JPH10152627A - Photosensitive colored resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored resin composition which can form a colored layer having a food surface smoothness and excellent heat resistance. SOLUTION: This composition essentially consists of a colorant being a grafted coloring pigment obtained by reacting a coloring pigment with a compound having at least one type of reactive group such as aziridine group, N- hydroxyalkylamido, epoxy and thioepoxy in the molecule and a photosensitive resin component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive colored resin composition, and more particularly to a photosensitive colored resin composition capable of forming a colored layer requiring good surface smoothness such as a color filter. .

[0002]

2. Description of the Related Art For example, in a liquid crystal display (LCD), a color filter is used in both an active matrix system and a simple matrix system in order to meet the recent demand for colorization. For example, in an active matrix type liquid crystal display using a thin film transistor (TFT), three primary colors of red (R), green (G), and blue (B) are used as color filters, and each pixel of R, G, and B is used. The liquid crystal operates as a shutter by turning on and off the electrodes corresponding to the above, and light is transmitted through each of the R, G, and B pixels to perform color display. Color mixing is visually performed on the retina by the principle of additive color mixing in which liquid crystal shutters corresponding to pixels of two or more colors are opened to mix colors and make the colors look different.

[0003] The above-mentioned color filter manufacturing method includes a dyeing method in which a dyed base material is applied and exposed and developed through a photomask to dye a formed pattern, and a color pigment is dispersed in a photosensitive resin composition in advance. A pigment dispersion method of exposing and developing through a photomask, a printing method of printing each color with a printing ink, and applying a voltage to a transparent electrode of a predetermined pattern formed on a substrate to form a colored electrodeposition bath. An electrodeposition method in which a colored layer is formed by performing electrodeposition in the inside is exemplified.

[0004]

Among the above-mentioned various methods for producing a color filter, the pigment dispersion method involves the steps of exposing the photosensitive resin composition to light when the proportion (P / V ratio) of the coloring pigment contained in the photosensitive resin composition is increased. -There was a problem that the surface smoothness of the colored layer formed by development was reduced, and display unevenness in the liquid crystal display and poor alignment of the liquid crystal layer occurred.

[0005] Further, depending on the coloring pigment used, sublimation may occur in a vacuum or high-temperature environment in the transparent electrode forming step and the alignment film forming step after the formation of the colored layer. For this reason, it is necessary to lower the set temperature in the step after the formation of the colored layer to such an extent that the sublimation of the colored pigment does not occur. However, if there is such a limitation, for example, in a transparent electrode forming step, a high-temperature process higher than a predetermined temperature required for forming a transparent electrode having good electric characteristics may not be set, and particularly a large liquid crystal may be set. This is a major problem in displays.

The present invention has been made in view of the above circumstances, and has a good surface smoothness and a photosensitive colored resin composition capable of forming a colored layer having excellent heat resistance. The purpose is to provide.

[0007]

In order to achieve the above object, the present invention comprises at least a colorant and a photosensitive resin component, wherein the colorant comprises an aziridine group, an oxazoline group, an N-hydroxyalkyl group. The structure was such that it was a graft coloring pigment obtained by reacting a compound having at least one reactive group of an amide group, an epoxy group and a thioepoxy group in the molecule with a coloring pigment.

In the present invention, the graft coloring pigment contained as a coloring material contains at least one reactive group such as an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group and a thioepoxy group. Are coated on the surface of the color pigment as a graft chain, and the graft chain improves the surface characteristics of the color pigment and makes the molecular weight of the graft color pigment larger than the molecular weight of the color pigment.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will be described below.

[0010] The photosensitive colored resin composition of the present invention contains at least a coloring material and a photosensitive resin component.

The coloring material constituting the photosensitive colored resin composition of the present invention has at least one reactive group of aziridine group, oxazoline group, N-hydroxyalkylamide group, epoxy group and thioepoxy group in the molecule. It is a graft coloring pigment obtained by reacting a compound with a coloring pigment.

As the coloring pigment used in the above-mentioned graft coloring pigment, known red pigments, green pigments, blue pigments,
Purple pigments, yellow pigments, black pigments and the like can be used. As a specific example of the color pigment, the red pigment is CIPigme
nt Red 9, 97, 122, 123, 149, 168, 1
77, 180, 192, 215, 216, 217, 22
0, 223, 224, 226, 227, green pigment is C.
I. Pigment Green 7, 36, orange pigment is CIPigmen
t Orange 36, 43, 51, 55, 59, 61, blue pigment is CI Pigment Blue 15, 15: 6, 22, 6
0, 64, purple pigment is CIPigment Violet 19,2
3, 29, 30, 37, 40, 50, yellow pigment is CIP
igment Yellow 20, 24, 86, 93, 109, 11
0, 117, 125, 137, 138, 148, 15
3, 154, 166, 168, and black pigments include furnace black, channel black, acetylene black, and lamp black. The above-mentioned color pigments include, for example, color pigments that cause sublimation in a vacuum state at 170 ° C., such as an anthraquinone red pigment of a red pigment. Such a color pigment preferably has an average particle size in the range of 0.1 to 0.5 μm.

