles having a primary particle diameter of 20 to 100 nm correspond to all the pigment particles. A coloring composition for a color filter, which is a treated pigment having a particle size distribution of 60% by weight or more of the color filter.

[0016] According to a second aspect of the present invention, the organic pigment includes a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof, and an organic pigment, wherein the organic pigment is a crude product having an average particle diameter of greater than 100 nm. The organic pigment is dried and pulverized by adding a small amount of an organic solvent having a crystal growth action to the crude organic pigment, and all pigment particles having an average primary particle diameter of 10 lOOnm and a primary particle diameter of lOOnm or more are obtained. Provided is a coloring composition for a color filter, which is a treated pigment having a particle size distribution of not more than 20% by weight of the pigment particles and having a primary particle diameter of 20 to 100 nm in a range of not less than 60% by weight of all the pigment particles. Is done.

According to a third aspect of the present invention, there is provided a color filter including a filter segment formed from the coloring composition for a color filter of the present invention.

Brief Description of Drawings

FIG. 1 is a conceptual diagram of a measuring device for measuring a contrast ratio.

BEST MODE FOR CARRYING OUT THE INVENTION

First, the coloring composition for a color filter of the present invention will be described.

[0020] The coloring composition for a color filter of the present invention contains a pigment carrier composed of a transparent resin, a precursor thereof, or a mixture thereof, and an organic pigment.

According to the first aspect of the present invention, the organic pigment is a pre-pigment having an average primary particle diameter of 10-lOO nm obtained by dry-pulverizing a crude organic pigment having an average particle diameter of more than 100 nm, On the other hand, a small amount of an organic solvent having a crystal growth effect is added and dry-pulverized, and the particles are sized while suppressing the change in the average primary particle diameter of the pigment to 30 nm or less. The treated pigment has a particle size distribution of not more than 20% by weight of the pigment particles and having a primary particle diameter of 20 to 100 nm in the range of not less than 60% by weight of all the pigment particles. [0022] Alternatively, according to the second aspect of the present invention, the organic pigment includes a crude organic pigment having an average particle size of greater than 100 nm and a small amount of an organic solvent having a crystal growth effect on the crude organic pigment. The pigment particles with an average primary particle size of 10-100 nm and a primary particle size of 100 nm or more are less than 20% by weight of all pigment particles, and a primary particle size of 20-100 nm. Is a treated pigment having a particle size distribution in which 60% by weight or more of the total pigment particles are present. The treated pigment according to the first aspect and the treated pigment according to the second aspect are collectively referred to simply as treated pigments.

[0023] In the above treated pigment, even in the case of V or deviation, the primary particles are refined and sized in a uniform particle shape. Therefore, the coloring composition for a color filter of the present invention, in which the treated pigment is uniformly dispersed in the pigment carrier while maintaining the fine particle state, has stable viscosity characteristics. Further, the color filter formed using the coloring composition for a color filter of the present invention has a high contrast ratio.

As the crude organic pigment having an average particle size of greater than 100 nm, a commercially available large-particle-size organic pigment or a large-particle-size organic pigment synthesized by a known method can be used. It is preferable to use a crude organic pigment having an average particle size larger than 11Onm, since a treated pigment having a desired particle size distribution can be easily obtained.

[0025] The organic pigments used in the present invention are shown below by color index (C.I.) numbers.

[0026] The red coloring composition for forming the red filter segment includes, for example, ι.

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, 226, 227, 228, 240, 246, 254, 255, Red pigments such as 264 and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red composition.

[0027] Green coloring compositions for forming green filter segments include, for example, C 丄

Green pigments such as Pigment Green 7, 10, 36, and 37 can be used. A yellow pigment can be used in combination with the green coloring composition.

[0028] The blue coloring composition for forming the blue filter segment includes, for example, C 丄 Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, can Ru possible force ^s use blue Pigments of 64, and the like. Blue pigments can be combined with purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50.

[0029] Cyan colored yarn components for forming a cyan filter segment include, for example, C 丄

Pigment Blue 5: l, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81, etc. Blue pigments can be used.

In general, when a copper phthalocyanine pigment, which is a blue pigment, is ground in a dry state with a pulverizing medium, an α-type copper phthalocyanine pigment (CI. Pigment Blue 15: 1) is formed, and an ε-type copper phthalocyanine pigment is formed. In some cases, copper phthalocyanine pigment (Blue. Pigment Blue 15: 6) cannot be obtained with high purity. However, in the treatment of the organic pigment of the present invention, since the organic solvent present at the time of dry pulverization has the effect of suppressing the formation of the type copper phthalocyanine pigment, an appropriate organic solvent type is selected and the optimum amount is selected. By coexisting with ε, it is possible to obtain an ε-type copper phthalocyanine pigment having a fine and uniform particle diameter.

[0031] The yellow colored yarn composition for forming the yellow color filter segment includes, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 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, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, etc. .

[0032] As the orange coloring composition for forming the orange filter segment, for example, orange pigments such as C.I. Pigment orange 36, 43, 51, 55, 59, 61 and the like can be used.

[0033] 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 and the like are used. Can be. Magenta color composition is combined with yellow pigment can do.

[0034] These organic pigments may be used alone or in combination, and two or more of them may be mixed and dry-pulverized. For example, green pigments and yellow pigments, red pigments and orange pigments or yellow pigments may be used. Pigments having different hues can be mixed and treated.

