KR20060132623A - Coloring composition for color filter and color filter - Google Patents

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

Color composition and color filter for color filters {COLORING COMPOSITION FOR COLOR FILTER AND COLOR FILTER}

 This invention relates to the coloring composition used for manufacture of the optical color filter which comprises a liquid crystal color display, a video camera, etc., and the color filter using this coloring composition. More particularly, the invention relates to a coloring composition for color filters for forming filter segments of color filters, commonly referred to as stripe filters or matrix filters.

The color filter consists of arranging two or more kinds of fine stripe (stripe) shaped filter segments in parallel or intersecting on the surface of a transparent substrate such as glass, or arranging the fine filter segments in a vertical and horizontal constant arrangement. The filter segments are fine from several microns to several hundred microns, and are arranged in a predetermined arrangement for each color.

In general, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal on a color filter is formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a predetermined direction is formed thereon. In order to fully acquire the performance of these transparent electrodes and an oriented film, the formation needs to be performed generally at 200 degreeC or more, Preferably it is 230 degreeC or more high temperature.

For this reason, as a manufacturing method of a color filter, the method called the pigment dispersion method which makes a pigment excellent in light resistance and heat resistance into a coloring material now becomes the mainstream.

In the case of the pigment dispersion method, the photosensitive coloring composition (pigment resist) which disperse | distributed the pigment in the photosensitive transparent resin solution is apply | coated to transparent substrates, such as glass, and after removing a solvent by drying, pattern exposure of one filter color is performed, Subsequently, the unexposed part is removed in a developing step to form a first color pattern, and a treatment such as heating is applied if necessary, and then the same operation can be repeated for all the filter colors to produce a color filter.

In the liquid crystal display, a twisted nematic (TN) type liquid crystal in which a liquid crystal layer sandwiched by two polarizing plates controls the degree of polarization of light passing through the first polarizing plate and displays by controlling the amount of light passing through the second polarizing plate is used. The type that is doing is mainstream. Although color display is enabled by providing a color filter between these two polarizing plates, the color filter which disperse | distributed the organic pigment generally dissolves the degree of polarization which the liquid crystal controlled by the scattering of the light by a pigment particle, etc. have. That is, there is a phenomenon in which light leaks when light must be blocked (OFF state) and transmitted light attenuates when light must be transmitted (ON state). Although the ratio of the brightness | luminance on a display in an ON state and an OFF state is called contrast ratio, it is generally known that the smaller the particle size of a pigment in a color filter, the higher the contrast ratio.

In general paints and inks, the transparency of the pigment is generally improved by increasing the dispersion of the pigment. However, in the case of ordinary dispersers such as sand mills, three-roll mills, ball mills, and the like, the transparency is further increased when the pigment is dispersed to the primary particles. Will not. A dispersion process in a conventional disperser is a process of mainly dissolving secondary particles, which are aggregates of primary particles of a pigment, to obtain a dispersion in a state close to the primary particles. Further, in order to improve transparency, the primary particles need to be made finer. .

High-speed sand mills are excellent for finely granulating pigments, and depending on the pigments, it is possible to make primary particles fine, but in this case, very large energy is required.

As a means for making the primary particles of the pigment fine, a method in which a pigment dissolved in a strong acid such as concentrated sulfuric acid or polyphosphoric acid is added to cold water or ice water to precipitate the pigment as fine particles (for example, Japanese Patent Laid-Open Application 8-179111). However, in this method, the pigment which can be used is remarkably limited from the point of the solubility and stability with respect to the strong acid of a pigment. In addition, since the pigment micronized by this method causes strong secondary aggregation when dried, it is generally very difficult to redisperse to primary particles.

In addition, as another means for making the primary particles of the pigment fine, a dry grinding method, a solvent salt milling method and the like are widely known.

Dry pulverization is a method of finely pulverizing primary particles of pigments by dry pulverization with a ball mill, attritor, vibratory mill, etc., compared to the solvent salt milling method, the production efficiency per unit energy is good, and an industrial waste that puts a load on the environment. This is a preferable method in that this does not occur. However, if dry pulverization is simply applied to coarse pigment particles, the primary particles of the pigment can be made fine, but the variation in particle diameter is large, and the cohesion force between the particles is extremely strong. Therefore, in many cases, only a large aggregate obtained by binding the primary particles of a plurality of micronized pigments with a strong force was obtained, and it was very difficult to disperse the pigment particles.

In the solvent salt milling method, in the presence of inorganic salts such as sodium chloride or sodium sulfate, and highly viscous water-soluble organic solvents such as ethylene glycol, diethylene glycol, polyethylene glycol, and the like, the pigment is mechanically ground by kneading to finely prepare the primary particles of the pigment. How to make However, the solvent salt milling method is poor in productivity per unit energy because the power consumption is large. Moreover, since several times or more of inorganic salts and the organic solvent of the same amount to several times are used with respect to a pigment, the water washing and filtration process for separating these inorganic salts and the organic solvent from a pigment are required. In addition, the pigment becomes an agglomerate by the drying process performed after washing and filtration, and in order to obtain a color filter having a high contrast, the finer the finer the primary particles of the pigment, the more intense the agglomerates than the dry pulverization method, and disperse the pigment particles. It becomes difficult. Therefore, even if the pigment which refined the primary particle by this method is used, the contrast improvement of the above is difficult.

In addition, the thickness of the filter segment of a color filter is about 1 micrometer, and the dispersion | variation in film thickness is suppressed to 100 nm or less. Since the photosensitive coloring composition is usually coated by a spin coater or the like, in order to achieve this accuracy, the photosensitive coloring composition is required to have an extremely low viscosity. However, in general, the finer the pigment is dispersed, the more the photosensitive coloring composition becomes high in viscosity and tends to thicken over time.

Disclosure of the Invention

An object of the present invention is to provide a coloring composition capable of producing a color filter having a high contrast ratio and a color filter having a high contrast ratio as a coloring composition in which fine pigment particles are stably dispersed and extremely low in viscosity.

According to a first aspect of the present invention, there is provided a pigment carrier composed of a transparent resin, a precursor thereof, or a mixture thereof and an organic pigment, wherein the organic pigment is an average of dry grinding of a crude organic pigment having an average particle diameter of more than 100 nm. To a pre-pigment having a primary particle size of 10 to 100 nm, a small amount of an organic solvent having a crystal growth action with respect to the pre-pig is added and dry pulverized, and particles are adjusted while suppressing a change in the average primary particle size of the pigment to 30 nm or less. For color filters, wherein the pigment particles having a primary particle size of 100 nm or more are 20% by weight or less of the total pigment particles, and the pigment particles having a primary particle size of 20 to 100 nm are treated pigments having a particle size distribution of 60% by weight or more of the total pigment particles. A coloring composition is provided.

