JP2012226130A - Photosensitive composition and color filter using the same, liquid crystal display and organic el display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter which uses a photosensitive composition containing a dye, has high transmittance and has excellent light resistance, and to provide a liquid crystal display and an organic EL display using the color filter.SOLUTION: In the photosensitive composition which contains at least (A) a transparent resin, (B) a photopolymerizable monomer, (C) a dye, (D) a photoinitiator and (C) a solvent, (A) the transparent resin contains 30-80 wt.% of benzyl methacrylate as a copolymerization component, and (C) the dye is 3-10 wt.% in the total solid content.

Description

  The present invention relates to a photosensitive composition used for a color filter used in a color liquid crystal display, an organic EL display, and the like, a color filter using the same, and a liquid crystal display and an organic EL display formed using the color filter. It is about.

  In recent years, with the diversification of information equipment and the like, the need for flat display displays that consume less power and occupy less space than conventional CRTs has increased, and liquid crystal displays are one of such flat display displays. In addition, color displays using organic electroluminescence (organic EL) elements have attracted attention.

  At present, reduction of power consumption is demanded for color displays as an environmental consideration. A simple structure of a liquid crystal display is shown in FIG. In the liquid crystal display, a liquid crystal (2) is sealed between substrates of a color filter (1) formed on one substrate and a TFT array (3) formed on a counter substrate, and a polarizing plate (11) is disposed outside the two substrates. ) And a backlight (4). In the case of a liquid crystal display, a display is made by applying an electric charge to the liquid crystal and making the light from the backlight bright and dark using the birefringence of the liquid crystal. In this case, 50% of the backlight light is blocked by the polarizing plate, and 70% of the light is blocked by the color filter. Therefore, a color filter with higher transmittance is required as a color filter.

  A simplified diagram of the organic EL display is shown in FIG. In the top emission structure of the organic EL display, the color filter (1) is formed on one substrate, the TFT (9) and the organic EL element (12) are formed on the opposite substrate, as in the liquid crystal display. An adhesive layer is provided between the substrates. Important issues for organic EL displays include extending the life of elements and reducing power consumption. Therefore, as an element, improvement of luminous efficiency has been actively researched. Until now, a light emitting element using fluorescence emission has been a tributary, but it is known that the generation probability of a singlet necessary for emitting the fluorescence is statistically 25%. Therefore, theoretically, only 1/4 of the injected electrons and holes can be extracted as light. In contrast, organic EL elements using phosphorescence from excited triplets have been proposed (see Non-Patent Document 1, etc.), and in recent years, materials that exhibit phosphorescence at room temperature have been actively studied.

  As described above, in the organic EL device, improvement of light emission efficiency, that is, improvement of light emission efficiency, extension of the lifetime of the device, and reduction of power consumption are addressed as important issues. Accordingly, sufficient performance is not obtained in terms of color reproducibility, and a color filter is required for this purpose, and it plays a role of correcting the color from the light emitting element. However, even if the color reproduction region can be expanded by the color filter, if the color filter blocks a large amount of light from the organic EL element, the effect of improving the light emission efficiency of the organic EL element is reduced. Therefore, a color filter with higher transmittance is required as a color filter.

  In a conventional color filter, a pigment having excellent light resistance and heat resistance has been used as a colorant for the photosensitive composition. However, the pigment is excellent in light resistance and heat resistance, but on the other hand, it has a large particle size, which causes light scattering and has a limit in transmittance.

  Therefore, in recent years, in order to obtain a color filter with higher transmittance, a color filter using a dye as a colorant has been developed. However, the dye has a problem that light transmittance is inferior although it has high transmittance.

M.M. A. Baldo et al., Nature, 395, 151 (1998).

  It is an object of the present invention to provide a color filter having high transmittance and excellent light resistance using a photosensitive composition containing a dye, and a liquid crystal and an organic EL display using the color filter. To do.