In the present invention, it is particularly preferable to use yellow pigments, particularly C Pigment Yellow 138, 139, and 185, as the organic pigment, because the effect of improving the contrast ratio is high.

[0036] Examples of the organic solvent having a crystal growth effect on the pre-pigment and the crude organic pigment include benzene, tonolenene, xylene, ethynolebenzene, benzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, methanol, Ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether ether, diethylene glycol monobutyl ether ether, Propylene glycol, propylene glycol monomethyl ether acetate, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, pendeca It can include dodecane, cyclohexane, Sasan methylcyclohexane, halogenated hydrocarbon, acetone, methylcarbamoyl Ruechiruketon, methyl isobutyl ketone, cyclohexanone, dimethylformamide, di-methyl sulfoxide, N- methylpyrrolidone. The above organic solvents may be used as a mixture of two or more as necessary.

As the organic solvent having a crystal growth action, it is necessary that the crude organic pigment / pre-pigment coexist with the crude organic pigment / pre-pigment without being evaporated in the dry pulverization step. It is preferable to use an organic solvent at a temperature of ° C.

[0038] The organic solvent having a crystal growth effect is not particularly required to be removed as long as it does not hinder the preparation of the coloring composition for a color filter. However, if necessary, it can be easily removed by a method such as drying under reduced pressure or freeze-drying. Can be removed. The removal of the organic solvent may be carried out using the apparatus used for dry grinding in the presence of the organic solvent as it is, or may be transferred to another apparatus.

Further, before or during the step of adding an organic solvent and performing dry pulverization, a dye derivative, a resin, a surfactant and the like may be added. [0040] The dye derivative is a compound in which a substituent is introduced into an organic dye, and is added for the purpose of accelerating the refinement of a crude organic pigment or preventing the generation of another crystalline pigment due to crystal rearrangement. . Organic dyes also include naphthalene-based and anthraquinone-based pale yellow aromatic polycyclic compounds and heterocyclic compounds such as triazine, which are not generally referred to as dyes. By dry-grinding with the addition of the dye derivative, the average primary particle diameter can be made smaller and the contrast ratio can be improved. Dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5-9469. Can be used, and these can be used alone or in combination of two or more.

Specific examples of the dye derivative include a dye derivative having a basic group represented by the following general formulas (1), (2), (3) and (4).

[Formula 1] Equation (1)

[Formula 2] Equation (2):

~ CH ₂ N

R

[Formula 3] Equation (3)

[Formula 4] Equation (4):

In the above formulas (1)-(4), X represents —SO 1, CO—, 1 CH NHCOCH 1, CH— or

Represents a 2 2 2 or a single bond. X is preferably -so or a single bond.

2

[0043] n represents an integer of 110. n is preferably 1 to 3.

[0044] R and R are each independently unsubstituted or substituted having 1 to 36 carbon atoms.

1 2

A substituted alkyl group, an unsubstituted or substituted alkenyl group having 2 to 36 carbon atoms or an unsubstituted or substituted phenyl group, or R

1 and R

And 2 combine to form an unsubstituted or substituted heterocycle containing additional nitrogen, oxygen or sulfur atoms. R and R are

12 is preferably an unsubstituted or substituted alkyl group having 115 carbon atoms.

R is an unsubstituted or substituted alkyl group having 1 to 36 carbon atoms, 2 to 36

Three

Represents an unsubstituted or substituted alkenyl group having carbon atoms or an unsubstituted or substituted phenyl group. R is preferably an unsubstituted or substituted alkyl having 114 carbon atoms.

Three

It is a quinole group.

R, R, R and R each independently represent a hydrogen atom, having 1 to 36 carbon atoms

4 5 6 7

Represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkyl group having 2 to 36 carbon atoms, or an unsubstituted or substituted phenyl group. R, R, R and R are Preferably, each is an unsubstituted or substituted alkyl group having 114 carbon atoms.

[0047] Y represents -NR-Z-NR or a single bond.

8 9

[0048] R and R each independently represent a hydrogen atom, an unsubstituted group having 1 to 36 carbon atoms.

8 9

Or a substituted alkyl group, an unsubstituted or substituted alkenyl group having 2 to 36 carbon atoms, or an unsubstituted or substituted phenyl group. R and R are preferably

8 9 is a hydrogen atom.

[0049] Z is an unsubstituted or substituted alkylene group having 1 to 36 carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 36 carbon atoms, or an unsubstituted or substituted phenylene group Represents Z is preferably an unsubstituted or substituted phenylene group.

[0050]

[Formula 5] Equation (5)

[0051] a substituent represented by

[Formula 6] Equation (6)

[0052] represents a substituent represented by In the above formulas (5) and (6),! /, R—R, and n are as defined above.

[0053] Q is a hydroxyl group, an alkoxyl group, a substituent represented by the above formula (5) or a group represented by the above formula (6) Represents the substituent shown. Q is preferably a substituent represented by the above formula (5).

Examples of the organic dye residue constituting the dye derivative include azo dyes such as diketopyrrolopyrrole dyes, azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthrachinone, anthrapyrimidine, and furano. Anthraquinone dyes, such as anthrone, anthantrone, indanthrone, pyranthrone, and biolanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, and quinophthalones Dyes, sulene dyes, metal complex dyes and the like. Further, a pigment used in a coloring composition for a color filter described later may be used.

