KR20070116183A - Pigment dispersion liquid, process for producing the same, colored resin composition, color filter and liquid crystal display - Google Patents

Abstract

A pigment dispersion liquid excelling in depolarization characteristics and capable of forming red pixels of high contrast. There is provided a pigment dispersion liquid comprising a pigment, a solvent and a dispersant, characterized in that when red pixels are formed on a glass substrate with the use of a colored resin composition containing the pigment dispersion liquid and when the substrate is interposed between two polarizing plates and measured by means of a color brightness meter, the contrast (C) being the ratio of light intensity (B) exhibited at arranging of the polarizing plates in parallel relationship to light intensity (A) exhibited at arranging in orthogonal relationship, B/A, satisfies the relationship C >= 4000x - 2000 wherein x is the value of chromaticity of transmitted light with light source (C) as measured by means of a spectrophotometer, and that the pigment contains an anthraquinone red pigment (preferably, C.I. pigment red 177) and an azo yellow pigment (preferably, C.I. pigment yellow 150) and has a particle diameter ranging from 30 to 500 nm. There is further provided a process for producing the pigment dispersion liquid, characterized in that a mixture of pigment, solvent and dispersant is dispersed by the use of beads of 30 to 500 mum average grain diameter.

Description

Pigment Dispersion, Manufacturing Method of Pigment Dispersion, Colored Resin Composition, Color Filter and Liquid Crystal Display {PIGMENT DISPERSION LIQUID, PROCESS FOR PRODUCING THE SAME, COLORED RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY}

 This invention relates to a pigment dispersion liquid, the manufacturing method of a pigment dispersion liquid, a colored resin composition, a color filter, and a liquid crystal display device. In detail, the pigment dispersion liquid which can form the red (R) pixel which is excellent in a depolarizing characteristic and has high contrast, the method for manufacturing this pigment dispersion liquid, the colored resin composition containing this pigment dispersion liquid, this coloring It relates to a color filter using a resin composition and a liquid crystal display device using the color filter.

Conventionally, as a method of manufacturing the color filter used for a liquid crystal display device etc., the pigment dispersion method, the dyeing method, the electrodeposition method, the printing method are known. Especially, the pigment dispersion method which has the average outstanding characteristic from a viewpoint of spectral characteristics, durability, a pattern shape, precision, etc. is employ | adopted most widely.

As the pigment dispersion method, a black matrix is usually formed on a transparent support such as a glass substrate by a metal light shielding film such as chromium or chromium oxide, and then, for example, a colored resin composition in which red pigment is dispersed (hereinafter, The colored resin composition which disperse | distributed the red, blue, or green pigment is described as "color resist," and the colored resin composition which disperse | distributed black pigment may be described as "black resist." It apply | coats, exposes through a mask, develops after exposure, and forms a red pixel. By applying, exposing and developing the color resist in the same order, pixels of blue and green are formed, and pixels of three colors are formed. Since the black matrix portion between the pixels becomes concave, in most cases, a protective film is formed by covering the pixel formation surface with a transparent resin such as an epoxy resin or an acrylic resin to smooth the surface. However, in some cases, such a protective film is not formed. . Further, a transparent conductive film such as an indium tin oxide (ITO) film is formed on the protective film by sputtering, vacuum deposition, or the like. In addition, in recent years, the pigment dispersion method is often adopted to form a black matrix, for example, a black matrix is formed by coating, exposing and developing a colored resin composition (black resist) in which a black pigment is dispersed.

In recent years, the flow of technological innovation is rapid, and the large screen of a liquid crystal display device and the expansion to a television use are progressing rapidly. As a television use, high brightness and a high viewing angle are calculated | required more than now, As a liquid crystal drive system, the method of wide viewing angles, such as VA (vertical orientation) system and IPS (plane orientation) system, is used, for example. On the other hand, when the viewing angle is widened, the luminance decreases in inverse proportion to it. For this reason, generally, the fall of this luminance is compensated by increasing the number of lamps of a backlight. However, when the brightness of the backlight rises, the contrast decreases due to leakage light during black display, which may lead to a deterioration in image quality. For this reason, the color filter is more excellent than before, and the thing with high contrast is calculated | required.

Conventionally, the red pixel of a color filter has a diketopyrrolopyrrole red pigment, especially C.I. Pigment Red 254 is used preferably, and has contributed to the brightness improvement (refer patent document 1). However, C.I. Pigment Red 254 has a limited contrast enhancement due to problems of primary particle size and anisotropy of grain shape.

Moreover, as a red pigment conventionally used, an anthraquinone type red pigment, especially C.I. Pigment Red 177, which is described in terms of C.I. Valid than Pigment Red 254. And C.I. The technique of mixing Pigment Red 177 and a yellow pigment is known (patent document 2), and has been widely used for liquid crystal display devices. However, depending on the yellow pigment to be mixed, the contrast may be adversely affected, the particle size distribution is inadequate, and the contrast is insufficient.

On the other hand, as a pigment dispersion method of a general pigment dispersion liquid, the pigment dispersion method using the specific zirconia baking beads for the purpose of the improvement of surface glossiness is disclosed (patent document 3). However, the use of the dispersing method for the purpose of improving the contrast of the color filter is not easily conceived by those skilled in the art in terms of the difference of the purpose, and the use of the dispersing method for the general pigment only means the improvement of the contrast. It was difficult to achieve the effect.

[Patent Document 1]

Japanese Unexamined Patent Publication No. 10-227911

[Patent Document 2]

Japanese Patent Application Laid-Open No. 10-148712

[Patent Document 3]

Japanese Patent Laid-Open No. 7-155577

<Start of invention>

As described above, while the liquid crystal display device has recently been spreading for television use, as the viewing angle is enlarged and the brightness is improved, the passive characteristics for the color filters, that is, the demand for the improvement of the contrast are increasing. In reality, these required characteristics are not fully satisfied.

Therefore, the subject of this invention is a pigment dispersion liquid which can form the red pixel which is excellent in a polar characteristic and has a high contrast, its manufacturing method, the colored resin composition containing this pigment dispersion liquid, the color filter using this colored resin composition, and It is providing the liquid crystal display device using this color filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it contains a pigment, a solvent, and a dispersing agent, a pigment is a mixture of an anthraquinone type red pigment and an azo type yellow pigment, and the particle size of a pigment is 30-500 nm. By using the pigment dispersion liquid in it, it discovered that high contrast red pixel can be formed and came to complete this invention.

That is, the summary of 1st invention of this invention is a pigment dispersion liquid containing a pigment, a solvent, and a dispersing agent WHEREIN: When the red pixel was formed on the glass substrate using the coloring resin composition containing the said pigment dispersion liquid, Contrast C calculated by the formula (1) from the light amount B when the polarizing plate is parallel to the light amount A when the polarizing plate is orthogonal when the substrate is sandwiched between the polarizing plates and measured by a color luminance meter, and measured by a spectrophotometer. The x value of the chromaticity of the transmitted light in the C light source at the time of being present is represented by Formula (2), It exists in the pigment dispersion liquid.