According to a second aspect of the present invention, there is provided a crude organic pigment comprising a pigment carrier composed of a transparent resin, a precursor thereof or a mixture thereof, and an organic pigment, wherein the organic pigment has an average particle diameter of more than 100 nm. A small amount of an organic solvent having a crystal growth action is added to the pigment, followed by dry pulverization, and the average primary particle size is 10 to 100 nm, and the pigment particles having a primary particle size of 100 nm or more are 20% by weight or less of the total pigment particles. There is provided a coloring composition for color filters, wherein the pigment particles in the range of primary particle diameters from 20 to 100 nm are treated pigments having a particle size distribution of at least 60% by weight of the total pigment particles.

According to the 3rd aspect of this invention, the color filter provided with the filter segment formed from the coloring composition for color filters of this invention is provided.

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

Best Mode for Carrying Out the Invention

First, the coloring composition for color filters of this invention is demonstrated.

The coloring composition for color filters of this invention contains the pigment carrier which consists of transparent resin, its precursor, or its mixture, and an organic pigment.

According to the first aspect of the present invention, the organic pigment has a crystal growth effect on the pre-pigment in a pre-pigment having an average primary particle size of 10 to 100 mm by dry pulverization of a crude organic pigment having an average particle diameter of more than 100 nm. A small amount of organic solvent is added and dry pulverization is carried out by particle adjustment while suppressing the change of the average primary particle size of the pigment to 30 nm or less, and the pigment particles having a primary particle size of 100 nm or more are 20% by weight or less of the total pigment particles, and the primary The pigment particle of the range of particle size 20-100 mm is a process pigment which has a particle size distribution which is 60 weight% or more of all the pigment particles.

Alternatively, in the organic pigment, according to the second aspect of the present invention, dry grinding is performed by adding a small amount of a crude organic pigment having an average particle diameter greater than 100 mm and an organic solvent having a crystal growth effect with respect to the crude organic pigment. Pigment particles having an average primary particle size of 10 to 100 nm, a pigment particle having a primary particle size of 100 nm or more, and 20 wt% or less of all pigment particles, and a pigment particle having a primary particle size of 20 to 100 nm. A treatment pigment having a particle size distribution of at least 60% by weight. The treatment pigment according to the first aspect and the treatment pigment according to the second aspect are collectively referred to simply as the treatment pigment.

In either case, the treatment pigment is fine-tuned to the primary particles, and the particles are adjusted to a uniform particle shape. For this reason, the coloring composition for color filters of this invention in which the said process pigment is disperse | distributed uniformly in a pigment carrier, maintaining a fine particle state, has stable viscosity characteristic. Moreover, the color filter formed using the coloring composition for color filters of this invention has high contrast ratio.

As the crude organic pigment having an average particle diameter of more 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. In addition, the use of a crude organic pigment having an average particle diameter larger than 110 nm is preferable because a treated pigment having a desired particle size distribution can be easily obtained.

The organic pigment used for this invention is shown below with a color index (C.I) number.

Red coloring compositions for forming red filter segments include, for example, C.I. 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, 264, Red pigments, such as 272, can be used. A yellow pigment and an orange pigment can be used together in a red composition.

Green coloring compositions for forming green filter segments include, for example, C.I. Green pigments, such as Pigment Green 7, 10, 36, 37, can be used. A yellow pigment can be used together in a green coloring composition.

Blue coloring compositions for forming blue filter segments include, for example, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be used. Blue compositions include C.I. Purple pigments, such as Pigment VioIet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, can be used together.

Cyan coloring compositions for forming the cyan filter segments include, for example, C.I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and the like can be used.

In general, when the phthalocyanine pigment, which is a blue pigment, is pulverized with a pulverizing medium in a dry state, an α-type copper phthalocyanine pigment (CI Pigment Blue 15: 1) is produced to form an ε-type copper phthalocyanine pigment (CI Pigment Blue 15). : 6) may not be obtained with high purity. However, in the treatment of the organic pigment of the present invention, since the organic solvent coexisting at the time of dry grinding has an effect of suppressing the production of the α-type copper phthalocyanine pigment, it is fine by selecting an appropriate organic solvent species and coexisting the optimum amount. Furthermore, the epsilon type copper phthalocyanine pigment particle | grains adjusted by the uniform particle diameter can be obtained.

Yellow colored compositions for forming yellow filter segments include, for example, C.I. Pigment 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, 179, 180, Yellow pigments, such as 181, 182, 185, 187, 188, 193, 194, 199, can be used.

Orange coloring compositions for forming orange filter segments include, for example, C.I. Pigment orange Orange pigments such as 36, 43, 51, 55, 59, 61 can be used.

Magenta coloring compositions for forming magenta filter segments include, for example, C.I. Pigment Violet 1, 19, C.I. Purple pigments and red pigments such as Pigment Red 144, 146, 177, 169 and 81 can be used. A yellow pigment can be used together in a magenta composition.

These organic pigments may be subjected to dry pulverization alone or by mixing two or more kinds thereof. For example, pigments having different colors may be mixed and treated, such as green pigments and yellow pigments, red pigments and orange pigments or yellow pigments. .

In the present invention, yellow pigments, especially C.I. It is particularly preferable to use Pigment Yellow 138, 139 and 185 because the effect of improving the contrast ratio is high.

Organic solvents having a crystal growth action on pre- and crude organic pigments include benzene, toluene, xylene, ethyl benzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, methanol, ethanol, Isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate Ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Warm, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like. You may use the said organic solvent in mixture of 2 or more types as needed.

As the organic solvent having a crystal growth action, it is necessary to coexist with the crude organic pigment and the pre-pigment without evaporating in the dry grinding step of the crude organic pigment and the pre-pigment. It is preferable to use.

The organic solvent having a crystal growth action does not need to be removed in particular if the preparation of the color composition for color filters is not hindered, but if necessary, it can be easily removed by a method such as vacuum drying or freeze drying. Removal of the organic solvent may be performed using the apparatus used at the time of dry grinding in the presence of the organic solvent, or may be carried out by transferring to another apparatus.

Moreover, you may add a pigment derivative, resin, surfactant, etc. before the process of dry grinding by adding an organic solvent.