  The present invention is for solving the above-mentioned problems. The invention according to claim 1 of the present invention includes (A) a transparent resin, (B) a photopolymerizable monomer (C) dye, and (D) a photoinitiator. (E) In the photosensitive composition containing a solvent, the transparent resin (A) contains 30 to 80% by weight of benzyl methacrylate as a copolymerization component, and (C) the dye is 3% in the total solid content. It is a photosensitive composition characterized by being 10 to 10% by weight.

  The invention according to claim 2 of the present invention is the photosensitive composition characterized in that (B) the photopolymerizable monomer is 20% to 50% by weight in the total solid content.

  The invention according to claim 3 of the present invention is the photosensitive composition characterized in that the (C) dye of the present invention is a triarylmethane dye.

  An invention according to claim 4 of the present invention is a color filter comprising the dye-containing photosensitive composition according to any one of claims 1 to 3.

  The invention according to claim 5 of the present invention is a liquid crystal display using the color filter according to claim 4.

  The invention according to claim 6 of the present invention is an organic EL display using the color filter according to claim 4.

  According to the present invention, a color filter having high transmittance and excellent light resistance can be obtained by using a dye, and the color display efficiency is not reduced by using such a color filter. It is possible to provide a color display having a low power consumption, a long life, and a bright and clear color image.

It is a figure for demonstrating the simple structure of a liquid crystal display. It is a figure for demonstrating the simple structure of an organic electroluminescent display.

  Hereinafter, the present invention will be summarized first, and then the details of the material surface, the general production method of the photosensitive coloring composition, the production method of the color filter substrate, and the examples will be described in detail.

  The photosensitive composition according to the present invention contains (A) a transparent resin, (B) a photopolymerizable monomer (C) dye, (D) a photoinitiator, and (E) a solvent as essential components. . Moreover, you may contain additives, such as surfactant and a photosensitizer.

  In the photosensitive composition, (A) the transparent resin contains 30 to 80% by weight of benzyl methacrylate as a copolymerizable component, and (C) the dye is 3 to 10% by weight in the total solid content. It is characterized by.

  When the amount of benzyl methacrylate contained as a copolymerizable component of (A) the transparent resin in the photosensitive composition is less than 30% by weight, the light resistance improving effect is not sufficient. On the other hand, if the amount of benzyl methacrylate exceeds 80% by weight, the proportion of other copolymerization components decreases, resulting in poor pattern linearity due to a decrease in alkali developability during the preparation of the color filter, and resistance to the color filter itself. Problems arise in chemical properties.

  Moreover, since the film thickness as a color filter becomes thick when the ratio in the total solid content of the (C) dye in the photosensitive composition is less than 3% by weight, coating unevenness and film thickness Inferior in uniformity. On the other hand, if the proportion of the dye exceeds 10% by weight, the light resistance improving effect cannot be obtained sufficiently.

(Transparent resin)
The transparent resin used in the photosensitive composition of the present invention is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a non-photosensitive resin such as a thermoplastic resin and a thermosetting resin, and a photosensitive resin. If necessary, the transparent resin can be used alone or in admixture of two or more monomers or oligomers that are precursors thereof that are cured by irradiation with radiation to produce a transparent resin.

  The non-photosensitive resin is a resin having no ethylenically unsaturated double bond, and examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, and polychlorinated resin. Vinyl, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polybutadiene, A polyimide resin etc. are mentioned. Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a phenol resin, a melamine resin, and a urea resin. However, these resins do not exhibit alkali solubility.

  At present, as the developer, an alkaline developer having a small influence on the environment is often used. For this reason, it is desirable to use an alkali-soluble resin as the resin binder. The alkali-soluble non-photosensitive transparent resin is a transparent resin having a property of dissolving in an alkaline aqueous solution and having no ethylenically unsaturated double bond. For example, an acidic functional group such as a carboxyl group or a sulfone group A non-photosensitive transparent resin having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 10,000 is mentioned. Of the acidic functional groups, a carboxyl group is preferred. In order to stabilize dispersion and improve the development performance of the color filter coloring composition, the acid value of the non-photosensitive transparent resin is preferably higher than the acid value of the photosensitive transparent resin. The patterning property of the transparent colored coating film made of the composition is improved, and a transparent colored pixel having a stable shape is obtained.