C = B / A (1)

C≥4000x-2000 (2)

The gist of the second aspect of the present invention is a pigment dispersion containing a pigment, a solvent and a dispersant, wherein the pigment contains an anthraquinone-based red pigment and an azo-based yellow pigment, and the particle size of the pigment is 30-500 nm. It is in a pigment dispersion in the range.

The gist of the third invention lies in the method for producing the pigment dispersion, in which the mixture of the pigment, the solvent, and the dispersant is dispersed using beads having an average particle diameter of 30 to 500 nm in producing the pigment dispersion.

The summary of a 4th invention exists in the colored resin composition containing the pigment dispersion liquid of the said this invention.

The fifth aspect of the present invention is a colored resin composition containing a pigment, a solvent, a dispersant, a binder resin, a monomer, and a photopolymerization initiation system. When a red pixel is formed on a glass substrate using the colored resin composition, two polarizing plates are used. Contrast C calculated by the formula (1) from the light quantity B when the polarizing plate is parallel with the light quantity A when orthogonal to the light quantity A when the substrate is inserted into the substrate and measured by a color luminance meter, and a C light source measured by a spectrophotometer X value of the chromaticity of the transmitted light in is represented by Formula (2), It exists in the colored resin composition characterized by the above-mentioned.

C = B / A (1)

C≥4000x-2000 (2)

The summary of a 6th invention exists in the color filter which has a pixel formed using the colored resin composition of the said invention.

The gist of the seventh invention resides in a liquid crystal display device including the color filter.

The present invention has the following excellent effects, the industrial value of use is very large.

1. According to the pigment dispersion liquid of this invention and the coloring resin composition of this invention containing this pigment dispersion liquid, the red pixel which is excellent in a unipolar characteristic and has high contrast can be formed.

2. According to the manufacturing method of the pigment dispersion liquid of this invention, such a pigment dispersion liquid can be manufactured easily.

3. The color filter of the present invention and the liquid crystal display device of the present invention including the color filter are very high quality and effective for high luminance and high viewing angle for large screens because of excellent polarization characteristics of red pixels and high contrast. Do.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described in detail.

First, the contrast of the red pixel formed using the pigment dispersion liquid of this invention is demonstrated.

When the pigment dispersion liquid of this invention forms the red pixel on the glass substrate using the coloring resin composition containing this, sandwiches the said board | substrate between two polarizing plates, and when it measures by a color luminance meter, the polarizing plate is orthogonal. The x value of the chromaticity of the transmitted light in the C light source measured in the contrast C calculated by the formula (1) and the C light source measured by the spectrophotometer from the light quantity B when parallel with the light quantity A of is characterized by to be.

C = B / A (1)

C≥4000x-2000 (2)

Here, formation of a red pixel is performed as follows. That is, the colored resin composition is spin-coated so that the film thickness after drying on a glass substrate becomes 2 micrometers, and it dries at 80 degreeC for 10 minutes, after that, it irradiates with UV irradiation and hardens resin, and heat crosslinking is carried out at 230 degreeC for 30 minutes. To form a red pixel.

A spectrophotometer ("U4100" manufactured by Hitachi, Ltd.) is used for measuring the chromaticity of transmitted light in the C light source. In addition, the measurement of the light quantity A, B (cd / cm <2>) when a polarizing plate is parallel and orthogonal is carried out by putting two polarizing plates in close contact, without leaving a gap with a board | substrate, and a color luminance meter (made by Topcon Corporation "BM -5A ") is used.

If C <4000x-2000, the contrast becomes low, and since light leakage occurs during black display, the image quality deteriorates.

In the present invention, the contrast C and x values are preferably represented by the following (2-1) formulas, and more preferably by the following (2-2) formulas.

C≥4000x-1800 (2-1)

C≥4000x-1400 (2-2)

Next, the structural component of the pigment dispersion liquid of this invention is demonstrated.

[1] pigment dispersions

The pigment dispersion liquid of this invention makes a pigment, a solvent, and a dispersing agent an essential component, and the other additives other than the said component etc. are mix | blended as needed. Hereinafter, each component is demonstrated.

[1-1] pigments

A pigment means coloring the pigment dispersion liquid which concerns on this invention. In this invention, it is preferable to mix and use an anthraquinone type red pigment and an azo type yellow pigment as a pigment.

As an anthraquinone type red pigment, it is C.I. Pigment Red 177, C.I. Pigment Orange 51, C.I. Pigment Orange 168, such as one or two or more may be mentioned, C.I. excellent in terms of ease of atomization, dispersion stability, spectral transmittance, fastness and the like. Pigment Red 177 (P.R. 177) is particularly preferably used.

As an azo yellow pigment, it is C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 10, C.I. Pigment Yellow 12, C.I Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 55, C.I Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I Pigment Yellow 97, C.I Pigment Yellow 150, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow 167, C.I. Pigment Yellow 180, etc. 1 type, or 2 or more types can be mentioned, Among these, C.I. Pigment Yellow 83, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 is preferable, and C.I. C.I. is excellent in terms of easy atomization, dispersion stability, spectral transmittance, and fastness. Pigment Yellow 150 (P.Y. 150) is particularly preferably used.

The ratio of the pigment with respect to the total solid in a pigment dispersion liquid is 10-90 weight% normally, Preferably it is 30-90 weight%, More preferably, it is 50-90 weight%. If the ratio of the pigment in the pigment dispersion is too small, the coloring power is lowered, and the film thickness tends to be too thick with respect to the color density. On the contrary, if the ratio of the pigment is too large, dispersion stability is deteriorated, and problems such as reagglomeration and thickening are caused. There is a risk of this happening. In addition, in this invention, "all solid content" means all components other than the solvent component mentioned later.

In addition, the mixing ratio of the anthraquinone type red pigment and an azo type yellow pigment is 0.1 to 99 weight% normally, Preferably it is 3 to 80 weight% in the weight ratio of the azo type yellow pigment with respect to an anthraquinone type red pigment, More preferably, it is 5 to 60 weight%. If there are too few azo-based yellow pigments than this range, the color becomes too close to blue, and the transmittance (Y value in the XYZ color system) decreases. On the contrary, if there are too many azo-based yellow pigments, the color becomes too close to yellow and the color of the red pixel is too low. As not preferred.

In addition, when the pigment dispersion liquid of this invention mixes and uses an anthraquinone type red pigment and an azo yellow pigment as a pigment, you may use another pigment together in the range which does not impair the effect of this invention. In this case, as another pigment which can be used together, it is an isoindrin type pigment, for example, C.I. Pigment Yellow 139, C.I. Pigment Orange 66, C.I. Pigment Orange 69, C.I. Pigment Red 260 is an isoindrinone pigment, for example C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 173, C.I. Pigment Orange 61 is, for example, C.I Pigment Yellow 138 as the quinophthalone pigment, and one or two or more thereof can be used. When using another pigment together, it is preferable to make the ratio into 20 weight% or less, especially 10 weight% or less by weight ratio with respect to an anthraquinone type red pigment.

[1-2] Solvent

In the pigment dispersion liquid of this invention, a solvent shows the function which melt | dissolves or disperse | distributes a pigment, a dispersing agent, the component other than the above mix | blended as needed, etc., and adjusts a viscosity.