As the compound for producing the graft color pigment by reacting with the above color pigment, a hydrophilic and / or lipophilic compound is appropriately selected and used according to the characteristics of the photosensitive resin component described later. Can be. Examples of the hydrophilic compound include vinyl polymers and polyethers containing acrylic acid as a main component and those containing at least one type of reactive group, and examples of the hydrophilic compound include styrene. Examples of the component include vinyl polymers and polyesters which contain at least one type of reactive group described above. Such a compound is obtained by polymerizing a polymerizable monomer having the above reactive group in the molecule, or a method of polymerizing with another polymerizable monomer, or having the above reactive group in the molecule. The compound can be produced by, for example, a method of reacting the compound with a polymer having a group capable of reacting with the compound and introducing the reactive group into the polymer, and the number average molecular weight is in the range of 300 to 2,000. Is preferred.

Specific examples of such a compound include a compound having an aziridine group; a compound having an oxazoline group such as a styrene-isopropenyl oxazoline copolymer; a compound having an N-hydroxyalkylamide group; Compounds having an epoxy group as described in (1); compounds having a thioepoxy group; and compounds having an isocyanate group such as styrene-isopropenyl isocyanate copolymer.

[0015]

Embedded image The reaction for obtaining the graft color pigment from the color pigment and the compound as described above is performed at 50 to 250 ° C., preferably at 10 to 250 ° C.
It is preferable to carry out the heating and mixing of the color pigment and the compound in a temperature range of 0 to 200 ° C. In this case, the mixing ratio of the coloring pigment and the compound is preferably in a range such that the compound is 5 to 200 parts by weight based on 100 parts by weight of the coloring pigment.
If the ratio of the compound to 100 parts by weight of the coloring pigment is less than 5 parts by weight, the modification of the coloring pigment is insufficient and the effect of the present invention is not exhibited. On the other hand, when the proportion of the compound exceeds 200 parts by weight, the viscosity of the photosensitive coloring resin composition becomes too high even when the content of the coloring material in the photosensitive coloring resin composition is in a range as described later, and the coating suitability is poor. It is not preferable because it decreases.

As described above, the graft coloring pigment obtained by the reaction between the coloring pigment and the compound has at least one reactive group such as an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group and a thioepoxy group possessed by the compound. It reacts with the surface functional group of the color pigment, and this compound coats the surface of the color pigment as a graft chain. The graft chains improve the surface properties of the color pigment and make the molecular weight of the graft color pigment larger than the molecular weight of the color pigment before the reaction.

The content of the coloring material comprising such a graft coloring pigment in the photosensitive coloring resin composition can be in the range of 1 to 60% by weight, preferably 10 to 50% by weight. If the content of the coloring material is less than 1% by weight, the film thickness for obtaining necessary optical properties becomes large and fine processing is difficult. The strength deteriorates significantly, which is not preferable.

The photosensitive resin component constituting the photosensitive colored resin composition of the present invention contains a binder polymer, a monomer and an initiator.

Examples of the alkali developing type binder polymer include acrylic acid, methacrylic acid, a dimer of acrylic acid (for example, M-5600 manufactured by Toa Gosei Chemical Co., Ltd.), itaconic acid, crotonic acid, maleic acid, and fumaric acid. , Vinyl acetic acid, one or more of these acid anhydrides, and methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate,
n-butyl methacrylate, sec-butyl acrylate,
sec-butyl methacrylate, isobutyl acrylate,
Isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n- Copolymers comprising one or more of octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, styrene, α-methylstyrene, and 1-vinyl-2-pyrrolidone are exemplified.

Examples of the copolymer include a polymer obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the above copolymer, but the present invention is not limited thereto.

Further, as the non-alkali developing type polymer, polyvinyl alcohol, polyvinyl butyral,
Acrylic acid ester polymers, methacrylic acid ester polymers, polystyrene, α-methylstyrene polymers, 1-vinyl-2-pyrrolidone polymers, and copolymers thereof can be mentioned.