A dye derivative is a compound which introduce | transduced a substituent into an organic pigment, and is added for the purpose of promoting refinement | purification of a crude organic pigment, and the objective of preventing generation of another crystalline pigment by a crystal potential. Organic dyes also include heterocyclic compounds such as pale yellow aromatic polycyclic compounds such as naphthalene and anthraquinone, and triazines, which are not generally called dyes. By adding a pigment derivative and dry grinding, the average primary particle size can be made smaller, and there is an effect of improving the contrast ratio. As a pigment derivative, it describes in Unexamined-Japanese-Patent No. 63-305173, Japan Unexamined-Japanese-Patent No. 57-15620, Japan Unexamined-Japanese-Patent No. 59-40172, Japan Unexamined-Japanese-Patent No. 63-17102, Japan Unexamined-Japanese-Patent No. 5-9469, etc. They can be used and these can be used individually or in mixture of 2 or more types.

As a pigment derivative, the pigment derivative which has a basic group represented by following General formula (1), (2), (3) and (4) is mentioned specifically ,.

General formula (1)

General formula (2)

General formula (3)

General formula (4)

In the formulas (1) to (4), X represents -SO _2- , -CO-, -CH ₂ NHCOCH _2- , -CH ₂ -or a single bond. X is preferably -SO ₂ -or a single bond.

n represents the integer of 1-10. n becomes like this. Preferably it is 1-3.

R ₁ and R ₂ each independently represent an unsubstituted or substituted alkyl group having 1 to 36 carbon atoms, an unsubstituted or substituted alkenyl group or unsubstituted or substituted phenyl group having 2 to 36 carbon atoms, or R ₁ and R ₂ combine to form an unsubstituted or substituted heterocycle that further contains nitrogen, oxygen, or sulfur atoms. R ₁ and R ₂ are preferably an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms.

R ₃ represents an unsubstituted or substituted alkyl group having 1 to 36 carbon atoms, an unsubstituted or substituted alkenyl group or unsubstituted or substituted phenyl group having 2 to 36 carbon atoms. R ₃ is preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 36 carbon atoms, an unsubstituted or substituted alkenyl group or unsubstituted having 2 to 36 carbon atoms Or a substituted phenyl group. R ₄ , R ₅ , R ₆ and R ₇ are each preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

Y represents -NR ₈ -Z-NR ₉ -or a single bond.

R ₈ and R ₉ each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 36 carbon atoms, an unsubstituted or substituted alkenyl group or unsubstituted or substituted phenyl group having 2 to 36 carbon atoms . R ₈ and R ₉ are each preferably a hydrogen atom.

Z represents an unsubstituted or substituted alkylene group having 1 to 36 carbon atoms, an unsubstituted or substituted alkenylene group or unsubstituted or substituted phenylene group having 2 to 36 carbon atoms. Z is preferably an unsubstituted or substituted phenylene group.

R is

General formula (5)

A substituent represented by, or

General formula (6)

The substituent represented by this is shown. In the formulas (5) and (6), R ₁ to R ₇ and n are as defined above.

Q represents a hydroxyl group, an alkoxyl group, the substituent represented by the said Formula (5), or the substituent represented by the said Formula (6). Q is preferably a substituent represented by the said Formula (5).

As an organic pigment | dye residue which comprises a pigment derivative, For example, diketopyrrolopyrrole pigment | dye, azo pigment | dyes, such as azo, disazo, and polyazo, phthalocyanine pigment | dye, diamino dianthraquinone, anthrapyrimidine, a flaming Anthraquinone pigments such as vantron, anthrone, indanthrone, pyrantrone, and violatron, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, Isoindolinone pigments, quinophthalone pigments, styrene dyes, and metal complex dyes. Moreover, the pigment used for the coloring composition for color filters mentioned later may be sufficient.

In addition, the pigment derivative is an alkyl group such as a methyl group or an ethyl group, an amino group or an dimethyl amino group, an alkyl amino group such as a diethyl amino group or a dibutyl amino group, an alkoxy group such as a nitro group, a hydroxyl group or a methoxy group, an ethoxy group or a butoxy group, or a chlorine group. Phenyl group or methyl group, ethyl group, methoxy group, ethoxy group, amino group, dimethyl amino group, diethyl amino group, nitro group, hydroxyl group which may be substituted by halogen or methyl group, methoxy group, amino group, dimethyl amino group, hydroxyl group, etc. You may have substituents, such as the phenyl amino group which may be substituted by these.

The dye derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, the amine component which introduce | transduces the substituent represented by following formula (7)-formula (10) to an organic pigment | dye, reacts with this substituent, and forms the substituent represented by Formula (1)-formula (4). For example N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5 -Triazine-2-ylamino] aniline or the like to react.

Formula (7): -SO ₂ Cl

Formula (8): -COCl

Formula (9): -CH ₂ NHCOCH ₂ Cl

Formula (10): -CH ₂ Cl

When an organic pigment | dye is an azo dye, a basic group which comprises the pigment derivative represented by General formula (1)-(4) is introduce | transduced into a diazo component or a coupling component previously, and a coupling group is then performed by carrying out a coupling reaction. Azo dye derivatives may be prepared.

In addition, the triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, the amine component which uses a cyanuric chloride as a starting material and forms the substituent represented by general formula (1)-(4) in at least 1 chlorine of a cyanuric chloride, for example, N, N-dimethyl It is obtained by reacting aminopropylamine or N-methylpiperazine and the like, followed by reacting the remaining chlorine of cyanuric chloride with various amines or alcohols and the like.

As an amine component used in order to form the substituent represented by General Formula (1)-(6), for example, dimethylamine, diethylamine, 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, diisoamamine, dihexylamine, di (2- Ethylhexyl) amine, dioctylamine, N, N--methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, diol Railamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethyl Aminoethylamine, N, N-diethylaminopropylamine, N, N- Ethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-di Butylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyllaurylaminopropylamine, 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, pipecolinic acid, isonifecotic acid, isonifecotate methyl, isonifecotate ethyl, 2-piperidine ethanol, pyrrolidine, 3-hydroxy pyrrolidine, N-aminoethyl piperidine, N-aminoethyl-4-pipecoline, N-aminoethyl morpholine, N-aminopropyl piperi Dean, N-aminopropyl-2-pipecoline, N-aminoprop -4-pipecoline, N-aminopropyl morpholine, N-methyl piperazine, N-butyl piperazine, N-methyl homopiperazine, 1-cyclopentyl piperazine, 1-amino-4-methyl piperazine, 1 -Cyclopentyl piperazine, and the like.

Although the thing shown in Tables 1-9 can be used as a dye derivative, It is not limited to these. A pigment derivative can be used individually or in mixture of 2 or more types.