As a solvent, for example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane , Varsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apco thinner, butyl ether, diisobutyl ketone, methylcyclohexene, methylnonyl ketone, propyl ether, dodecane, Socal solvent Nos. 1 and 2, amyl formate, dihexyl ether, diisopropyl ketone, Solveso # 150, (n, sec, t-) butyl acetate, hexene, Shell TS28 solvent, butyl chloride, ethyl amyl Ketones, ethylbenzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethylpentanone, methylbutyl ketone, methylhexyl ketone, methyl isobutylate, benzonitrile, ethyl propionate, methylcello Solvate, methyl iso Milk ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl Ropionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3 Ethoxypropionic acid, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol Monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. These solvents may be used individually by 1 type, or may mix and use 2 or more types.

Although the content of the solvent in the whole pigment dispersion liquid of this invention does not have a restriction | limiting in particular, The upper limit is 99 weight% normally. When the solvent exceeds 99% by weight, there are too few pigments, dispersants, and the like, which are inappropriate to form a dispersion. On the other hand, the lower limit of the solvent content is usually 70% by weight, preferably 75% by weight, more preferably 80% by weight in consideration of viscosity and the like.

[1-3] Dispersants

As the dispersant, a polymer dispersant and / or a pigment derivative is preferably used.

Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like. have. Specific examples of such a dispersant include "EFKA" (manufactured by EFKA Chemicals Co., Ltd.), "Disperbyk" (manufactured by BICCHEM Corporation), "DISPARLON" (manufactured by Kusumoto Kasei Co., Ltd.), " SOLSPERSSE "(made by Geneca Co.)," KP "(made by Shin-Etsu Chemical Co., Ltd.)," POLYFLOW "(made by Kyueisha Chemical Co., Ltd.), etc. are mentioned. These polymeric dispersants can be used individually by 1 type or in mixture of 2 or more types.

The ratio of the polymer dispersant to the total solids of the pigment dispersion is usually 10 to 90% by weight, preferably 10 to 70% by weight, more preferably 10 to 50% by weight. When the ratio of the polymer dispersant in the pigment dispersion is too large, the pigment ratio is relatively low due to the relatively low proportion of the pigment, and the film thickness tends to be too thick with respect to the color density. On the contrary, when the ratio of the polymer dispersant is too small, the dispersion stability is low. There is a risk of deterioration and problems such as reagglomeration and thickening.

On the other hand, examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, Although derivatives of diketopyrrolopyrrole pigments and dioxadine pigments may be mentioned, in the present invention, it is preferable to use anthraquinone pigments and azo pigment derivatives as derivatives of the same system. These pigment derivatives can be used individually by 1 type or in mixture of 2 or more types.

As a substituent of a pigment derivative, a sulfonic acid group, a sulfonamide group and its quaternary salt, a phthalimide methyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. are mentioned, These substituents are directly in a pigment skeleton, or It is couple | bonded through the linking groups, such as an alkyl group, an aryl group, and a heterocyclic group. As a substituent of a pigment derivative, Preferably a sulfonamide group, its quaternary salt, and a sulfonic acid group are mentioned, More preferably, it is a sulfonic acid group. In addition, these substituents may be substituted by two or more in one pigment skeleton, and the mixture of the compound from which a substitution number differs may be sufficient.

Preferable specific examples of the pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of anthraquinone pigments, and the like.

The ratio of the pigment derivative with respect to the total solid of a pigment dispersion liquid is 0.1-20 weight% normally, Preferably it is 0.5-15 weight%, More preferably, it is 1-10 weight%. When the proportion of the pigment derivative in the pigment dispersion is too small, the dispersion stability is deteriorated, and there is a risk of problems such as reagglomeration and thickening. On the contrary, when too much, the contribution to the dispersion stability is saturated, resulting in a decrease in color purity. It is not desirable to have.

In this invention, even if it uses together the above-mentioned polymer dispersing agent and pigment derivative as a dispersing agent, there is no obstacle.

[1-4] Other Ingredients

There is no restriction | limiting in particular as other components mix | blended with the pigment dispersion liquid of this invention as needed, When the pigment dispersion liquid of this invention is mix | blended with the coloring resin composition for color filters mentioned later, the pigment dispersion liquid of this invention is the binder resin mentioned later A part of may be included and dispersion stability at the time of manufacturing the pigment dispersion liquid of this invention can be improved by including such binder resin.

In this case, it is preferable that the addition amount of binder resin shall be 5-100 weight%, especially 10-80 weight% with respect to the whole pigment in a pigment dispersion liquid. If the added amount of the binder resin is less than 5% by weight, the effect of improving dispersion stability is insufficient. If the amount of the binder resin exceeds 100% by weight, the pigment concentration is lowered, so that sufficient color concentration cannot be obtained.

[1-5] Particle Size Distribution of Pigments

In the pigment dispersion of the present invention, the particle diameter of the pigment is 30 nm or more, preferably 50 nm or more, more preferably 80 nm or more, 500 nm or less, preferably 350 nm or less, and more preferably 250 nm or less. to be. In addition, it is preferable that the half value width of a particle size distribution is 250 nm or less, especially 150 nm or less, especially 100 nm or less.

That is, in the present invention, it is important to realize a combination of a specific pigment and excellent small-pole characteristics and high contrast in the specific particle size range, and the particle size, preferably the half-value width is in the above range, and is out of the range. If it is possible to obtain excellent quenching characteristics and high contrast according to the present invention.

[1-6] Manufacturing Method of Pigment Dispersion

In order to realize the particle size distribution described above, various methods can be employed as the method for producing the pigment dispersion of the present invention, but the beads mill method of colliding hard spheres (beads) to disperse the pigment is particularly preferably used. The beads to be used include glass, zirconia (ZrO ₂ ), chromium, and the like. Among them, zirconia beads having a specific gravity and having a small amount of contami such as wear powder are suitable. Moreover, the average particle diameter of the beads to be used is 30-500 micrometers normally, Preferably it is 30-300 micrometers, More preferably, it is 40-200 micrometers. If the average particle diameter of the beads is less than 30 µm, the beads are light in weight, the collision energy is small, and the dispersibility is reduced. If the average particle diameter of the beads is larger than 500 µm, the void volume between the beads is large, which makes it difficult to form the pigment. In addition, bead weight is heavy, excessive collision energy is added to a pigment, and it is difficult to make particle size of a pigment into the range of 30-500 nm.

The disperser used for the dispersion treatment may be a disperser capable of using the beads, and is not particularly limited. For example, "TORUSMILL" manufactured by Getzmann, and "Agitator Mill" manufactured by Ashizawa Corporation in a batch manner. , "Pico mill" manufactured by Asada Iron Works, and "Apex mega" manufactured by Kotobuki R & D Institute.

Although there is no restriction | limiting in particular in the preparation process of a pigment dispersion liquid, The dispersion by the said dispersion facility is performed during the manufacturing process of a pigment dispersion liquid. For example, the above-described pigment, dispersant, solvent, binder resin, etc. may be mixed in advance as necessary as a dispersion liquid composition to make a liquid phase, and the blended solution may be subjected to dispersion treatment by beads using the above-mentioned dispersion machine. Obtain a pigment dispersion.