Specific examples of such alkali-soluble non-photosensitive resins include acrylic resins having acidic functional groups, α-olefin- (anhydrous) maleic acid copolymers, styrene- (anhydrous) maleic acid copolymers, and styrene. -Styrenesulfonic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene- (anhydrous) maleic acid copolymer and the like. Among them, at least one selected from an acrylic resin having an acidic functional group, an α-olefin- (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene-styrene sulfonic acid copolymer. Resins are preferably used. Among these, acrylic resins having acidic functional groups are preferably used because of their high heat resistance and transparency. A resin having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000 can be preferably used.

  As the photosensitive resin, a linear polymer having a reactive functional group is allowed to react with a (meth) acrylic compound having a substituent capable of reacting with the reactive functional group, cinnamic acid, or the like to react with ethylenically unsaturated dicarboxylic acid. Examples thereof include resins in which a double bond is introduced into the linear polymer. In addition, a linear polymer having a substituent capable of reacting with the reactive functional group is reacted with a (meth) acrylic compound having a reactive functional group, cinnamic acid, or the like, to thereby form an ethylenically unsaturated double bond. Resin introduced into the polymer. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group, and examples of the substituent capable of reacting with the reactive functional group include an isocyanate group, an aldehyde group, and an epoxy group.

  In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Those half-esterified with can be used as the photosensitive resin.

The amount of ethylenically unsaturated double bonds introduced through a hydroxyl group or the like into the photosensitive transparent resin, which indicates the ease of photocuring, is indicated by the “double bond equivalent” of the resulting photosensitive transparent resin. .
The double bond equivalent of the photosensitive transparent resin in the present invention is preferably 200 to 1200, and more preferably 300 to 900. When the double bond equivalent of the photosensitive transparent resin is less than 200, the ratio of the ethylenically unsaturated monomer having a reactive substituent for introducing an ethylenically unsaturated double bond is increased, and various characteristics are maintained. A sufficient amount of other ethylenically unsaturated monomers cannot be copolymerized. When it exceeds 1200, sufficient sensitivity cannot be obtained because the number of ethylenically unsaturated double bonds is small. Moreover, the weight average molecular weight (Mw) of photosensitive transparent resin becomes like this. Preferably it is 2000-200000, More preferably, it is 5000-50000.

  In the present invention, the photosensitive resin or the non-photosensitive resin contains 30 to 80% by weight of benzyl methacrylate as a polymerization component, and the dye is 3 to 10% by weight in the total solid content. The present invention provides a color filter having excellent characteristics.

  The benzene ring possessed by benzyl methacrylate has a steric effect in addition to the effect of π electrons, and can form a better adsorption / orientation surface for coloring materials such as dyes. By setting it within this range, it is possible to provide a color filter having excellent light resistance, good linearity of the color filter pattern, and excellent chemical resistance.

(Photopolymerizable monomer)
The said (B) photopolymerizable monomer which concerns on this invention superposes | polymerizes by irradiation of exposure light, and changes the colored photosensitive layer produced using the photosensitive composition to insoluble in a developing solution. Generally, it is a monomer whose polymerization is induced by radicals.

As such a photopolymerizable monomer, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate can be used.

  For example, as the (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide Modified penta (meth) acrylate, dipentaerythritol caprocalactone modified penta (meth) acrylate, glycerol acrylate Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloyl propyl methacrylate, epoxy group-containing compound and the carboxy (meth) reaction product of acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

  In the present invention, the photopolymerizable monomer is preferably 20% to 50% by weight in the total solid content. This is because if it is less than 20% by weight, the sensitivity in the exposure process is lowered, which is not preferable. On the other hand, when the amount is more than 50% by weight, the vicinity of the surface of the coating film is remarkably cured as compared with the deep part of the coating film, so that an overhang in which the pattern shape is reversely tapered tends to occur.