Pigment derivatives 1

Pigment derivatives 2

Pigment derivatives 3

Pigment derivatives 4

Pigment derivatives 5

Pigment derivatives 6

Pigment derivatives 7

Pigment derivatives 8

Pigment derivatives 9

Pigment Derivatives 10

Pigment derivatives 11

Pigment Derivatives 12

Pigment derivatives 13

Pigment Derivatives 14

Pigment Derivatives 15

Pigment Derivatives 16

Pigment Derivatives 17

Pigment Derivatives 18

Pigment Derivatives 19

Pigment Derivatives 20

Pigment Derivatives 21

Pigment Derivatives 22

Pigment Derivatives 23

Pigment Derivatives 24

Pigment Derivatives 25

Pigment Derivatives 26

Pigment Derivatives 27

Pigment Derivatives 28

Pigment Derivatives 29

Pigment Derivatives 30

Pigment derivatives 31

Pigment Derivatives 32

Pigment Derivatives 33

Pigment derivatives 34

Pigment derivatives 35

Pigment Derivatives 36

Pigment Derivatives 37

Pigment Derivatives 38

Pigment Derivatives 39

Pigment Derivatives 40

Pigment derivatives 41

Pigment derivatives 42

Pigment Derivatives 43

Pigment Derivatives 44

Pigment Derivatives 45

Pigment Derivatives 46

Pigment Derivatives 47

Pigment Derivatives 48

Pigment Derivatives 49

Pigment Derivatives 50

Pigment derivatives 51

Pigment Derivatives 52

Pigment Derivatives 53

The pigment derivative may be used in a proportion of 0.1 to 30% based on the weight of the crude organic pigment.

There is no restriction | limiting in particular as resin added when dry-crushing the said pre pigment or a crude pigment, Rosin, rosin derivative, rosin modified maleic acid resin, rosin modified phenol resin, rubber derivative, protein derivative, chlorinated polyethylene, chlorinated poly Propylene, polyvinyl chloride, vinyl polyacetate, epoxy resin, acrylic resin, maleic acid resin, styrene resin, styrene-maleic acid copolymer resin, butyral resin, polyester resin, melamine resin, phenolic resin, polyurethane resin, And polyamide resins, polyimide resins, alkyd resins, rubber resins, celluloses, benzoguanamine resins, urea resins, oligomers and monomers of the above resins. These resins can be used in the amount of 0.1-50% based on the weight of a crude organic pigment.

The dry grinding of the crude organic pigment and the pre-pigment is not particularly limited, but may be performed using a conventional dry grinding device incorporating grinding media such as beads, for example, a ball mill, an attritor, a vibration mill, or the like. have. Grinding of the crude organic pigment and pre-pigment proceeds through collision or friction between the grinding media. Moreover, you may carry out by pressure-reducing the inside of a grinding container or filling inert gas, such as nitrogen gas, as needed.

The operating conditions of the dry grinding device are not particularly limited, but the following conditions are particularly preferable in order to effectively advance the crystal growth of the crude organic pigment and pre-pigment by grinding with the grinding media and contact with the organic solvent. Do.

That is, when the dry grinding device is an attritor, the rotation speed of the device is preferably 100 to 500 rpm, and the time of dry grinding (when manufacturing the treated pigment via the pre-pigment, dry grinding and 0.5 to 8 hours are preferable, and, as for the internal temperature of an apparatus, 50-150 degreeC is preferable for the time which combined dry grinding in presence of an organic solvent. The grinding media is preferably spherical with a diameter of 4 to 30 mm, and the amount of the media used is preferably 5 to 50 weight times of the crude organic pigment or pre-pigment to be treated.

In the case where the dry grinding device is a ball mill, the rotation speed of the device is preferably 50 to 200 rpm, and the time of dry grinding (when manufacturing the treated pigment via the pre-pig, dry grinding and organic 1 to 12 hours are preferable, and, as for the internal temperature of the apparatus, 30-100 degreeC is preferable. In addition, the grinding media is preferably a spherical shape having a diameter of 10 to 50 mm, and the amount of the media used is preferably 5 to 50 weight times of the crude organic pigment or pre-pigment to be treated.

The usage-amount of the organic solvent which has a crystal growth effect with respect to a crude organic pigment or a pre pigment is the range of 0.5-50 weight% of the weight of a crude organic pigment or a pre pigment, Preferably it is the range of 1-30 weight%. That is, the dry grinding after adding the organic solvent is in a state of completely dry stirring. Most organic solvents coexist in the state of being adsorbed on the surface of the pigment. Particularly, in the case of using a low boiling point organic solvent, some of them are volatilized and coexist in a mixed stirring system as a gas. What is important here is that the grinding by dry grinding continues to occur even during mixing and stirring. However, due to the effect of coexisting organic solvents, the crystal growth of the particles proceeds at the same time, so that the mixing and stirring conditions are optimized to achieve a good balance of grinding and crystal growth, thereby adjusting the particle size to a uniform particle diameter that could not be realized in the conventional dry grinding method. Can be.

In the present invention, the term " particle adjustment while suppressing the change of the average primary particle size to 30 nm or less " refers to a pre-pigment containing a large variation in particle diameter and containing coarse primary particles, in which the shape of the particles is used to determine the particle size. It means to make a process pigment with a small deviation range, and this means that the average primary particle diameter of the whole particle | grains changes only in the range of 30 nm or less.

The deviation range of the particle size of the treated pigment is that the pigment particles having a primary particle size of 100 nm or more should be 20% by weight or less of the total pigment particles, and the pigment particles having a primary particle size of 20 to 100 nm should be 60% by weight or more of the total pigment particles. It is preferable that the pigment particle of the range of particle size 30-80 nm is 80 weight% or more of all the pigment particles.

The pigment carrier contained with the process pigment in the coloring composition for color filters of this invention is comprised by transparent resin, its precursor, or its mixture as above-mentioned. 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 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 which is the visible light region. A thermoplastic resin, a thermosetting resin, and a photosensitive resin are contained in the transparent resin, The precursor contains the monomer or oligomer which hardens | cures by radiation and produces a transparent resin, These can be used individually or in mixture of 2 or more types. When hardening this composition by ultraviolet irradiation, the photoinitiator etc. are added to the coloring composition for color filters of this invention.

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, polyester resin, Acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polybutadiene, polyimide resin, etc. are mentioned. Moreover, as a thermosetting resin, an epoxy resin, benzoguanamine resin, a melamine resin, urea resin, a phenol resin etc. are mentioned, for example.