The amount of beads used is not particularly limited, but is preferably about 50 to 90% by volume of the vessel volume of the disperser used for the dispersion treatment. If the amount of beads filled is too small, it takes time to obtain a pigment dispersion having a desired particle size distribution by dispersion treatment. If the amount of beads is too large, mechanical load increases and beads are broken, and the particle size distribution of the pigment is widened.

Moreover, you may perform preprocessing, such as a dispersion | distribution process by a roll mill, a kneader, or a large particle size beads exceeding an average particle diameter of 500 micrometers, as a preprocess of the dispersion process using the beads whose average particle diameters are 30-500 micrometers. In addition, the prepared pigment dispersion may be further subjected to post-treatment. As a post-treatment method, the process by "T.K. Filmics" by Tokushu Kigusa, "Ultimaizer" by Suginoma Shin-Shi etc. is mentioned, for example.

[2] colored resin compositions

Next, the colored resin composition of this invention is demonstrated.

Although the pigment dispersion liquid of the present invention mentioned above can be used for various uses, it is especially used as a coloring resin composition for the purpose of pixel image formation of a color filter, etc. especially. As a coloring resin composition, binder resin, a monomer, a photoinitiator, and other solid content may be mix | blended with the pigment dispersion liquid of this invention. Hereinafter, each component is demonstrated.

[2-1] binder resin

As binder resin, homopolymers, such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, maleimide, for example Or copolymers containing these monomers, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, novolac resin, resol resin, polyvinylphenol And polyvinyl butyral.

In addition, in this invention, "(meth) acrylic acid" means including both acrylic acid and methacrylic acid, (meth) acrylate, a (meth) acryloyl group, etc. are synonymous, and "(co) polymer "Means containing both a homopolymer (homopolymer) and a copolymer (copolymer), and" an acid (anhydride) "means containing both an acid and the anhydride. In addition, in this invention, an "acrylic resin" means the (co) polymer containing the (co) polymer containing (meth) acrylic acid and the (meth) acrylic acid ester which has a carboxyl group.

Preferred among them is an acrylic resin containing a monomer having a carboxyl group or a phenolic hydroxyl group in the side chain or the main chain. When acrylic resin which has such a functional group is used as binder resin, image development in alkaline solution is at the time of manufacture of a color filter. Among them, preferred are acrylic resins having a carboxyl group that can be developed in a highly alkaline solution, such as acrylic acid (co) polymers, styrene-maleic anhydride resins, and acid anhydride modified resins of novolac epoxyacrylates. Especially, especially preferable is the (co) polymer containing the (co) polymer containing (meth) acrylic acid or the (meth) acrylic acid ester which has a carboxyl group. These acrylic resins are excellent in developability, transparency, etc., can obtain a copolymer with different performance in combination with various monomers, and there exists an advantage which is easy to control a manufacturing method.

Acrylic resin as binder resin is the (co) polymer which has the following monomer as a main component, for example.

That is, as this monomer, the compound etc. which added the acid (anhydride) to hydroxyalkyl (meth) acrylate are mentioned. And as said hydroxyalkyl (meth) acrylate, (meth) acrylic acid, succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (Meth) acryloyloxypropyl) ester, adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- ( (Meth) acryloyloxypropyl) ester, maleic acid (2- (meth) acryloyloxypropyl) ester, succinic acid (2- (meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acrylic acid Loyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxybutyl) ester, phthalic acid (2- (meth) acrylic Iloxybutyl) ester, maleic acid (2- (meth) acryloyloxybutyl) ester, etc. are mentioned, As an acid (anhydride), succinic acid (succinic anhydride), phthalic acid (phthalic anhydride), maleic acid (maleic anhydride), etc. are mentioned. Can be mentioned.

As a monomer which can be copolymerized with said monomer, Styrene-type monomers, such as styrene, (alpha) -methylstyrene, and vinyltoluene, unsaturated group containing carboxylic acids, such as cinnamic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid, methyl (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, aryl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) Ester of (meth) acrylic acid, such as acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, and methoxyphenyl (meth) acrylate, (meth) acrylic acid Compounds which added lactones, such as (epsilon) -caprolactone, (beta) -propiolactone, (gamma) -butyrolactone, and (epsilon) -valerolactone, acrylonitrile, such as acrylonitrile and methacrylonitrile, (meth Arc Amide, N-methylol acrylamide, N, N-dimethyl acrylamide, N-methacryloyl morpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl acrylamide And vinyl acids such as acrylamide, vinyl acetate, vinyl vatate, vinyl propionate, vinyl cinnamate, and vinyl pivalate.

In particular, as a preferable binder resin for improving the intensity | strength of the coating film on a board | substrate, acrylic resin which copolymerized at least 1 sort (s) of the monomer (a) listed below and at least 1 sort (s) of the monomer (b) listed below is mentioned. have.

Monomer (a): styrene, (alpha) -methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl ( Monomers having phenyl groups, such as meth) acrylsulfonamide

Monomer (b): (2- (meth) acryloyloxyethyl) succinate, (2-acryloyloxyethyl) adipate, (2- (meth) acryloyloxyethyl) phthalate, (2- ( (Meth) acrylates having (meth) acrylic acid and carboxyl groups such as (meth) acryloyloxyethyl) hexahydrophthalate and (2- (meth) acryloyloxyethyl) maleate.

The monomer (a) is usually 10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and the monomer (b) is usually 2 to 90 mol%, preferably 20 to 80 mol %, More preferably 30 to 70 mol%.

Moreover, as binder resin, acrylic resin which has ethylenic double bond in a side chain is preferable. Since the photocurability of the colored resin composition of this invention improves by use of such an acrylic resin, the resolution of the color filter which concerns on 2nd invention, and adhesiveness of a pixel and a board | substrate can be improved further.

As a method of introducing an ethylenic double bond into the side chain of acrylic resin, the method described in Unexamined-Japanese-Patent No. 50-34443, Japan Unexamined-Japanese-Patent No. 50-34444, etc.,

(1) The method of making the carboxyl group which acrylic resin has react with the compound which has glycidyl group, an epoxy cyclohexyl group, and a (meth) acryloyl group.

(2) The method of making acrylic acid chloride etc. react with the hydroxyl group which acrylic resin has is mentioned.

Specifically, (meth) acrylic acid glycidyl, allyl glycidyl ether, (alpha)-ethyl acrylate glycidyl, crotonyl glycidyl ether, (iso) crotonic acid glycidyl to acrylic resin which has a carboxyl group and a hydroxyl group By reacting compounds such as ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic acid chloride and (meth) aryl chloride, an acrylic resin having an ethylenic double bond group in the side chain can be obtained. have. Especially, it is preferable to make the alicyclic epoxy compound like (3, 4- epoxycyclohexyl) methyl (meth) acrylate react with acrylic resin which has a carboxyl group and a hydroxyl group.