As the reactive monomer constituting the photosensitive resin component, a compound having at least one polymerizable carbon-carbon unsaturated bond can be used. Specifically, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate, isobonyl acrylate,
Isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1, 5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3
-Propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate,
Tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyl trimethylolpropane triacrylate , Butylene glycol diacrylate, 1,2,4-butanetriol triacrylate, 2,2,4-trimethyl-1,
3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and those obtained by changing the above acrylate to methacrylate, γ-methacryloxypropyltrimethoxysilane,
1-vinyl-2-pyrrolidone and the like. In the present invention, the above-mentioned reactive monomers can be used as one kind or a mixture of two or more kinds, or as a mixture with other compounds.

Examples of the photopolymerization initiator constituting the photosensitive resin component include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone,
4,4-bis (diethylamine) benzophenone, α-
Amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone,
Dibenzyl ketone, fluorenone, 2,2-diethoxyacetophonone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methyl Thioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethylacetal, benzoin methyl ether, benzoin butyl ether, anthraquinone,
2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibensuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-
Bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2-
(O-methoxycarbonyl) oxime, 1-phenyl-
Propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2-
(O-ethoxycarbonyl) oxime, 1-phenyl-
3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-1-propane, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, n-phenylthioacridone,
4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosine, methylene blue Examples include a combination of reducing agents such as ascorbic acid and triethanolamine. In the present invention, one or more of these photopolymerization initiators can be used.

The content of such a photosensitive resin component in the photosensitive colored resin composition can be in the range of 10 to 50% by weight, preferably 20 to 40% by weight.

The photosensitive colored resin composition of the present invention is prepared by mixing the above-mentioned coloring material and photosensitive resin component in a solvent and kneading them by a roll mill or the like to form a paste-like coating solution, or by a ball mill or the like. It can be kneaded to obtain a slurry coating solution. As the solvent used in the photosensitive colored resin composition, for example, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, xylene, anons such as cyclohexanone, methylene chloride, 3-methoxybutyl acetate, ethylene glycol monoalkyl ethers, Examples include ethylene glycol dialkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ether acetates, and terpenes such as α- or β-terpineol.

The photosensitive colored resin composition of the present invention may further contain, as additives, a sensitizer, a polymerization terminator, a chain transfer agent,
A leveling agent, a dispersant, a plasticizer, a surfactant, an antifoaming agent and the like are used as needed. Among them, sensitizers include xanthone, dimethylxanthone, thioxanthone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzophenone, anthracene, 2,2-diethoxyacetophenone, benzyl dimethyl ketal, diphenyl disulfide, anthraquinone, and 1-chlorine. Anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, methylanthraquinone, 1-chloromethylnaphthalene, N, N'-tetraethyl-4,4'-diaminobenzophenone, 1,1
-Dichloroacetophenone and the like.

[0027]

Next, the present invention will be described in more detail with reference to examples. (1) Preparation of Compound Compound A having an isocyanate group as a reactive group was prepared as follows.

Preparation of Compound A A flask equipped with a stirrer, an inert gas inlet tube, a reflux condenser and a thermometer was charged with 400 parts by weight of toluene, and a polymerizable polymer comprising 196 parts by weight of styrene and 4 parts by weight of isopropenyl isocyanate was used. A mixture in which 10 parts by weight of benzoyl peroxide was dissolved in the monomer was charged, and the mixture was stirred and refluxed at 80 ° C. for 4 hours. According to GPC measurement, Mn was 5000. (2) Preparation of Colorant (Graft Color Pigment) 50 parts by weight of the following color pigment was mixed with 100 parts by weight of the compound A, and the mixture was stirred at 150 ° C. (1
(200 rpm), and the mixture was cooled and pulverized to prepare a coloring material of a graft red pigment, a graft green pigment, a graft blue pigment, and a graft black pigment. Red pigment: Chromophthal Red BR manufactured by Ciba Geigy
N Green pigment: Lionol Green 2 manufactured by Toyo Ink Co., Ltd.
Y301 Blue pigment: Chromophthal Blue A3 manufactured by Ciba Geigy
R Black pigment: MA-100 manufactured by Mitsubishi Chemical Corporation (3) Preparation of photosensitive colored resin composition First, a photosensitive resin having the following composition was prepared.

(Composition of photosensitive resin) o-cresol novolak epoxy acrylate: 60 parts by weight (50% of hydroxyl groups reacted with phthalic anhydride) Pentaerythritol tetraacrylate: 30 parts by weight Irgacure (Ciba Geigy) 10 parts by weight Ethyl cellosolve 100 parts by weight Next, using this photosensitive resin and the coloring materials prepared in the above (2), four kinds of photosensitive colored resin compositions (red, Green, blue and black).