As photosensitive resin, (meth) acrylic compound and cinnamic acid which have reactive substituents, such as an isocyanate group, an aldehyde group, and an epoxy group, react with resin which has reactive substituents, such as a hydroxyl group, a carboxyl group, an amino group, and a (meth) acryloyl group Resin which introduce | transduced photocrosslinkable groups, such as a styryl group, is used. Moreover, resin containing acid anhydrides, such as a styrene-maleic anhydride copolymer and the (alpha)-olefin-maleic anhydride copolymer, by the (meth) acryl compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, Half esterified is also used.

As monomers and oligomers, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, trimetholpropane tri ( Meta) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecaneyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, etc. Various acrylic esters and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1one, Acetophenone photoinitiators such as 1-hydroxychlorohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, Benzoin-type photoinitiators, such as benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, benzoyl benzoate, 4-phenylbenzo phenone, hydroxy benzophenone, acrylated benzophenone, and 4-benzoyl- Benzophenone series photoinitiators, such as 4'-methyl diphenyl sulfide, a thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, a 2, 4- diisopropyl thioxanthone, etc. Thioxanthone type photopolymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s- Lysine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naph To-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl)- triazine photopolymerization such as s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine An initiator, a borate-type photoinitiator, a carbazole-type photoinitiator, an imidazole-type photoinitiator, etc. are used. The photopolymerization initiator may be used in an amount of 5 to 150% based on the weight of the treated pigment.

Although the said photoinitiator is used individually or in mixture of 2 or more types, As a sensitizer, (alpha)-acyloxy ester, acyl phosphine oxide, methylphenylglyoxylate, benzyl, 9,10- phenanthrene quinone, camphor quinone, ethyl anthra Compounds such as quinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone You can also use together. The sensitizer may be used in an amount of 0.1 to 30% based on the weight of the photopolymerization initiator.

The color composition for color filters of the present invention may be produced by finely dispersing a treated pigment in a pigment carrier, using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, together with the photopolymerization initiator as necessary. Can be. Moreover, when the coloring composition for color filters of this invention contains 2 or more types of process pigments, it can also manufacture by mixing what disperse | distributed each process pigment to the pigment carrier, respectively.

When disperse | distributing a process pigment in a pigment support | carrier, dispersion adjuvant, such as a resin pigment dispersing agent, surfactant, and a pigment derivative, can be contained suitably. The dispersing aid is excellent in the dispersion of the pigment and has a great effect of preventing reagglomeration of the treated pigment after dispersion. Therefore, in the case of using a coloring composition obtained by dispersing the treating pigment in the pigment carrier using the dispersing aid, a color filter having excellent transparency Is obtained.

The resinous pigment dispersant has a pigment affinity site having a property of adsorbing to the pigment and a site compatible with the pigment carrier, and is adsorbed on the pigment to stabilize the dispersion of the pigment in the pigment carrier. Specific examples of the resinous pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxes. Amides formed by the reaction of acidic alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters or modified substances thereof, poly (lower alkyleneimines) and polyesters having free carboxyl groups Oily dispersants such as salts thereof; Water-soluble resins, such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble high molecular compound, polyester type , Modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphate esters and the like are used, and these can be used alone or in combination of two or more thereof.

As surfactant, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, the alkali salt of a styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate Anionic surfactants such as triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc .; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; Amphoteric surfactants, such as alkyl betaine, such as alkyl dimethyl amino acetic acid betaine, and alkyl imidazoline, These can be used individually or in mixture of 2 or more types.

A dye derivative is a compound which introduce | transduced the substituent into the organic pigment | dye, It is preferable that it is close to the color of the pigment to be used, but if there is little addition amount, you may use a thing with a different color. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalenes and anthraquinones, which are not generally called dyes. As a pigment derivative, it describes in Unexamined-Japanese-Patent No. 63-305173, Japan Unexamined-Japanese-Patent No. 57-15620, Japan Unexamined-Japanese-Patent No. 59-40172, Japan Unexamined-Japanese-Patent No. 63-17102, Japan Unexamined-Japanese-Patent No. 5-9469, etc. They can be used and these can be used individually or in mixture of 2 or more types.

These dispersing aids can be used in amounts of 0.1 to 30% based on the weight of the treated pigment.

Furthermore, in the coloring composition for color filters of this invention, it is easy to form a filter segment by disperse | distributing a process pigment fully in a pigment support | carrier, and apply | coating so that dry film thickness may be set to 0.2-5 micrometers on transparent substrates, such as a glass substrate. It may contain a solvent for that purpose. As a solvent, for example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cello Sorb, 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. Use or mix. The solvent contained in the coloring composition of this invention can contain the organic solvent which has the said crystal growth action in addition to these solvents. The solvent can be used in an amount of 500 to 4000% based on the weight of the treated pigment in total.

Moreover, in order to stabilize the viscosity with time of a composition, the coloring composition for color filters of this invention can contain a storage stabilizer. As a storage stabilizer, organic acids, such as quaternary ammonium chloride, such as benzyl trimethyl chloride and diethyl hydroxyamine, lactic acid, and oxalic acid, its methyl ether, t-butyl pyrocatechol, tetraethylphosphine, tetraphenyl phosphose, for example Organic phosphines, phosphites, such as pin, etc. are mentioned. Storage stabilizers can be used in amounts of 0.1% to 5% by weight of the treated pigment.

In addition, the coloring composition for color filters of this invention can contain an inorganic pigment, in order to ensure favorable applicability | paintability, a sensitivity, developability, etc., balancing the saturation and lightness. Inorganic pigments include titanium oxide, barium sulfate, zincated, lead sulfate, yellow lead, zinc sulfur, bengal (red iron (III)), cadmium red, ultramarine blue, blue blue, chromium oxide rust, cobalt rust, umber, titanium black , Synthetic iron black, carbon black, and the like. An inorganic pigment can be used individually or in combination of 2 or more types. The inorganic pigment may be used in an amount of 0.1 to 10% based on the weight of the treated pigment.

In addition, the coloring composition for color filters of this invention can be made to contain dye within the range which does not reduce heat resistance for coloring. The dye may be used in an amount of 0.1 to 10% based on the weight of the treated pigment.

The coloring composition for color filters of this invention can be prepared in the form of the printing ink for gravure offset, anhydrous offset ink, the ink for silkscreen printing, the solvent developing type, or the alkali developing type coloring resist material. A coloring resist material disperse | distributes a processing pigment in the composition containing the said thermoplastic resin, a thermosetting resin, or the photosensitive resin, the said monomer, and the said photoinitiator.

The treated pigment is preferably contained in a coloring composition containing a solvent in a proportion of 1.5 to 7% by weight when the filter segment is formed by a photolithography method, and a solvent when the filter segment is formed by a printing method. It is contained in the ratio of 1.5-40 weight% in the coloring composition containing these. In any case, the treated pigment is preferably contained in the proportion of 10 to 55% by weight, more preferably 20 to 50% by weight in the final filter segment, and the balance is substantially composed of a resinous binder provided by the pigment carrier.