[0055] Further, the dye derivative may be an alkyl group such as a methyl group or an ethyl group, an amino group or a dimethylamino group, an alkylamino group such as a acetylamino group, a dibutylamino group, a nitro group, a hydroxyl group or a methoxy group, an ethoxy group, Alkoxy groups such as butoxy groups, halogens such as chlorine or methyl groups, methoxy groups, amino groups, dimethylamino groups, phenyl groups which may be substituted with hydroxyl groups, etc., methyl groups, ethyl groups, methoxy groups, ethoxy groups, It may have a substituent such as a phenylamino group which may be substituted with an amino group, a dimethylamino group, a acetylamino group, a nitro group, a hydroxyl group or the like.

[0056] The dye derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after a substituent represented by the following formula (7) -formula (10) is introduced into an organic dye, it reacts with the substituent to form a substituent represented by formula (1) and set (4). For example, N, N-dimethylaminopropylamine, N-methylbiperazine, getylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] —1,3,5-triazine—2— It can be obtained by reacting the compound.

Formula (7): -SO C1

2

Equation (8): -COC1

Formula (9): -CH NHCOCH C1

twenty two

Formula (10): -CH C1

2

When the organic dye is an azo dye, a basic group constituting the dye derivative represented by the general formula (1)-(4) is introduced into the diazo component or the coupling component in advance, and then the coupling reaction is performed. Producing azo dye derivative having basic group by performing Talk about this.

[0058] The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component forming a substituent represented by the general formula (1)-(4) on at least one chlorine of the salt of cyanide, for example, N, N-dimethylamino It can be obtained by reacting propylamine or N-methylbiperazine and the like, and then reacting the remaining chlorine of the salt with various amines or alcohols.

[0059] Examples of the amine component used to form the substituent represented by the general formula (1)-(6) include dimethylamine, getylamine, N, N-ethylisopropylamine, 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, di (2-ethyl) Hexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diarylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine Min, N, N—Jetylaminoethylamine, N, N—Jetylaminopropylamine, N, N—Jetylaminohexylamine, N, N—Jetylaminobutyramine, N, N—Jetyl Aminopentylamine, N, N-dipropylaminobutylamine, N, N dibutylaminopropylamine, N, N dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylamine Minopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N distearylaminoethylamine N, N-Dioleylaminoethylamine, N, N Distearylaminobutylamine, Piberidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4 Norepetidine, 2,6-Lupetidine, 3, 5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isodipecotic acid, methyl isodicopectate, ethyl ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3 —Hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N—Aminoethylmorpholine, N-aminopropylpiperidine, N—Aminopropyl 2-pipecoline, N-Aminopropyl 4-pipecoline, N-Aminopropylmorpholine, N-Methylpilineぺ Lazine, N-butylpiperazine, N-methylhomopirazine, 1-cyclopentylpiperazine, 1-amino-4-methylbiperazine, 1-cyclopentylbiperazine and the like. Dye derivatives can be any of those shown in Table 119. However, the present invention is not limited to these. The dye derivatives can be used alone or in combination of two or more.

[Formula 7]

Dye derivative 1

Dye derivative 3

[Formula 8] Dye derivative 4

Dye derivative 5

Dye derivative 6

Dye derivative 7

[Formula 9]

Dye derivative 12

[Formula 10] Dye translation 1 3

[Formula 11]

[Formula 12] Dye derivative 2 2

[Formula 13]

Dye derivative 2 6

Dye derivative 2 9

[Formula 14]

Plastid 31

[Formula 15] Dye derivative 3 4

[Formula 16]

Dye derivative 3 6

Dye derivative 3 9

[Formula 17] Dye derivative 4 0

^ ΙΐΙ conductor 4 1

[Formula 18]

Pigment orchid book 47

[Formula 20] Dye derivative 4 9

[Formula 21]

Pigment ¾ 5 1

[0061] The dye derivative may be used in a ratio of 0.1 to 30% based on the weight of the crude organic pigment.

[0062] The resin added when the above-mentioned pre-pigment or crude pigment is dry-pulverized is not particularly limited, but rosin, rosin derivative, rosin-modified maleic acid resin, rosin-modified phenol resin, rubber derivative , Protein derivatives, chlorinated polyethylene, chlorinated polypropylene, polychloride butyl, polyacetate butyl, epoxy resin, acrylic resin, maleic acid resin, styrene resin, styrene maleic acid copolymer resin, petitlar Grease, polyester grease, melamine grease, phenol grease, polyurethane grease, polyamide grease, polyimide grease, Examples thereof include liquid resin, rubber resin, celluloses, benzoguanamine resin, urea resin, and oligomers and monomers of the above resins. These resins can be used in an amount of 0.1 to 50% based on the weight of the crude organic pigment.

The dry pulverization of the crude organic pigment / pre-pigment is not particularly limited, but may be carried out using a conventional dry pulverization apparatus incorporating a pulverization medium such as beads, for example, an apparatus such as a ball mill, an attritor, and a vibration mill. Can be done. The grinding of the crude organic pigment / pre-pigment proceeds through the collision and friction between the grinding media. If necessary, the inside of the pulverizing vessel may be depressurized or filled with an inert gas such as nitrogen gas.

[0064] There are no particular restrictions on the operating conditions of the dry pulverizer; however, it is important that grinding by a pulverizing medium and crystal growth of a crude organic pigment / pre-pigment by contact with an organic solvent include: The following conditions are particularly preferred in order for each to proceed effectively.