As described above, as a method of introducing an ethylenic double bond into an acrylic resin having a carboxylic acid group or a hydroxyl group in advance, it is usually 2 to 50 mol%, preferably 5 to 40 mol% of a carboxyl group or a hydroxyl group. Preference is given to a method of bonding a compound having a double bond. Moreover, the range of 5-200 mg-KOH / g is preferable as content of content of a carboxyl group. When the acid value is less than 5 mg-KOH / g, it becomes insoluble in the alkaline developer, and when it exceeds 200 mg-KOH / g, the developing sensitivity may decrease.

The weight average molecular weight (Mw) measured by GPC of said acrylic resin has the preferable range of 1,000-100,000. When the weight average molecular weight is less than 1,000, it is difficult to obtain a uniform coating film, and when it exceeds 100,000, developability tends to decrease.

The ratio of binder resin is 10-80 weight% normally with respect to the total solid in the colored resin composition of this invention, Preferably it is 20-70 weight%.

[2-2] monomers

The monomer contained in the colored resin composition is not particularly limited as long as it is a polymerizable low-molecular compound, but an addition polymerizable compound having at least one ethylenic double bond (hereinafter, abbreviated as "ethylenic compound") is preferable. When the colored resin composition of this invention is irradiated with actinic light, such an ethylenic compound add-polymerizes and hardens | cures by the action of the photoinitiator system mentioned later. In addition, in this invention, a "monomer" is a meaning corresponding to what is called a high molecular substance, and it is a meaning including a dimer, a trimer, an oligomer, etc. other than a narrow monomer (monomer).

As said ethylenic compound, For example, ester of unsaturated carboxylic acid, unsaturated carboxylic acid, and monohydroxy compound, ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, aromatic polyhydroxy compound, Esters obtained by esterification with esters of unsaturated carboxylic acids, unsaturated carboxylic acids and polyhydric carboxylic acids, and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above, and poly And ethylenic compounds having a urethane skeleton in which an isocyanate compound and a (meth) acryloyl-containing hydroxy compound are reacted.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, Acrylic esters, such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, are mentioned. . Moreover, the methacrylic acid ester which changed the acrylic acid part of these acrylates into the methacrylic acid part, the itaconic acid ester which changed into the itaconic acid part, the crotonic acid ester which changed into the crotonic acid part, or the maleic acid ester which changed into the maleic acid part etc. are mentioned. have.

As ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, a pyrogallol triacrylate, etc. are mentioned. Can be.

The esters obtained by esterification of unsaturated carboxylic acid, polyhydric carboxylic acid, and polyhydric hydroxy compound need not necessarily be a single substance, and may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensation of acrylic acid, adipic acid, butanediol and glycerin Water and the like.

As an ethylenic compound which has a urethane frame which made the polyisocyanate compound and the (meth) acryloyl-group containing hydroxy compound react, Aliphatic diisocyanates, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, iso Alicyclic diisocyanates such as poron diisocyanate, aromatic diisocyanates such as triylene diisocyanate, diphenylmethane diisocyanate and the like, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1 Reactants with (meth) acryloyl group-containing hydroxy compounds such as 1,1-triacryloyloxymethyl) propane and 3-hydroxy (1,1,1-trimethacryloyloxymethyl) propane Can be mentioned.

Examples of ethylenic compounds other than those mentioned above include acrylamides such as ethylenebisacrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate.

The ratio of a monomer is 10-80 weight% normally with respect to the total solid in the colored resin composition in this invention, Preferably it is 20-70 weight%.

[2-3] photopolymerization initiator system

When the colored resin composition of this invention contains the ethylenic compound as the above-mentioned monomer component, it absorbs light directly, or photosensitizes, and produces | generates a decomposition reaction or a hydrogen drawing reaction, and produces | generates a polymerization active radical. It is preferable to mix | blend the photoinitiator type component which has. In addition, in this invention, a "photoinitiator type component" means the mixture in which additives, such as a photoinitiator, an accelerator, and a sensitizing dye, are used together.

As a photoinitiator which comprises a photoinitiator type component, For example, the metalocene compound containing the titanocene compound of each Unexamined-Japanese-Patent No. 59-152396, Unexamined-Japanese-Patent No. 61-151197, , N-aryl-α-amino acids such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in JP-A-10-39503, N-aryl-α-amino acids Salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone compounds, and oxime ester initiators described in JP-A-2000-80068. Specific examples of the polymerization initiator that can be used in the present invention are listed below.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloro Halomethylated triazine derivatives such as rhomethyl) -s-triazine;

2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2'-benzofuryl) vinyl] -1,3 , 4-oxadiazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 Halomethylated oxadiazole derivatives such as furyl-1,3,4-oxadiazole;

2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'- Imidazole derivatives such as methoxyphenyl) -4,5-diphenylimidazole dimer;

Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether;

Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone;

Benzo, such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone Phenone derivatives;

2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropaneone, 1-hydroxy-1-methyl Ethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1- Acetophenone derivatives such as propane, 1,1,1-trichloromethyl- (p-butylphenyl) ketone;

Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-di Thioxanthone derivatives such as isopropyl thioxanthone;

benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;

Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine;

Anthrone derivatives such as benzanthrone;

Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Phen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4, 6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-difluorophene -1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-di- Titanocene derivatives such as fluorophen-1-yl and di-cyclopentadienyl-Ti-2,6-difluoro-3- (phyl-1-yl) -phen-1-yl;

2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-dimethylaminoacetophenone, 4-dimethylaminoflophyophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4- Α-aminoalkylphenone compounds such as diethylaminobenzoyl) coumarin and 4- (diethylamino) chalcone;

1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbox Oxime ester compounds, such as bazol 3-yl]-and 1- (O-acetyl oxime).

As an accelerator which comprises a photoinitiator type component, For example, N, N- dialkylamino benzoic acid alkyl esters, such as N, N- dimethylamino benzoic acid ethyl ester, 2-mercapto benzothiazole, and 2-mercapto benzo, for example. Mercapto compounds having heterocycles such as oxazole and 2-mercaptobenzoimidazole, aliphatic polyfunctional mercapto compounds and the like.

A photoinitiator and an accelerator may be used individually by 1 type, respectively, and may mix and use 2 or more types.

As a specific photoinitiator type component, For example, the dialkyl acetphenone type described in pages 16-26 of "Fine Chemical" (March 1, 1991, vo1.20, No. 4), Hexaaryl biimidazole type, S-trihalomethyl triazine system, Unexamined-Japanese-Patent No. 58-403023, Unexamined-Japanese-Patent No. 45-37377, etc. other than a benzoin, a thioxanthone derivative, etc. The system which combined the titanocene described in Unexamined-Japanese-Patent No. 4-221958, Unexamined-Japanese-Patent No. 4-219756, etc., and the ethylenic saturated double bond containing compound which can add-polymerize which has a xanthene dye, an amino group, or a urethane group, etc. are mentioned. Can be.

The compounding ratio of the said photoinitiator type component is 0.1-30 weight% normally in the total solid of the colored resin composition of this invention, Preferably it is 0.5-20 weight%, More preferably, it is 0.7-10 weight%. If this blending ratio is significantly low, it may cause a decrease in sensitivity to exposure light rays. On the contrary, if it is significantly high, the solubility of the unexposed portion in the developing solution may decrease, causing development failure.