The color composition for color filters of the present invention is a coarse particle of 5 μm or more, preferably 1 μm or more of coarse particles, and more preferably 0.5 μm or more of coarse particles and mixed dust by means of centrifugation, sintering filter, membrane filter, or the like. It is preferable to remove.

Next, the color filter of this invention is demonstrated.

The color filter of this invention is equipped with the filter segment formed using the coloring composition of this invention, and forms the filter segment of each color on a transparent substrate using the coloring composition of this invention by the printing method or the photolithographic method. It can manufacture by doing. As a transparent substrate, resin plates, such as a glass plate, a polycarbonate, polymethyl methacrylate, and a polyethylene terephthalate, are used.

Formation of each color filter segment by a printing method can be patterned only by repeating printing and drying of the coloring composition prepared as said various printing inks, and is low cost as a manufacturing method of a color filter, and is excellent in mass productivity. In addition, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable to set it as the composition which ink does not dry and solidify on a printing plate or a blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity by the dispersant or the extender pigment can be adjusted.

When forming each color filter segment by the photolithography method, the coloring composition prepared as the said solvent developing type or alkali developing type coloring resist material is applied to application methods, such as spray coating, spin coating, slit coating, roll coating, etc., on a transparent substrate. It apply | coats so that dry film thickness may be 0.2-5 micrometers. If necessary, the dried film is subjected to ultraviolet exposure through a mask having a predetermined pattern provided in contact or non-contact state with the film. Thereafter, the developer can be immersed in a solvent or an alkaline developer or sprayed with a spray or the like to remove the uncured portion to form a desired pattern, and then the same operation can be repeated for another color to produce a color filter. Moreover, in order to accelerate superposition | polymerization of a coloring resist material, you may heat as needed. According to the photolithography method, a color filter having a higher precision than the printing method can be produced.

At the time of image development, aqueous solution, such as sodium carbonate and sodium hydroxide, is used as alkaline developing solution, Organic alkali, such as dimethylbenzylamine and triethanolamine, can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In addition, after coating and drying the colored resist material in order to increase the ultraviolet exposure sensitivity, after coating and drying a water-soluble or alkali water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin to form a film to prevent polymerization inhibition by oxygen Ultraviolet exposure can also be performed.

Although the color filter of this invention can be manufactured by electrodeposition method, the transfer method, etc. other than the said method, the coloring composition of this invention can be used for any method. In addition, the electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on a transparent conductive film by the electrophoresis of colloidal particle using the transparent conductive film formed on the transparent substrate. In addition, the transfer method is a method of previously forming a color filter layer on the surface of a peelable transfer base sheet, and transferring this color filter layer to a desired transparent substrate.

EMBODIMENT OF THE INVENTION Although this invention is demonstrated based on an Example below, this invention is not limited by this. In addition, in an Example and a comparative example, "part" means "weight part" and "%" means "weight%", respectively.

<Measurement of Contrast Ratio>

Next, the measuring method of the contrast ratio of the coating film produced using the resist is demonstrated with reference to FIG. Light emitted from the backlight unit 7 for liquid crystal display is polarized through the polarizing plate 6, passes through the dry coating film 4 of the coloring composition applied on the glass substrate 5, and reaches the polarizing plate 3. do. When the polarizing planes of the polarizing plate 6 and the polarizing plate 3 are parallel, the light passes through the polarizing plate 3, but when the polarizing planes are orthogonal, the light is blocked by the polarizing plate 3. However, when light polarized by the polarizing plate 6 passes through the dry coating film 4 of the coloring composition, scattering due to pigment particles occurs, and when a deviation occurs in a part of the polarizing surface, the polarizing plate is parallel. The amount of light passing through (3) decreases, and when the deflection plate is straight, part of the light passes through the polarizing plate 3. The transmitted light is measured by the luminance meter 1 as the luminance on the polarizing plate, and the ratio (contrast ratio) of the luminance (parallel luminance) when the polarizing plates 3 and 6 are parallel and the luminance (orthogonal luminance) when going straight Calculated.

Contrast Ratio = Parallel Luminance / Orthogonal Luminance

Therefore, when scattering is caused by the pigment of the dry coating film 4 of the coloring composition, the parallel luminance is lowered and the orthogonal luminance is increased, so the contrast ratio is lowered.

As the luminance meter 1, a color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used, and a commercially available polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In addition, at the time of a measurement, in order to block unnecessary light, the black mask 2 which drilled the hole of 1 cm in width and length was applied to the measurement part.

<Preparation of acrylic resin solution>

800 parts of cyclohexanone was put into a reaction vessel, heated to 100 DEG C while injecting nitrogen gas into the vessel, and at the same temperature, 60.0 parts of styrene, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate, and The mixture of 10.0 parts of azobisisobutyronitrile was dripped over 1 hour, and the polymerization reaction was performed. After the 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, followed by further reaction at 100 ° C. for 1 hour, where the weight average molecular weight was about 40000. A solution of acrylic resin was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and based on this measurement result, cyclohexane was added so that the nonvolatile content was 20% in the synthesized resin solution. One was added to prepare an acrylic resin solution.

Pigment Treatment 1

80 g of quinophthalone pigments (CI pigment yellow 138, `` palliotol yellow K0961HD '' made by BASF Corporation, average particle diameter 120nm, pigment A), 2 kg of steel beads of 8mm in diameter dry dry writer (Mitsui mine Co., Ltd. MA01D type It was put in the tank capacity 0.8L), it operated for 1 hour at rotation speed 300rpm, internal temperature of 80 degreeC, and it was made into the pre pigment (pigment B). 4 g of xylene was added to a dry attritor, and the treated pigment (pigment C) was obtained by operating at a rotational speed of 300 rpm and an internal temperature of 80 ° C for 1 hour.

Pigment Treatment 2

70 g of quinophthalone pigment "paliotol yellow K0961HD", 2 kg of steel beads of diameter 8mm are put into a dry attritor (MA01D type made by Mitsui Mine Co., Ltd., tank capacity 0.8L), rotation speed 350rpm, internal temperature 60 After operating for 1 hour at 0 ° C. to prepare a pre-pigment (average primary particle size of 40 nm), 3.5 g of diethylene glycol was further added to the dry attritor, and then operated at a rotational speed of 350 rpm and an internal temperature of 60 ° C. for 1 hour to treat the treated pigment ( Pigment D) was obtained.