[0065] That is, when the dry grinding device is an attritor, the rotation speed of the device is preferably 100 to 500 rpm, and the dry grinding time (preferably, when the treated pigment is produced via the pre-pigment, the pre-pigment is produced). (The combined time of dry pulverization and dry pulverization in the presence of an organic solvent) is preferably 0.5 to 8 hours, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Also, the crushing media is preferably spherical with a diameter of 430 mm. The amount of media used is preferably 5 to 50 times the weight of the crude organic pigment or pre-pigment to be processed!

[0066] Further, when the dry grinding apparatus is a ball mill, the rotation speed of the apparatus is preferably 50 to 200 rpm. The total time of the dry pulverization and the dry pulverization in the presence of an organic solvent) is preferably 11 to 12 hours, and the internal temperature of the apparatus is preferably 30 to 100 ° C. Also, the grinding media is preferably spherical with a diameter of 10-50 mm. The amount of media used is 5-50 times the weight of the crude organic pigment pre-pigment to be processed!

The amount of the organic solvent having a crystal growth effect on the crude organic pigment or pre-pigment is in the range of 0.5 to 50% by weight of the weight of the crude organic pigment or pre-pigment, and preferably 1 to 30%. % By weight. That is, the dry pulverization after the addition of the organic solvent is a completely dry mixing and stirring state. Most of the organic solvents coexist in a state adsorbed on the pigment surface.However, when an organic solvent with a low boiling point is used, a part of And coexist in the mixing and stirring system. What is important here is that milling by dry milling continues even during mixing and stirring. However, due to the effect of the coexisting organic solvent, the crystal growth of the particles also progresses at the same time.By optimizing the mixing and stirring conditions, the grinding and the crystal growth are balanced, and the particle size can be realized by the conventional dry grinding method. It is possible to regulate the particle size to a uniform particle size.

[0068] In the present invention, the term "sizing while suppressing the change in the average primary particle diameter to 30 nm or less" refers to a pre-pigment containing coarse primary particles having a large variation in the particle diameter and a particle shape. Means that the treated pigment has a small range of variation in particle size, and at this time, the average primary particle size of the entire particle changes only within a range of 30 nm or less.

[0069] The range of variation in the particle diameter of the treated pigment is as follows: pigment particles having a primary particle diameter of lOOnm or less account for 20% by weight or less of all pigment particles, and pigment particles having a primary particle diameter of 20 lOOnm correspond to all pigment particles. It must be at least 60% by weight, and it is preferable that the pigment particles having a particle diameter in the range of 30 to 80 nm be at least 80% by weight of all the pigment particles.

[0070] The pigment carrier contained in the coloring composition for color filter of the present invention together with the treated pigment is composed of a transparent resin, a precursor thereof, or a mixture thereof. Here, the pigment carrier can be used in an amount of preferably 50 to 700%, more preferably 100 to 400%, based on the weight of the treated pigment.

The transparent resin constituting the pigment carrier has 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. Transparent resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and their precursors include monomers or oligomers that cure by irradiation to produce transparent resins. These can be used alone or in combination of two or more. When the composition is cured by irradiation with ultraviolet light, a photopolymerization initiator and the like are added to the coloring composition for a color filter of the present invention.

[0072] Examples of the thermoplastic resin include butyral resin, styrene / maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, and polyvinyl chloride. Vinyl acetate, polyurethane resin, polyester resin, acrylic resin Fat, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polybutadiene, polyimide resin and the like. Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, melamine resin, urea resin, phenol resin and the like.

[0073] As the photosensitive resin, a resin having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group has a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group. ) A resin obtained by reacting an acrylic conjugate or Keihi's acid to introduce a photocrosslinkable group such as a (meth) atalyloyl group or a styryl group is used. In addition, a resin containing an acid anhydride such as a styrene maleic anhydride copolymer or an α-olefin maleic anhydride copolymer is half-etched by a (meth) acrylic conjugate having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A stealed version is also used.

[0074] Examples of the monomer and oligomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, and trimethylol. Propane tri (meth) acrylate, pentaerythritol tri (meta) acrylate, dipentaerythritol hex (meth) acrylate, tricyclodehydryl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate And various acrylates and methacrylates such as acrylates, (meth) acrylic acid, styrene, butyl acetate, (meth) acrylamide, Ν-hydroxymethyl (meth) acrylamide, and acryl-tril.

[0075] Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4t-butyldichloroacetophenone, diethoxyacetophenone, and 1- (4-isopropylphenyl) 1-2-hydroxy-2-hydroxy. Methylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane 1-one, etc., acetophenone photopolymerization initiators, benzoin, benzoin methyl ether Benzoin-based photopolymerization initiators such as benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; benzophenone; benzoyl benzoic acid; methyl benzoyl benzoate; Ben Zylou 4, -methyldihue Benzophenone-based photopolymerization initiators such as Thioxanthone-based photopolymerization initiators such as xanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanson, and 2,4-diisopropylthioxanthone; 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-piper-lu 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-methoxynaphtho-1yl) 4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl Roux (Pi-mouth)-6- Triazine photopolymerization initiators such as lyazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, borate photopolymerization initiator, carbazole photopolymerization initiator, imidazole photopolymerization initiator Are used. The photopolymerization initiator can be used in an amount of 5 to 150% based on the weight of the treated pigment.

[0076] The above photopolymerization initiators are used alone or as a mixture of two or more kinds. As sensitizers, a-siloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10F Enanthrene quinone, camphor quinone, ethilan anthraquinone, 4,4'-ethylethyl isophthalene phenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbol) benzophenone, 4,4, -A compound such as dimethylaminobenzophenone can also be used in combination. The sensitizer can be used in an amount of 0.1 to 30% based on the weight of the photopolymerization initiator.