(dye)
As the dye (C) according to the present invention, azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, triarylmethane dyes, oxazine dyes, thiazine dyes, methine dyes, quinoline dyes, perinone dyes and the like can be used. More preferably, a triarylmethane dye is used. As the triarylmethane-based dye, conventionally known triarylmethane-based colored dyes can be widely used. Specifically, methyl violet, crystal violet, Victoria Blue B, OIL Blue 613 (manufactured by Orient Chemical Industries), VALIFAST Blue 1621 (manufactured by Orient Chemical Co., Ltd.), SBN Blue 701 (manufactured by Hodogaya Chemical Co., Ltd.) and derivatives thereof are preferred. These triarylmethane dyes can be used alone or in combination of two or more.

(Photoinitiator)
Examples of the (D) photoinitiator according to the present invention include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- Acetophenone compounds such as 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether Benzoin compounds such as benzoin isopropyl ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4- Benzophenone compounds such as nzoyl-4′-methyldiphenyl sulfide, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2.4-diisopropylthioxanthone, 2, 4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,
6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s- Triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy -Naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) Triazine compounds such as -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) -2- (o-benzoyloxime)], o- (acetyl) -N- (1- Oxime ester compounds such as phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl Examples include phosphine compounds such as diphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, and titanocene compounds. These can be used singly or in combination of two or more.

  The amount of the photoinitiator used is preferably 0.5 to 50% by weight, more preferably 3 to 30% by weight based on the total solid content (components other than the solvent) of the photosensitive composition.

  As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like can also be used in combination.

(solvent)
Examples of the solvent (E) according to the present invention include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, and ethyl cellosolve. , Methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

  A surfactant or the like may be added to the photosensitive composition of the present invention. Surfactants include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, and higher amine halogens. Cationic surfactants such as acid salts and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as these can be used, and these may be used in combination. Add conventional additives such as plasticizers, adhesion promoters, fillers, antifoaming agents, and leveling agents as needed, as well as thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, tert-butylcatechol, and phenothiazine. be able to.

The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the photosensitive composition of this invention by the printing method or the photolithographic method. The transparent substrate is not particularly limited as long as it is transparent and has a certain degree of rigidity, but a film or thin plate of glass, polyester, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, acrylic resin or the like is used. Can do.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.

<Example 1>
Transparent resin 1 was prepared by the following method.
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 20.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, 30 parts of benzyl methacrylate, n -A mixture of 10.0 parts of butyl methacrylate, 25.0 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) and 0.4 part of 2,2'-azobisisobutyronitrile for 2 hours The polymerization reaction was carried out dropwise. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. The transparent resin 1 was prepared by adding.

Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.5 μm filter to obtain a photosensitive composition 1.
SBN Blue 701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 1.20 parts transparent resin 1 42.73 parts photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals) 3.42 parts photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M402") 6.84 parts cyclohexanone 45.82 parts

<Example 2>
Transparent resin 2 was prepared by the following method.
370 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 20.0 parts of methacrylic acid, 10.0 parts of 2-hydroxyethyl methacrylate, 50.0 parts of benzyl methacrylate A mixture of 5.0 parts of n-butyl methacrylate, 15.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) and 0.4 part of 2,2′-azobisisobutyronitrile. The polymerization reaction was performed dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. The transparent resin 2 was prepared by adding.

  Next, a photosensitive composition 2 was obtained in the same manner as in Example 1 except that the transparent resin 1 was changed to the transparent resin 2.