Pigment Treatment 3

80 g of quinophthalone pigment "paliotol yellow K0961HD", 2 g of xylene, and 2 kg of steel beads of diameter 8 mm are put in a dry attritor (MA01D type manufactured by Mitsui Mine Co., Ltd., tank capacity 0.8 L), and the rotation speed is 300 rpm. And 1 hour at internal temperature of 80 degreeC, and obtained the pigment (pigment E).

Pigment Treatment 4 (Salt Milling Treatment)

250 g of quinophthalone pigment "paliotol yellow K0961HD", 700 g of sodium chloride, 107 g of hydrogenated rosin ester ("ester gum HP" made by Arakawa Kagaku Co., Ltd.) and 160 g of polyethylene glycol ("polyethylene glycol 300" made by Tokyo Kasei Co., Ltd.) It put into the stainless steel 1 gallon kneader (made by Inoue Co., Ltd.), and knead | mixed for 3 hours. Next, the mixture was poured into about 3 liters of hot water, stirred at a high speed mixer for about 1 hour while heated to about 80 ° C to form a slurry, and then filtered and washed with water to remove sodium chloride and polyethylene glycol, followed by 60 ° C. It dried in the hot air oven of about 24 hours, and obtained the salt milling pigment (pigment F).

Pigment Treatment 5

60 g of isoindolin pigments (CI pigment yellow 139, `` palliotol yellow D1819 '' made by BASF Corporation, average particle diameter 110nm), 2.3 kg of steel beads of 8mm in diameter dry typewriter (MA01D type made by Mitsui Mine Co., Ltd., tank capacity 0.8 L), the mixture was operated at a rotational speed of 250 rpm and an internal temperature of 100 ° C for 1 hour to prepare a pre-pigment (average primary particle size of 60 nm), and then 6 g of isobutanol was further added to the dry attritor, and the rotational speed was 250. It operated by rpm and the internal temperature of 80 degreeC for 1 hour, and obtained the process pigment (pigment G).

Pigment Treatment 6

60 g of isoindolin pigments (CI pigment yellow 139, `` palliotol yellow D1819 '' made by BASF Corporation, average particle diameter 110nm), 2.3 kg of steel beads of 8mm in diameter dry typewriter (MA01D type made by Mitsui Mine Co., Ltd., tank capacity 0.8 L), and a pre-pigment (average primary particle size: 60 nm) was prepared by operating at 250 rpm and an internal temperature of 100 ° C. for 1 hour, and then 3 g of a pigment derivative 19 and 6 g of isobutanol in a dry attritor. It injected | thrown-in, it operated for 1 hour at 250 rpm of rotation speed, and internal temperature of 80 degreeC, and obtained the process pigment (pigment H).

Pigment Treatment 7

80 g of isoindolin pigment (CI Pigment Yellow 185, `` Palitolol Yellow D1155 '' manufactured by BASF Corporation, average particle diameter 110 nm) and 3 kg of steel balls having a diameter of 25 mm were put into a ball mill (tank capacity 1.0L), and the rotation speed was 100 rpm. After operating for 2 hours at a temperature of 40 ° C. to prepare a pre-pigment (average primary particle size of 40 nm), 6 g of cyclohexanone was further added to a ball mill, and then operated at a rotational speed of 100 rpm and an internal temperature of 40 ° C. for 2 hours to treat pigment (pigment). 1) was obtained.

Pigment Treatment 8

80 g of isoindolin pigments (CI Pigment Yellow 185, `` Paliotol Yellow D1155 '' manufactured by BASF, 110 nm average diameter) and 3 kg of steel balls having a diameter of 25 mm are placed in a ball mill (tank volume 1.0 L) and rotated. A pre-pigment (average primary particle size of 40 nm) was prepared by operating at 100 rpm for several hours at an internal temperature of 40 ° C., and then 8 g of a pigment derivative 38, 8 g of maleic acid resin and 6 g of cyclohexanone were added into a ball mill. It injected | thrown-in and operated at rotation speed 100 rpm and internal temperature 40 degreeC for 2 hours, and obtained the process pigment (pigment J).

Pigment Treatment 9

Except for changing the quinophthalone pigment to a diketopyrrolopyrrole pigment (CI Pigment Red 254, "Irugin Red 2030" made by Chiba Specialty Chemical Co., Ltd., average particle diameter 200 nm), the same treatment as in Pigment Treatment 1 was performed to give a treated pigment ( Pigment K) was obtained. The average primary particle diameter of the pre pigment was 40 nm.

Pigment Treatment 10

Except for changing the quinophthalone pigment to a copper phthalocyanine pigment (CI Pigment Green 36, Toyo Ink Manufacturing Co., Ltd. "Rionol Green 6YK", an average particle diameter of 105 nm), the treatment pigment (pigment L) was subjected to the same treatment as in Pigment Treatment 1. Got it. The average primary particle diameter of the pre pigment was 40 nm.

Pigment Treatment 11

Except for changing the quinophthalone pigment to a copper phthalocyanine pigment (CI Pigment Blue 15: 6, Toyo Ink Manufacturing Co., Ltd. "Rionol Blue E", an average particle diameter of 400 nm), the same treatment as in Pigment Treatment 1 was performed to give a treatment pigment (pigment M ) The average primary particle diameter of the pre pigment was 40 nm.

Obtained pigment A-M was observed with the electron microscope, the primary particle diameter was measured, and the deviation range of the average primary particle diameter and primary particle diameter was calculated | required. The results are shown in Table 1. In addition, the deviation range of a primary particle diameter was shown by the range of the particle diameter which contains 80% or more of pigment particle of all the pigment particle.

Pigment Remarks Average primary particle size (nm) Deviation range of primary particle size (nm) Pigment A K0961HD 120 100-140 Pigment B Pigment A, Dry Grinding Pre-Pigment  45 20-80 Pigment C Prex Pigment B Xylene Treatment  50 40-60 Pigment D Preg Pigment B DEG Treatment  45 35-70 Pigment E Xylene Dry Grinding of Pigment A  60 40-80 Pigment F Dry Salt Milling of Pigment A  55 40-60 Pigment G Treatment Pigment Of PY139  65 30-60 Pigment H Treatment Pigment of PY139 1  60 30-55 Pigment I Treatment Pigment Of PY185  45 30-50 Pigment J Treatment Pigment of PY185 1  40 25-45 Pigment K Treatment Pigment Of PR254  45 30-60 Pigment L Treatment Pigment Of PG36  45 30-60 Pigment M Treatment Pigment Of PB156  40 30-70

Example 1

The mixture of the following composition was uniformly stirred and mixed, and then dispersed in an eiger mill using zirconium oxide beads having a diameter of 1 mm for 5 hours, and filtered through a 5 μm filter to prepare a pigment dispersion.