[0077] The coloring composition for a color filter of the present invention is prepared by dispersing the treated pigment in a pigment carrier together with the above-mentioned photopolymerization initiator, if necessary, using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, and a kneader. And finely dispersed using the same. When the coloring composition for a color filter of the present invention contains two or more kinds of treated pigments, each of the treated pigments may be separately dispersed in a pigment carrier and then mixed.

[0078] When the treated pigment is dispersed in the pigment carrier, a dispersing aid such as a resin-based pigment dispersant, a surfactant, and a dye derivative can be appropriately contained. The dispersing aid is excellent in dispersing the pigment and has a large effect of preventing re-aggregation of the treated pigment after the dispersion. Transparency when used A color filter excellent in the above is obtained.

[0079] The oil-based pigment dispersant has a pigment affinity site having a property of adsorbing to the pigment, and a site compatible with the pigment carrier, and adsorbs on the pigment to disperse the pigment in the pigment carrier. It works to stabilize. Specific examples of the lipophilic pigment dispersant include polycarboxylic acid esters such as polyurethane and polyatalylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, and polycarboxylic acid ammonium salts. , Polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic esters, modified products thereof, and the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups Oil-based dispersants such as amides and salts thereof formed by the method; (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polybutyl Water-soluble resins such as alcohol and polyvinylpyrrolidone; water-soluble polymer compounds; polyesters; For example, a reactive polyatalylate type, an ethylene oxide Z-propylene oxide addition conjugate, a phosphate ester type, or the like can be used, and these can be used alone or as a mixture of two or more.

[0080] Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl difluoroether disulfonate, and monoethanol lauryl sulfate. Amin, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene acrylic acid copolymer monoethanolamine, polyoxyethylene alkyl ether Anionic surfactants such as phosphate esters; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene phenol ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; alkylene quaternary ammonium salts, and their chaotic surfactants such as their ethylene oxide adducts. Agents: alkyl betaines such as alkyl dimethylaminoacetate betaines and amphoteric surfactants such as alkyl imidazolines, which can be used alone or as a mixture of two or more. [0081] The dye derivative is a compound in which a substituent is introduced into an organic dye, and is preferably a compound having a color close to the hue of the pigment to be used. Organic dyes also include naphthalene-based and anthraquinone-based light yellow aromatic polycyclic compounds that are not generally called dyes. Dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5-9469. And these can be used alone or in combination of two or more.

[0082] These dispersing aids can be used in an amount of 0.1 to 30% based on the weight of the treated pigment.

Further, in the coloring composition for a color filter of the present invention, the treated pigment is sufficiently dispersed in a pigment carrier so that the dry film thickness becomes 0.2 to 5 m on a transparent substrate such as a glass substrate. A solvent can be included to facilitate the formation of the filter segment by coating on the substrate. Solvents include, for example, cyclohexanone, ethyl acetate solvent acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethynoate ethereol, etinolebenzene, ethylene glycolone regentinoate ethereol, xylene, ethyl sorbe methylate, methyl n-amyl ketone Propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvents and the like. These may be used alone or as a mixture. The solvent contained in the coloring composition of the present invention may include, in addition to these solvents, the organic solvent having the above-described crystal growth action. The solvent can be used in a total amount of 500-4000%, based on the weight of the treated pigment.

[0084] The coloring composition for a color filter of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and getylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butyl pyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Organic phosphine, phosphite and the like. Storage stabilizers can be used in amounts of 0.1% to 5%, based on the weight of the treated pigment. [0085] The coloring composition for a color filter of the present invention may contain an inorganic pigment in order to ensure good coating properties, sensitivity, developability, etc. while maintaining a balance between saturation and lightness. it can. Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron, red cadmium red, ultramarine blue, navy blue, chrome oxide green, cobalt green, Amber, titanium black, synthetic iron black, carbon black and the like. The inorganic pigments may be used alone or in combination of two or more. The inorganic pigment can be used in an amount of 0.1 to 10% based on the weight of the treated pigment.

[0086] The coloring composition for a color filter of the present invention may contain a dye for the purpose of toning, as long as the heat resistance is not reduced. The dye can be used in an amount of 0.1 to 10% based on the weight of the treated pigment.

[0087] The colored yarn composition for a color filter of the present invention is prepared in the form of a gravure offset printing ink, a waterless offset printing ink, a silk screen printing ink, a solvent development type or an alkali development type coloring resist material. Can be. The colored resist material is obtained by dispersing a treated pigment in a composition containing the thermoplastic resin, the thermosetting resin or the photosensitive resin, the monomer, and the photopolymerization initiator.

[0088] Preferably, when the filter segment is formed by a photolithographic method, the treated pigment is contained in the solvent-containing coloring composition at a ratio of 1.5 to 7% by weight, and the filter segment is formed by a printing method. When formed by the method described above, it is contained in the coloring composition containing a solvent at a ratio of 1.5 to 40% by weight. In any case, the treated pigment is preferably present in the final filter segment in a proportion of from 10 to 55% by weight, more preferably from 20 to 50% by weight, the balance being the lipid binder provided by the pigment carrier. Kara becomes substantially.

[0089] The colored composition for a color filter of the present invention is obtained by means of centrifugation, a sintered filter, a membrane filter, or the like, using coarse particles of 5 µm or more, preferably 1 µm or more, more preferably It is preferable to remove coarse particles of 0.5 m or more and mixed dust.