<Example 3>
Transparent resin 3 was prepared by the following method.
370 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 15.0 parts of methacrylic acid, 5.0 parts of 2-hydroxyethyl methacrylate, 70.0 parts of benzyl methacrylate at the same temperature. , 5.0 parts of n-butyl methacrylate, 5.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 0.4 part of 2,2′-azobisisobutyronitrile. The polymerization reaction was performed dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. The transparent resin 3 was prepared by adding.

  Next, a photosensitive composition 3 was obtained in the same manner as in Example 1 except that the transparent resin 1 was changed to the transparent resin 3.

<Example 4>
Transparent resin 4 was prepared by the following method.
370 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 10.0 parts of methacrylic acid, 5.0 parts of 2-hydroxyethyl methacrylate, 80.0 parts of benzyl methacrylate at the same temperature. , A mixture of 5.0 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.) and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours to conduct a polymerization reaction. Went. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. The transparent resin 4 was prepared by adding.

  Next, a photosensitive composition 4 was obtained in the same manner as in Example 1 except that the transparent resin 1 was changed to the transparent resin 4.

<Comparative Example 1>
Transparent resin 5 was prepared by the following method.
370 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 5.0 parts of methacrylic acid, 5.0 parts of 2-hydroxyethyl methacrylate, 85.0 parts of benzyl methacrylate at the same temperature. , A mixture of 5.0 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.) and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours to conduct a polymerization reaction. Went. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. The transparent resin 5 was prepared by adding.

  Next, a photosensitive composition 5 was obtained in the same manner as in Example 1 except that the transparent resin 1 was changed to the transparent resin 5.

<Comparative example 2>
Transparent resin 6 was prepared by the following method.
370 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 5.0 parts of methacrylic acid, 5.0 parts of 2-hydroxyethyl methacrylate, 90.0 parts of benzyl methacrylate at the same temperature. Then, a mixture of 0.4 part of 2,2′-azobisisobutyronitrile was dropped over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. The transparent resin 6 was prepared by adding.

  Next, a photosensitive composition 6 was obtained in the same manner as in Example 1 except that the transparent resin 1 was changed to the transparent resin 6.

<Comparative Example 3>
Transparent resin 7 was prepared by the following method.
370 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 20.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, 25.0 parts of benzyl methacrylate at the same temperature. , 10.0 parts of n-butyl methacrylate, 30.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) and 0.4 part of 2,2′-azobisisobutyronitrile. The polymerization reaction was performed dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. The transparent resin 7 was prepared by adding.

  Next, a photosensitive composition 7 was obtained in the same manner as in Example 1 except that the transparent resin 1 was changed to the transparent resin 7.

<Comparative example 4>
A mixture of the following composition was stirred and mixed using the transparent resin 2 so as to be uniform, and then filtered through a 0.5 μm filter to obtain a photosensitive composition 8.
SBN Blue701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 1.20 parts transparent resin 2 68.36 parts photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.71 parts photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M402") 3.42 parts cyclohexanone 25.31 parts

<Comparative Example 5>
A mixture of the following composition was stirred and mixed using the transparent resin 2 so as to be uniform, and then filtered through a 0.5 μm filter to obtain a photosensitive composition 9.
SBN Blue701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 1.20 parts transparent resin 2 17.57 parts photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals Co., Ltd.) 5.10 parts photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M402" manufactured) 10.19 parts cyclohexanone 65.94 parts

<Comparative Example 6>
Using transparent resin 2, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.5 μm filter to obtain photosensitive composition 10.
SBN Blue701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 2.20 parts transparent resin 2 40.45 parts Photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals) 3.24 parts photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M402" manufactured) 6.47 parts cyclohexanone 47.64 parts

<Comparative Example 7>
Using transparent resin 2, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.5 μm filter to obtain photosensitive composition 11.
SBN Blue 701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 0.40 parts Transparent resin 2 44.55 parts Photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals) 3.56 parts photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M402" manufactured) 7.13 parts cyclohexanone 44.36 parts

[Evaluation items and evaluation methods]
The (sensitivity), (pattern shape, linearity), (coating unevenness), (chemical resistance), and (light resistance) of the photosensitive compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 7 are as follows. The method was evaluated.