Pigment C 9.0 Part

Resin-type pigment dispersant (Aji Spa PB821 manufactured by Ajinomoto Co., Ltd.) 1.0 parts

50.0 parts acrylic resin solution

40.0 parts cyclohexanone

Next, the mixture of the following composition using the obtained pigment dispersion was stirred and mixed so that it may become uniform, and it filtered with the filter of 1 micrometer, and obtained the alkali developing resist material.

Pigment Dispersion 60.0 parts

Acrylic resin solution 11.0 parts

Trimetholpropane triacrylate 4.2 parts

(`` NK ester ATMPT '' made by Shinnakamura Kagaku Corporation)

1.2 parts of photoinitiators (Irugacure 907, manufactured by Chiba Electric Co., Ltd.)

Sensitizer (EAB-F manufactured by Hodogaya Kagaku Co., Ltd.) 0.4parts

Cyclohexanone 23.2 parts

Examples 2-10, Comparative Examples 1-8

An alkali developing resist material was produced in the same manner as in Example 1 except that Pigment C was changed to the pigment shown in Table 2.

The obtained resist material was apply | coated using the spin coater on the glass substrate of 100 mm x 100 mm, 1.1 mm thickness, and the coating substrate was obtained. Subsequently, after drying at 70 degreeC for 20 minutes, ultraviolet exposure was performed with the accumulated light amount 150mJ using the ultrahigh pressure mercury lamp. The coated substrate was heated at 230 ° C. for 1 hour to obtain a 2 micron identical film thickness substrate. The contrast ratio of this board | substrate was measured.

In addition, the viscosity of the obtained resist material was measured using the ELD type viscometer (made by Toki Sangyo Co., Ltd.) about what was stored immediately after adjustment and in 40 degreeC oven for 1 week. In addition, about the resist of Examples 1-8, the multiple of the contrast ratio with respect to the contrast ratio of the resist using each original pigment was computed. The above results are shown in Table 2.

Pigment Contrast Ratio Resist material viscosity (mPas) Contrast multiple for raw pigment Early After 1 week at 40 ℃ Viscosity change Example 1 Pigment C 450 7 7 0 4.5 Comparative Example 1 Pigment A 100 5 14 9 1.0 Comparative Example 2 Pigment B 383 11 34 23 3.8 Example 2 Pigment D 446 7 7 0 4.5 Example 3 Pigment E 441 7 7 0 4.4 Comparative Example 3 Pigment F 447 36 50 14 4.5 Example 4 Pigment G 320 7 7 0 4.0 Example 5 Pigment H 380 7 7 0 4.1 Example 6 Pigment I 640 10 10 0 7.1 Example 7 Pigment J 700 10 10 0 7.7 Example 8 Pigment K 890 7 7 0 1.7 Example 9 Pigment L 1030 10 10 0 1.3 Example 10 Pigment M 1030 10 10 0 1.3 Comparative Example 4 Paliotol Yellow D-1819 (raw pigment of Example 4) 80 7 7 0 One Comparative Example 5 Paliotol Yellow D-1155 (raw pigment of Example 6) 90 10 10 0 One Comparative Example 6 Irgin Red 203G (Primary Pigment of Example 8) 520 7 7 0 One Comparative Example 7 Lionol Green 6YK (Primary Pigment of Example 9) 790 10 10 0 One Comparative Example 8 Lionol Blue (Primary Pigment of Example 10) 690 10 10 0 One

The resist material obtained in Example 1 had a higher contrast ratio than the resist material obtained in Comparative Example 1. Moreover, although the resist material obtained by the comparative example 2 and the comparative example 3 had high contrast ratio, the viscosity stability of a resist is very bad. The resists obtained in the examples all have high contrast ratios and good viscosity stability.

As described above, in the coloring composition for color filters of the present invention, since a small amount of an organic solvent having a crystal growth action is added and dry pulverization is used, the pigment is made fine in primary particles. It is dispersed in a carrier and extremely low viscosity.

Further, the color filter of the present invention is excellent in various resistances and has a high contrast ratio because the color filter has a filter segment which is stably dispersed in the pigment carrier without aggregation and is formed of an extremely low viscosity coloring composition.

Claims (10)

In the coloring composition for color filters containing the pigment support which consists of transparent resin, its precursor, or its mixture, and an organic pigment, The average primary which the said organic pigment dry-pulverized the crude organic pigment with an average particle diameter larger than 100 nm. A small amount of an organic solvent having a crystal growth action with respect to the pre-pigment is added to a pre-pigment having a particle size of 10 to 100 nm, followed by dry pulverization. Color filter characterized in that the pigment particles of 100 nm or more are 20% by weight or less of the total pigment particles, and the pigment particles in the range of the primary particle diameter of 20 to 100 nm are treated pigments having a particle size distribution of 60% by weight or more of the total pigment particles. Coloring composition. The composition according to claim 1, wherein the organic solvent is an organic solvent having a boiling point of 50 to 250 ° C. The composition according to claim 1 or 2, wherein the organic pigment is a yellow pigment. The method of claim 3, wherein the yellow pigment is C.I. Pigment Yellow 138, C.I. Pigment Yellow 139 and C.I. Pigment Yellow 185, characterized in that the composition selected from the group consisting of. The filter segment formed from the coloring composition for color filters of Claim 1 is provided, The color filter characterized by the above-mentioned. In the coloring composition for color filters containing the pigment support which consists of transparent resin, its precursor, or its mixture, and an organic pigment, The said organic pigment is the crude organic pigment which the crude organic pigment whose average particle diameter is larger than 100 nm is mentioned. It is made by dry pulverization by adding a small amount of an organic solvent having a crystal growth action with respect to the above, and has an average primary particle size of 10 to 100 nm, and pigment particles having a primary particle size of 100 nm or more, at 20 wt% or less of the total pigment particles, The pigment particle of the range of 20-100 nm of particle diameters is a process pigment which has a particle size distribution which is 60 weight% or more of all the pigment particles, The coloring composition for color filters. The composition according to claim 6, wherein the organic solvent is an organic solvent having a boiling point of 50 to 250 ° C. 8. A composition according to claim 6 or 7, wherein said organic pigment is a yellow pigment. The method of claim 8, wherein the yellow pigment, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139 and C.I. Pigment Yellow 185, characterized in that the composition is selected from the group consisting of. The filter segment formed from the coloring composition for color filters of Claim 6 is provided. The color filter characterized by the above-mentioned.

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