(Composition of photosensitive colored resin composition) Colorant: 50 parts by weight Photosensitive resin: 200 parts by weight Ethyl cellosolve: 150 parts by weight (4) Production of color filter The colored resin composition was coated on a glass substrate (Corning Co., Ltd. 7059) by spin coating.
(Thickness: 1.1 mm)) and dried to form a coating film (1.0 μm thickness). The coating film is exposed and developed through a black matrix mask, and further washed and dried to form a black film. A matrix pattern was formed.

Next, the above-mentioned red photosensitive coloring resin composition is applied on the glass substrate by spin coating and dried to form a coating film (1.0 μm in thickness). It was exposed and developed through a mask for cleaning, and further washed and dried to form a red colored pattern.

In the same manner, a green colored pattern is formed using the green photosensitive colored resin composition,
A blue colored pattern was formed using the above-described blue colored photosensitive resin composition. (5) Evaluation of Color Filter The surface roughness of the black matrix and each colored pattern of the color filter manufactured in (4) was measured by the following measurement method, and the results are shown in Table 1 below.

Measurement of Surface Roughness The surface roughness was measured using an Alpha-Step 300 (a stylus-type film thickness meter) manufactured by Tencor Corporation under the conditions of a needle diameter of 5 μm and a needle pressure of 15 mg.

Further, a transparent electrode (thickness 2000 mm) made of indium tin oxide (ITO) is formed on the color filter manufactured in (4) under the following conditions, and a liquid crystal display is manufactured using this color filter, and display is performed. The quality was evaluated and the results are shown in Table 1 below.

Transparent electrode forming conditions and equipment: Batch type vacuum ITO film forming apparatus (manufactured by SYNCHRON Co., Ltd.) Substrate temperature: 200 ° C. Degree of vacuum: 5 × 10 ⁻⁶ Torr On the other hand, as a comparative example, In place of the coloring material (graft coloring pigment) prepared in 2), four types of photosensitive materials were used in the same manner as in the above Examples except that the coloring pigment of each color used in this coloring material was used in an untreated state. A colored resin composition (red, green, blue and black) was prepared. Using the photosensitive colored resin composition, a color filter was manufactured in the same manner as in the above example, and the surface roughness of the black matrix of the color filter and each colored pattern was measured in the same manner. Indicated. Further, a transparent electrode was formed on this color filter in the same manner as in Example 1. Thereafter, a liquid crystal display was manufactured and the display quality was evaluated. The results are shown in Table 1 below.

[0036]

[Table 1] As shown in Table 1, the photosensitive coloring resin compositions of the examples have a relatively high coloring material content (P / V ratio = 0.
In spite of 5), it was confirmed that the surface roughness of the black matrix and each colored pattern in the color filter was small, and that the color filter had good surface smoothness. Further, no sublimation phenomenon of the coloring material was observed at the time of forming the transparent electrode, and the display quality in the liquid crystal display was good without display unevenness.

On the other hand, in the photosensitive colored resin composition of the comparative example, the surface roughness of the black matrix and each colored pattern is large, especially the surface roughness of the red colored pattern is larger than that of the examples. Regarding the display quality of the liquid crystal display, the resistance value of the transparent electrode was large due to the sublimation of the red pigment during the formation of the transparent electrode, and the display was uneven.

[0038]

As described above in detail, according to the present invention, at least one reactive group of an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group and a thioepoxy group is added to the coloring pigment in the molecule. As a coloring material, a graft coloring pigment obtained by reacting a compound having a coloring agent, and a photosensitive coloring resin composition containing at least this coloring material and a photosensitive resin component, the graft coloring pigment contained as a coloring material is The above compound covers the surface of the coloring pigment as a graft chain, and since the surface characteristics of the coloring pigment are modified by the graft chain, a colored layer formed using the photosensitive coloring resin composition of the present invention. Has good surface smoothness, and the above graft chains make the molecular weight of the graft coloring pigment larger than the molecular weight of the coloring pigment. Ri, since the sublimation temperature increases in the sublimation of the colored pigment, it is possible to form a heat resistance superior color layer.

Claims (1)

[Claims] 1. A colorant comprising at least a colorant and a photosensitive resin component, wherein the colorant comprises at least one reactive group of an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group and a thioepoxy group. A photosensitive coloring resin composition, which is a graft coloring pigment obtained by reacting a compound contained in a molecule with a coloring pigment.