Next, the color filter of the present invention will be described.

[0091] The color filter of the present invention includes a filter segment formed using the coloring composition of the present invention. The color filter of the present invention is formed by a printing method or a photolithography method. It can be manufactured by forming filter segments of each color on a transparent substrate using a color composition. As the transparent substrate, a glass plate or a resin plate of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is used.

[0092] The formation of each color filter segment by the printing method can be patterned by simply repeating the printing and drying of the coloring composition prepared as the various printing inks described above. Excellent mass productivity. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, the composition is preferably such that the ink does not dry and solidify on a printing plate or on a blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender.

[0093] When forming each color filter segment by a photolithography method, the coloring composition prepared as the solvent-imageable or alkali-developable colored resist material is spray-coated, spin-coated, or slit-coated on a transparent substrate. By a coating method such as roll coating or the like, coating is performed so that the dry film thickness is 0.2-5 / zm. The film dried as necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact or non-contact with the film. Then, the developer is sprayed with a solvent or a spray dipped in a solvent or an alkaline developer to remove the uncured portion to form a desired pattern, and the same operation is repeated with another color. A color filter can be manufactured. Further, in order to promote 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 printing method can be manufactured.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developer. In order to increase the UV exposure sensitivity, the above-mentioned colored resist material is applied and dried, and then a water-soluble or alkali-water-soluble resin such as polybutyl alcohol or a water-soluble acrylic resin is applied and dried to inhibit polymerization by oxygen. After forming a film for preventing the occurrence of ultraviolet rays, ultraviolet exposure can be performed.

[0095] The color filter of the present invention can be manufactured by an electrodeposition method, a transfer method, or the like in addition to the above method. The coloring composition of the present invention can be used in any method. The electrodeposition method is a method in which a color filter is manufactured by using a transparent conductive film formed on a transparent substrate and electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloid particles. is there. The transfer method is a method in which a color filter layer is previously formed on the surface of a peelable transfer base sheet, and the color filter layer is transferred to a desired transparent substrate.

Example

[0096] Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” means “parts by weight”, and “%” means “% by weight”.

Next, a method for measuring the contrast ratio of a coating film produced using a resist will be described with reference to FIG. The light emitted from the backlight unit for liquid crystal display unit 7 is polarized by passing through the polarizing plate 6, passes through the dried coating film 4 of the colored composition applied on the glass substrate 5, and reaches the polarizing plate 3. . If the polarizing planes of the polarizing plates 6 and 3 are parallel, light passes through the polarizing plate 3, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate 3. However, when the light polarized by the polarizing plate 6 passes through the dried coating film 4 of the colored composition, scattering or the like by the pigment particles occurs, and if a part of the polarizing plane is shifted, when the polarizing plate is parallel, Means that the amount of light passing through the polarizing plate 3 is reduced, and when the polarizing plate is straight, some light is transmitted through the polarizing plate 3. This transmitted light is measured as the luminance on the polarizing plate with a luminance meter 1, and the ratio (contrast ratio) between the luminance when the polarizing plates 3 and 6 are parallel (parallel luminance) and the luminance when the polarizing plates 3 and 6 are perpendicular (orthogonal luminance) is used. Was calculated.

[0098] Contrast ratio = parallel luminance Z orthogonal luminance

Therefore, when scattering occurs due to the pigment of the dried coating film 4 of the colored composition, the parallel luminance decreases and the orthogonal luminance increases, so that the contrast ratio decreases.

[0099] Note that a color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter 1, and a commercially available polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. At the time of measurement, a black mask 2 with a lcm square hole was applied to the measurement area to block unnecessary light. I was

[0100] Preparation of Acrylic Resin Solution>

Pour 800 parts of cyclohexanone into a reaction vessel, heat the carohydrate to 100 ° C while injecting nitrogen gas into the vessel, and heat styrene 60.0 咅 ^ metac !; noreic acid 60.0 咅 ^ metac! At the same temperature. A mixture of 65.0 parts of methinolate acid, 65.0 parts of butyl methacrylate, and 10.0 parts of azobisisobutyral-tolyl was dropped over 1 hour to carry out a polymerization reaction. After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, then a solution prepared by dissolving 2.0 parts of azobisisobutyro-tolyl in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C for 1 hour. An acrylic resin solution having an average molecular weight of about 40,000 was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, dried by heating at 180 ° C for 20 minutes, and the nonvolatile content was measured. Based on the measurement result, the resin solution synthesized above had a nonvolatile content of 20%. % Of cyclohexanone to prepare an acrylic resin solution.

[0101] Pigment treatment 1

Quinophthalone pigment (CI Pigment Yellow 138, BALI “Palio Tol Yellow K0961HD”, average particle diameter 120nm, pigment A) 80g, 8mm diameter steel beads 2kg dry attritor (Mitsui Mining Co., Ltd. MA01D type, tank The mixture was charged in a capacity of 0.8 L) and operated for 1 hour at a rotation speed of 300 rpm at an internal temperature of 80 ° C to obtain a pre-pigment (pigment B). Further, 4 g of xylene was charged into a dry attritor and operated at 300 rpm for 1 hour at an internal temperature of 80 ° C to obtain a treated pigment (pigment C).