As needed, the photoinitiator type component can mix | blend the sensitizing dye according to the wavelength of an image exposure light source for the purpose of improving a sensitivity. As these increase-sensitizing dyes, the xanthene dyes of Unexamined-Japanese-Patent No. 4-221958, Unexamined-Japanese-Patent No. 4-219756, Unexamined-Japanese-Patent No. 3-239703, and Unexamined-Japanese-Patent No. 5-289335 The coumarin pigment | dye which has a heterocyclic ring of Unexamined-Japanese-Patent No. 3-239703, the 3-ketokumarin compound of Unexamined-Japanese-Patent No. 5-289335, and Unexamined-Japanese-Patent No. 6-19240 are described. Pyromethene dye, In addition, Unexamined-Japanese-Patent No. 47-2528, Unexamined-Japanese-Patent No. 54-155292, Unexamined-Japanese-Patent No. 45-37377, Unexamined-Japanese-Patent No. 48-84183, Unexamined-Japanese-Patent JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A 2-69, JP-A-JP JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP The pigment | dye which has the dialkylaminobenzene skeleton of Unexamined-Japanese-Patent No. 4-288818, etc. are mentioned.

Among these increasing dyes, an amino group-containing increasing dye is preferable, and more preferably, a compound having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzo Benzophenone compounds such as phenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzooxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p -Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-di Ethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) P-dialkylaminophenyl group-containing compounds such as quinoline, (p-dimethylaminophenyl) pyrimidine and (p-diethylaminophenyl) pyrimidine. Most preferable among these is 4,4'- dialkylamino benzophenone. These increasing sense pigment | dyes may also be used individually by 1 type, and may use 2 or more types together.

The compounding ratio of the increasing sense pigment | dye which occupies in the colored resin composition of this invention is 0-20 weight% normally in the total solid of a colored resin composition, Preferably it is 0.2-15 weight%, More preferably, it is 0.5-10 weight%.

[2-4] other solids

Solid content other than the said component can be mix | blended with the colored resin composition of this invention as needed. As these components, surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, an adhesion promoter, a development improving agent, etc. are mentioned.

Among these, various kinds of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. However, nonionic surfactants are used because they are unlikely to adversely affect various properties. It is preferable. As a compounding ratio of surfactant, it is 0.001-10 weight% normally with respect to the total solid in a colored resin composition, Preferably it is 0.005-1 weight%, More preferably, it is 0.01-0.5 weight%, Most preferably, it is 0.03-0.3 weight The range of% is used.

As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. It is preferable that the compounding ratio of a thermal polymerization inhibitor is 0 to 3 weight% with respect to the total solid in a colored resin composition.

As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine and the like are used. It is preferable that the compounding ratio of these plasticizers is 10 weight% or less with respect to the total solid in a colored resin composition.

[2-5] Preparation of colored resin composition

In order to prepare the colored resin composition of this invention, the solvent and binder resin which were illustrated by description of the colored resin composition of this invention mentioned above to the pigment dispersion liquid of this invention mentioned above may be a monomer and a photoinitiator system. A predetermined amount is mixed with a component and other components, and it is set as a uniform dispersion liquid. Moreover, in each process of a dispersion process and mixing, since fine dust may mix, it is preferable to filter the obtained colored resin composition with a filter etc. with a filter.

In the colored resin composition of this invention, it is 99 weight% or less especially 90 weight% or less for the same reason as content of the solvent in the above-mentioned pigment dispersion liquid, and it is 70 weight% or more especially 75 weight% or more. desirable.

In this way, also in the colored resin composition of this invention obtained by mixing and disperse | distributing compounding components, such as the pigment dispersion liquid, a solvent, and binder resin of this invention, the particle size distribution of the pigment contained does not change substantially with the particle size distribution in a pigment dispersion liquid. The particle diameter described above is maintained.

In the case of the colored resin composition of this invention prepared in this way, when the red pixel was formed on the glass substrate using this, the said board | substrate was inserted into two polarizing plates, and when the polarizing plate measured by the color luminance meter is orthogonal, Contrast C calculated by the formula (1) from the light quantity B in parallel with the light quantity A and the x value of the chromaticity of the transmitted light in the C light source measured by the spectrophotometer are high as represented by the formula (2). Contrast red pixels can be formed.

C = B / A (1)

C≥4000x-2000 (2)

If C < 4000x-2000, the contrast becomes low, and since light leakage occurs during black display, the image quality deteriorates.

In the colored resin composition of the present invention, the contrast C and x values are preferably represented by the following (2-1) formulas, and more preferably by the following (2-2) formulas.

C≥4000x-1800 (2-1)

C≥4000x-1400 (2-2)

[3] color filters

Next, the color filter of this invention is demonstrated.

After forming a black matrix on a transparent substrate, a color filter is manufactured by normally forming each pixel image of red, green, and blue (but there is no restriction | limiting in this order). In manufacture of such a color filter, the colored resin composition of this invention is used as a coating liquid for red pixel image formation. Metal formed on the transparent substrate with respect to the black resist, on the resin black matrix forming surface formed on the transparent substrate with respect to the color resist of red, green, or blue, or using a chromium compound or other light shielding metal material. On the black matrix formation surface, each process of application | coating, heat drying, image exposure, image development, and thermosetting is performed, respectively, and the pixel image of each color is formed.

[3-1] Transparent Substrate (Support)

As a transparent substrate of a color filter, if there is transparency and moderate intensity, the material is not specifically limited. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, epoxy resins, Thermosetting resin sheets, such as unsaturated polyester resin and poly (meth) acrylic-type resin, or various glass, etc. are mentioned. Especially, glass and heat resistant resin are preferable from a heat resistant viewpoint.

The transparent substrate and the black matrix forming substrate may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as a silane coupling agent or a urethane resin, and the like, in order to improve surface properties such as adhesion. . The thickness of a transparent substrate is 0.05-10 mm normally, Preferably it becomes the range of 0.1-7 mm. In addition, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

[3-2] black matrix

A black matrix is formed on a transparent substrate using the light shielding metal thin film or the colored resin composition for black matrices. As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide, chromium nitride, nickel and tungsten alloys, etc. may be used, and a plurality of layers of these may be laminated.

These metal light-shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape by positive photoresist, the etching solution which mixed dicerium ammonium nitrate, perchloric acid, and / or nitric acid about chromium is formed. And other materials can be etched using an etchant according to the material, and finally, the positive matrix photoresist can be peeled off with a dedicated release agent to form a black matrix.

In this case, first, a thin film of these metals or metal-metal oxides is formed on a transparent substrate by vapor deposition, sputtering, or the like. Next, after forming the coating film of a colored resin composition on this thin film, a coating film is exposed and developed using the photomask which has a repeating pattern, such as a stripe, a mosaic, and a triangle, and a resist image is formed. Thereafter, the coating film may be etched to form a black matrix.

When using the colored resin composition for black matrices, a black matrix is formed using the colored resin composition containing a black color material. For example, a mixture of red, green, blue, etc. suitably selected from black or black color materials such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or inorganic or organic pigments or dyes. The black matrix can be formed using the colored resin composition containing the black color material by the same method as the method of forming the following red, green, and blue pixel image.