[0102] Pigment treatment 2

70 g of quinophthalone pigment `` Pariotel Yellow K0961HD '' and 2 kg of 8 mm diameter steel beads were charged in a dry attritor (MA01D type, Mitsui Mining Co., Ltd., tank capacity 0.8 L), rotation speed 350 rpm, internal temperature 60 ° C To prepare a pre-pigment (average primary particle size: 4 Onm), further charge 3.5 g of diethylene glycol in a dry attritor, and operate for 1 hour at a rotation speed of 350 rpm and an internal temperature of 60 ° C. A treated pigment (Pigment D) was obtained.

[0103] Pigment treatment 3

80 g of quinophthalone pigment “Pariotel Yellow K0961HD”, 2 g of xylene, and 2 kg of steel beads with a diameter of 8 mm were dried using a dry attritor (MA01D made by Mitsui Mining Co., Ltd. And the mixture was operated at a rotation speed of 300 rpm and an internal temperature of 80 ° C. for 1 hour to obtain a treated pigment (Pigment E).

[0104] Pigment treatment 4 (Salt milling treatment)

250 g of quinophthalone pigment "Palio Tol Yellow K0961HD", 700 g of sodium salt sodium chloride, 107 g of hydrogen-added rosin ester ("Ester Gum HP" manufactured by Arakawa Chemical Co., Ltd.) and 160 g of polyethylene glycol ("Polyethylene glycol 300" manufactured by Tokyo Chemical Industry Co., Ltd.) It was charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into about 3 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C, turned into a slurry, filtered, washed with water, and washed with sodium chloride and sodium salt. Except for polyethylene glycol, the mixture was dried in a hot air oven at 60 ° C for about 24 hours to obtain a salt milled pigment (Pigment F).

[0105] Pigment treatment 5

Isoindoline pigment (CI Pigment Yellow 139, BASF “Palio Tol Yellow D1819”, average particle diameter 110 nm) 60 g, 8 mm diameter steel beads 2.3 kg are dry atrai ita (MA01D type, Mitsui Mining Co., Ltd. (Preparation of a pre-pigment (average primary particle diameter 60 nm) at 25 rpm, internal temperature of 100 ° C for 1 hour, and then 6 g of isobutanol in a dry attritor. The charged pigment was operated at a rotation speed of 250 rpm and an internal temperature of 80 ° C. for 1 hour to obtain a treated pigment (pigment G).

[0106] Pigment treatment 6

Isoindoline pigment (CI Pigment Yellow 139, BASF “Palio Tol Yellow D1819”, average particle diameter 110 nm) 60 g, 8 mm diameter steel beads 2.3 kg are dry atrai ita (MA01D type, Mitsui Mining Co., Ltd. (Preparation of a pre-pigment (average primary particle diameter 60 nm) at 25 rpm, at an internal temperature of 100 ° C for 1 hour, followed by 3 g of dye derivative 19 and isobutanol. It was charged in a 6 g dry attritor and operated for 1 hour at a rotation speed of 250 rpm and an internal temperature of 80 ° C. to obtain a treated pigment (pigment H).

[0107] Pigment treatment 7

80g of isoindoline pigment (CI Pigment Yellow 185, "Paliotol Yellow D1155" manufactured by BASF, average particle diameter 110nm) 80g, 3kg of 25mm diameter steel ball is ball milled (Tank capacity: 1.OL), prepare a pre-pigment (average primary particle diameter: 40 nm) by operating at 100 rpm and an internal temperature of 40 ° C for 2 hours, and further charge 6 g of cyclohexanone in a ball mill. , Operating at 100 rpm for 2 hours at an internal temperature of 40 ° C to obtain a treated pigment (Pigment I).

[0108] Pigment treatment 8

80 g of isoindoline pigment (CI Pigment Yellow 185, “Palio Tol Yellow D1155” manufactured by BASF, average particle size 110 nm), 3 kg of steel balls 25 mm in diameter are charged in a ball mill (tank capacity 1.0 L), and the rotation speed is 100 rpm. After operating for 2 hours at an internal temperature of 40 ° C to prepare a pre-pigment (average primary particle diameter 40 nm), 8 g of the dye derivative 38, 8 g of maleic acid resin, and 6 g of cyclohexanone were charged into a ball mill, By operating at a rotation speed of 100 rpm and an internal temperature of 40 ° C. for 2 hours, a treated pigment (Pigment J) was obtained.

[0109] Pigment treatment 9

Except that the quinophthalone pigment was changed to a diketopyrrolopyrrole pigment (CI Pigment Red 254, “Irazine Red 2030” manufactured by Ciba Supharti Chemicals, Inc., average particle diameter 200 nm), the same treatment as in Pigment Treatment 1 was performed. A pigment (Pigment K) was obtained. The average primary particle size of the pre-pigment was 40 nm.

[0110] Pigment treatment 10

Except that the quinophthalone pigment was changed to a copper phthalocyanine pigment (CI Pigment Green 36, “Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd., average particle size 105 nm), the same treatment as that of facial treatment 1 was performed. (Pigment L) was obtained. The average primary particle size of the pre-pigment was 40 nm.

[0111] Pigment treatment 11

Except that the quinophthalone pigment was changed to a copper phthalocyanine pigment (CI Pigment Blue 15: 6, “Lionol Blue E” manufactured by Toyo Ink Mfg. Co., Ltd., average particle diameter 400 nm) (Pigment M) was obtained. The average primary particle size of the pre-pigment was 40 nm.

The obtained pigments A to M were observed with an electron microscope to measure the primary particle diameter, and the average primary particle diameter and the range of variation of the primary particle diameter were determined. Table 1 shows the results. In addition, one The variation range of the secondary particle size is shown in the range of the particle size in which 80% or more of the total pigment particles are contained.

[Table 1] Table 1:

[0113] Example 1

After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed with an Eiger mill for 5 hours using dinorecobeads having a diameter of 1 mm, and filtered with a 5 m filter to prepare a pigment dispersion.

[0114] Pigment C 9.0 parts

榭 Resin type pigment dispersant (“Ajispar PB821” manufactured by Ajinomoto Co., Inc.) 1.0 part Acrylic resin solution 50.0 parts Cyclohexanone 40.0 parts

Then, a mixture having the following composition using the obtained pigment dispersion was stirred and mixed so as to be uniform, and then filtered with a 1 μm filter to obtain an alkali-developable resist material.

[0115] Pigment dispersion 60.0 parts

Acrylic resin solution 11.0 parts

Trimethylol pronontriatalylate 4.2 parts

(`` NK ester ATMPTJ '' manufactured by Shin-Nakamura Chemical Co., Ltd.)

Photopolymerization initiator (Irgacure-1 907, manufactured by Ciba-Geigy) 1.2 parts Sensitizer (保 -Fj, Hodogaya-Daigakusha) 0.4 part

Cyclohexanone 23.2 parts

Examples 2-10, Comparative Examples 1-8

An alkali developable resist material was prepared in the same manner as in Example 1, except that Pigment C was changed to the pigments shown in Table 2.

The obtained resist material was applied to a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater to obtain a coated substrate. Next, after drying at 70 ° C for 20 minutes, ultraviolet exposure was performed using an ultra-high pressure mercury lamp with an integrated light amount of 150 mJ. The coated substrate was heated at 230 ° C for 1 hour to obtain a substrate having the same thickness of 2 microns. The contrast ratio of this substrate was measured.

[0117] The viscosity of the obtained resist material was measured using an ELD viscometer (manufactured by Toki Sangyo Co., Ltd.) immediately after the adjustment and after storage for one week in an oven at 40 ° C. For the resists of Examples 18 to 18, multiples of the contrast ratio with respect to the contrast ratio of the resist using each original pigment were calculated. Table 2 shows the above results.

[Table 2] Table 2:

The resist material obtained in Example 1 has a higher contrast ratio than the resist material obtained in Comparative Example 1. Further, the resist materials obtained in Comparative Examples 2 and 3 have a high contrast ratio, but have very poor viscosity stability of the resist. All of the resists obtained in the examples have a high contrast ratio and good viscosity stability. [0119] As described above, the colored yarn composition for a color filter of the present invention is obtained by adding a small amount of an organic solvent having a crystal growth effect and dry-pulverizing the pigment to make the primary particles finer. Since the pigment is used, the pigment is stably dispersed on the pigment carrier without agglomeration, and has an extremely low viscosity.

[0120] Further, the color filter of the present invention includes a filter segment in which the pigment is stably dispersed without agglomeration in the pigment carrier, and includes a filter composition formed of a coloring composition having extremely low viscosity. Excellent durability and high contrast ratio.

Claims

The scope of the claims

[1] In a coloring composition for a color filter, comprising a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and an organic pigment, the organic pigment is a dry-processed crude organic pigment having an average particle size of greater than 100 nm. A small amount of an organic solvent having a crystal growth effect on the pre-pigment is added to the pulverized pre-pigment having an average primary particle diameter of 10-100 nm and dry-pulverized to suppress the change in the average primary particle diameter of the pigment to 30 nm or less. The pigment particles having a primary particle size of lOOnm or more account for 20% by weight or less of the total pigment particles, and the pigment particles having a primary particle size of 20-lOOnm account for 60% or more of the total pigment particles. A coloring composition for a color filter, which is a treated pigment having a particle size distribution of

[2] The composition according to claim 1, wherein the organic solvent is an organic solvent having a boiling point of 50 to 250 ° C.

3. The composition according to claim 1, wherein the organic pigment is a yellow pigment.

[4] The composition according to claim 3, wherein the yellow pigment is also selected from the group consisting of Cment Pigment Yellow 138, C.I. Pigment Yellow 139 and ΐ. Pigment Yellow 185.

[5] A color filter comprising a filter segment in which the color composition for a color filter according to claim 1 is formed.

[6] A coloring composition for a color filter comprising a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and an organic pigment, wherein the organic pigment is a crude organic pigment having an average particle size of greater than 100 nm. An organic solvent having a crystal growth effect is added to the crude organic pigment in a small amount, and the mixture is dried and pulverized. Pigment particles having an average primary particle diameter of 10 lOOnm and a primary particle diameter lOOnm or more are all pigments. A coloring composition for a color filter, which is a treated pigment having a particle size distribution in which pigment particles having a primary particle diameter of 20 to 100 nm or less and not more than 20% by weight of the particles are not less than 60% by weight of all the pigment particles.

[7] The composition according to claim 6, wherein the organic solvent is an organic solvent having a boiling point of 50 to 250 ° C.

[8] The composition according to claim 6, wherein the organic pigment is a yellow pigment.

[9] The composition according to claim 8, wherein the yellow pigment is selected from the group consisting of C 丄 Pigment Yellow 138, C.I. Pigment Yellow 139 and ΐ. Pigment Yellow 185.

[10] A color filter comprising a filter segment formed with the coloring composition for a color filter according to claim 6.