[3-3] pixel formation

[3-3-1] Formation of Coating Film

After apply | coating and drying the coloring resin composition containing the color material (pigment) of one of red, green, and blue on the transparent substrate in which the black matrix was formed, the photomask is superimposed on the formed coating film, and the image is imaged through this photomask. Exposure, development, and thermosetting or photocuring are performed as needed to form a pixel image, and the colored layer of a pixel image is created. A color filter image can be formed by performing this operation with respect to the colored resin composition of three colors of red, green, and blue, respectively.

Coating of the colored resin composition for color filters can be used by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Among them, the die coating method is preferable from a comprehensive point of view, such that the amount of coating liquid used is greatly reduced, and there is no influence of mist or the like to adhere when the spin coating method is used.

If the thickness of the coating film is too thick, the pattern development becomes difficult, and the gap adjustment in the liquid crystal selization step may become difficult. If the thickness of the coating film is too thin, it becomes difficult to increase the pigment concentration and the desired color expression may become impossible. have. It is preferable to make thickness of a coating film into the film thickness after drying normally in the range of 0.2-20 micrometers, More preferably, it is the range of 0.5-10 micrometers, More preferably, it is the range of 0.8-5 micrometers.

[3-3-2] drying of the coating film

It is preferable to dry the coating film formed by apply | coating a coloring resin composition to a transparent substrate by the drying method using a hotplate, an IR oven, and a recovery oven. Usually, after preliminary drying, the two stage drying to reheat and dry is performed. The conditions of predrying can be suitably selected according to the kind of the said solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 80 ° C, preferably 30 seconds to a temperature of 50 to 70 ° C, depending on the type of the solvent component, the performance of the dryer to be used, and the like. It is selected in the range of 3 minutes.

As for the temperature conditions of reheat drying, 50-200 degreeC higher than predrying temperature, especially 70-160 degreeC is preferable, and 70-130 degreeC is especially preferable. Moreover, although drying time is based also on heating temperature, it is preferable to set it as the range of 10 second-10 minutes, especially 15 second-5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the binder resin may decompose and cause thermal polymerization to cause development defects. In addition, the drying of this coating film may be a reduced pressure drying method which performs drying in a pressure reduction chamber, without raising a temperature.

[3-3-3] exposure process

Image exposure superimposes a negative matrix pattern on the coating film of the dried colored resin composition, and irradiates a light source of an ultraviolet-ray or a visible light through this mask pattern, and is performed. Under the present circumstances, you may perform exposure after forming oxygen blocking layers, such as a polyvinyl alcohol layer, on a colored resin composition film in order to prevent the fall of the sensitivity of the colored resin composition film by oxygen as needed.

The light source used for image exposure is not specifically limited, For example, xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, carbon arc, a fluorescent lamp, etc. Lamp light sources, laser light sources, such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, a semiconductor laser, etc. are mentioned. When irradiating and using light of a specific wavelength, an optical filter can also be used.

[3-3-4] Development Process

The image development can be used after the said image exposure using the organic solvent or the aqueous solution containing surfactant and an alkaline compound. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

As an alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate Inorganic alkaline compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- Or organic alkaline compounds such as diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be used individually by 1 type, and may mix and use 2 or more types.

As surfactant, For example, Nonionic surfactant, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, monoglyceride alkyl ester, Anionic surfactants, such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl sulfonate, and sulfosuccinic acid ester salt, amphoteric surfactants, such as alkyl betaine and an amino acid, These can be mentioned 1 type individually May be used, or may be used by mixing two or more kinds.

As an organic solvent, 1 type, or 2 or more types, such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, is mentioned, for example. The organic solvent may be used alone or in combination with an aqueous solution.

There is no restriction | limiting in particular in the conditions of image development processing, Usually, image development temperature is the range of 10-50 degreeC, especially 15-45 degreeC, Especially preferably, it is 20-40 degreeC, The image development method is an immersion developing method, a spray developing method, It is possible by any one of brush developing method, ultrasonic developing method and the like.

[3-3-5] Heat Curing Treatment

The color filter substrate after development is usually subjected to a thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment.

The thermosetting treatment conditions are selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.

Through these series of steps, monochromatic patterned image formation is completed. This process is repeated one by one, patterning (black), red, green, and blue to form a color filter. In addition, the patterning order of three colors of red, green, and blue is not limited to the order mentioned above.

Moreover, the color filter of this invention can be manufactured also by the method of apply | coating the coloring resin composition of this invention to a board | substrate, and forming a pixel image by an etching method other than said manufacturing method. Moreover, (2) using the coloring resin composition of this invention as a coloring ink, forming the pixel image directly on a transparent substrate with a printing machine, (3) using the coloring resin composition of this invention as an electrodeposition liquid, And a method of depositing a colored film on an ITO electrode having a predetermined pattern by immersing the substrate in the electrodeposition liquid. Furthermore, (4) the method which adheres and peels the film which apply | coated the colored resin composition of this invention to a transparent substrate, image exposure, develops, and (5) uses the colored resin composition of this invention as a coloring ink. And the method of forming a pixel image by an inkjet printer, etc. are mentioned. As a manufacturing method of a color filter, the method suitable for this is employ | adopted according to the composition of the colored resin composition for color filters.

[3-4] Formation of Transparent Electrode

Although the color filter of this invention forms a transparent electrode, such as ITO, on an image as it is, and is used as a part of components, such as a color display and a liquid crystal display device, in order to improve surface smoothness and durability, on the image as needed, Top coat layers, such as a polyamide and a polyimide, can also be formed in it.

Moreover, in some uses, such as a planar orientation type drive system (IPS mode), a transparent electrode may not be formed.

[4] liquid crystal displays (panels)

Next, the liquid crystal display device (panel) of this invention is demonstrated.

The liquid crystal display device of the present invention usually forms an alignment film on the color filter of the present invention, spreads a spacer on the alignment film, and then attaches the liquid crystal cell to an opposing substrate to form a liquid crystal cell. It is manufactured by injecting and connecting to the counter electrode.

As an orientation film, resin films, such as a polyimide, are suitable. The gravure printing method and / or the flexographic printing method are employ | adopted for formation of an alignment film normally, and the thickness of an alignment film is set to several 10 nm normally. After the alignment film is cured by heat firing, the alignment film is subjected to surface treatment by irradiation with ultraviolet rays or a rubbing cloth, and processed into a surface state in which the inclination of the liquid crystal can be adjusted.

As for a spacer, the thing of the magnitude | size according to the gap (gap) with an opposing board | substrate is used, and it is suitable that it is 2-8 micrometers normally. On the color filter substrate, the photospacer PS of a transparent resin film can be formed by the photolithographic method, and this can be utilized instead of a spacer.

As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.

Although the adhesion gap with an opposing board | substrate changes with the use of a liquid crystal display device, it is normally selected in the range of 2-8 micrometers. After sticking with the opposing substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell in which the periphery is sealed is cut into panel units, and the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking into the chamber. Although the pressure reduction degree in a liquid crystal cell is 1 * 10 <^-2> -1 * 10 <^-7> Pa normally, Preferably it is 1 * 10 <^-3> -1 * 10 <^-6> Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and a heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The heating and holding at the time of reduced pressure usually falls within a range of 10 to 60 minutes, and is then immersed in the liquid crystal. The liquid crystal cell which injected the liquid crystal hardens and seals a liquid crystal injection port with UV curable resin, and a liquid crystal display device (panel) is completed.

 There is no restriction | limiting in particular in the kind of liquid crystal, Conventionally known liquid crystals, such as an aromatic type, an aliphatic type, and a polycyclic compound, are used, and any of lyotropic liquid crystal and a thermotropic liquid crystal may be used. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any may be used.

Although an Example and a comparative example are given to the following and this invention is demonstrated to it further more concretely, this invention is not limited at all by the following example, It can implement by changing suitably in the range which does not exceed the summary. In addition, "part" in a composition shows the "weight part" below.

Example 1

<Preparation of Pigment Dispersion>

The pigment dispersion liquid of this invention was produced with the following compounding composition.

[Pigment dispersion formulation]

Anthraquinone Red Pigment (P.R.177) (DIC manufactured "ATY-TR"): 80 parts

Nickel Azo Yellow Pigment (P.Y.150) ("E4GN" manufactured by Bayer Corporation): 20 parts

Amine-based dispersant ("Disperbyk" manufactured by BIC Chem Corporation): 45 parts

Solvent (propylene glycol monomethyl ether acetate): 580 parts

After mixing the above materials to make a mill base, dispersion was carried out using "TORUSMILL" manufactured by Getzmann, which impinges and disperses beads in a container. The beads used at the time of dispersing were zirconia beads having an average particle diameter of 100 µm, and were dispersed at a circumferential speed of 12 m / min and a dispersion time of 4 minutes with a filling volume of 65 vol% and a millbase of 100 cc based on a vessel volume of 0.33 L of the disperser. Treatment was carried out.

Measurement of Particle Size Distribution of Pigment Dispersion

The obtained pigment dispersion liquid was diluted 5000 times with propylene glycol monomethyl ether acetate, the particle diameter was measured by dynamic light-scattering DLS ("DLS7000" by Otsuka Electronics Co., Ltd.), and the particle size range and half value width are shown in Table 1.

<Preparation of colored resin composition (color resist)>

Each component was mixed with the obtained pigment dispersion liquid by the mixture shown below, and it filtered with the 1 micrometer filter and produced the color resist.

[Color resist formulation]

Pigment Dispersion: 10.6 parts

Solvent (propylene glycol monomethyl ether acetate): 80.0 parts

Binder resin (benzyl methacrylate / methacrylic acid copolymer): 4.7 parts

Monomer (trimethylolpropanetriacrylate): 2.3 parts

Photoinitiator type component 1 (2-mercaptobenzothiazole): 0.8 part

Photoinitiator type component 2 (methyl p-dimethylaminobenzoate): 0.8 part

Photopolymerization initiator-based component 3 (Mihilerketone): 0.8 parts

<Formation of Red Pixels>

This color resist was spin-coated on the glass substrate so that the film thickness after drying might be set to 2 micrometers, and it dried at 80 degreeC for 10 minutes. Thereafter, after the UV irradiation cured the resin, heat crosslinking was performed at 230 ° C. for 30 minutes to form a red pixel.

<Measurement of chromaticity and contrast>

About the glass substrate with a red pixel obtained above, the chromaticity of the transmitted light in the C light source was measured using the spectrophotometer ("U4100" by Hitachi Ltd.).

Moreover, this board | substrate is stuck between two polarizing plates without gaps, and is parallel with the light quantity A (cd / cm <2>) when a polarizing plate is orthogonal using a color luminance meter ("BM-5A" by Topecon Corporation). The contrast was computed by the following formula (1) from the ratio of the light quantity B (cd / cm <2>) at the time. These results are shown in Table 1.

C = B / A (1)

Moreover, "4000x-2000" was computed from the measured x value of chromaticity, and it evaluated whether the following formula (2) is satisfied, and these results were shown in Table 1.

C≥4000x-2000 (2)

Example 2

Except for using "E5GN" manufactured by Bayer Corporation as "Chromophthalored A3B" manufactured by Chiba Specialty Chemicals Co., Ltd. as a anthraquinone-based red pigment (PR177) and nickel azo-based yellow pigment (PY150). The pigment dispersion liquid and the colored resin composition were produced, the same evaluation was performed, and the result was shown in Table 1.

Example 3

Except having made the particle size of the beads used at the time of the dispersion process of a pigment dispersion liquid into 500 micrometers, the pigment dispersion liquid and colored resin composition were produced like Example 1, the same evaluation was performed, and the result was shown in Table 1.

Comparative Example 1

A pigment dispersion and a colored resin composition were prepared in the same manner as in Example 1, except that "B-CF" manufactured by Chiba Chemical Co., Ltd., a diketopyrrolopyrrole red pigment (PR254), was used as the red pigment, and the same evaluation was performed. The results are shown in Table 1.

In Table 1, it can be seen that by mixing P.R.177 and P.Y.150 and using a pigment dispersion having a particle size in the range of the present invention, a high contrast red pixel satisfying the above formula (2) can be formed.

While the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

In addition, the present application is based on a Japanese patent application filed on October 22, 2003 (Japanese Patent Application 2003-362113), and a Japanese patent application filed on January 20, 2004 (Japanese Patent Application 2004-012061). The whole is used by quotation.

Claims (9)

In a pigment dispersion containing a pigment, a solvent and a dispersant, The pigment contains an anthraquinone-based red pigment and an azo-based yellow pigment, and other pigments which may be combined with the pigment components in an amount of 20% by weight or less relative to the anthraquinone-based red pigment, and the particle size of the pigment Pigment dispersion liquid in the range of this 30-500 nm. The method of claim 1, The half width of the particle size distribution of the said pigment is 250 nm or less, The pigment dispersion liquid characterized by the above-mentioned. The method according to claim 1 or 2, The anthraquinone-based red pigment is C.I. Pigment Red 177, wherein the azo yellow pigment is C.I. Pigment Yellow 150, characterized in that it comprises a pigment dispersion. The method according to claim 1 or 2, When the red pixel was formed on the glass substrate using the coloring resin composition containing the said pigment dispersion liquid, the polarizing plate when the said board | substrate was sandwiched between two polarizing plates, and it measured by the color luminance meter, and the light quantity A of orthogonality, The pigment dispersion liquid whose contrast C calculated by Formula (1) from the light quantity B in parallel, and the chromaticity of the transmitted light in C light source as measured by the spectrophotometer are represented by Formula (2): C = B / A (1) C≥4000x-2000 (2). A method for producing the pigment dispersion according to claim 1 or 2, A manufacturing method comprising dispersing a mixture of a pigment, a solvent and a dispersant using beads having an average particle diameter of 30 to 500 µm. The colored resin composition containing the pigment dispersion liquid of Claim 1. The colored resin composition of Claim 6 which further contains a binder resin, a monomer, and a photoinitiator. The color filter which has a pixel formed using the colored resin composition of Claim 6 or 7. A liquid crystal display device comprising the color filter according to claim 8.