(sensitivity)
On the glass substrate, the photosensitive compositions 1 to 11 obtained in the above examples and comparative examples were applied by spin coating so as to have a film thickness of 2 μm, dried, and then pre-baked at 70 ° C. for 20 minutes. Then, UV exposure was performed through a photomask having a fine line pattern of 50 μm by a proximity exposure method using a proximity aligner. The exposure amount was set to 11 levels of 10, 20, 30, 50, 80, 100, 150, ²⁰⁰ , 300, 400, and 500 mJ / cm ² .

Next, shower development was performed using a 1.25% by mass sodium carbonate solution, followed by washing with water to complete patterning. The film thickness of the obtained filter segment was divided by the film thickness of the unexposed / undeveloped portion to calculate the remaining film ratio. Then, the exposure sensitivity curve was plotted with the horizontal axis representing the common logarithm of the exposure dose and the vertical axis representing the remaining film ratio after development. From the resulting exposure sensitivity curve, saturation exposure the minimum exposure amount of development after the residual film ratio reaches more than 85%, i.e. the sensitivity of the photosensitive composition, and 〇 those less than 300mJ / cm ^2, 300mJ / cm ^Two or more were evaluated as x.

(Pattern shape, linearity)
On the glass substrate, the photosensitive compositions 1 to 11 obtained in the above Examples and Comparative Examples were applied by spin coating so as to have a film thickness of 2 μm, and then dried, and then at 70 ° C. for 20 minutes. After performing the pre-baking, exposure was performed with a saturated exposure amount of each photosensitive composition by a proximity exposure method using a proximity aligner. Next, after shower development using a 1.25 mass% sodium carbonate solution, and after washing with water, patterning is completed. The substrate for evaluation was baked at 180 ° C. for 20 minutes in a clean oven. The shape of the obtained pattern was observed with an SEM, and the case where there was no peeling and the shape was a forward taper shape was indicated by ◯, and the case where the pattern was peeled or an overhang shape was indicated by ×. In addition, as the evaluation of the linearity, the case where the linearity of the pattern edge portion was good was evaluated as ◯, and the case where the pattern was unstable due to poor developability was evaluated as ×.

(Coating unevenness)
The substrate coated with a spin coater was visually observed, and “◯” indicates that the substrate was uniformly applied, and “X” indicates that the film thickness was different in the surface and became uneven.

(chemical resistance)
The sample substrate patterned with the photosensitive composition was immersed in N-methyl-2-pyrrolidinone (hereinafter referred to as NMP) for a specified time, and the color difference ΔEab before and after that was measured.
A case where ΔEab was 5 or less was marked as “◯”, and a case where ΔEab exceeded 5 was judged as “x”.

(Light resistance)
The sample substrate patterned with the photosensitive composition was exposed to light with a light resistance evaluation apparatus (“Weather Meter Ci35A” manufactured by Atlas Co., Ltd.) for 100 hours, and the color difference ΔEab before and after the light resistance evaluation was measured.
A case where ΔEab was 5 or less was marked as “◯”, and a case where ΔEab exceeded 5 was judged as “x”.

[Evaluation results]
Table 1 shows the evaluation results obtained from the photosensitive compositions of Examples 1 to 4 and Comparative Examples 1 to 7.

  From the results in Table 1, the following is clear. That is, in the photosensitive composition containing at least (A) a transparent resin, (B) a photopolymerizable monomer (C) dye, (D) a photoinitiator, and (E) a solvent, the (A) transparent resin is a co-polymer. Color containing 30 to 80% by weight of benzyl methacrylate as a polymerization component and (C) dye in the range of 3 to 10% in the total solid content, small color difference in light resistance test, and no coating unevenness It turns out that a filter is obtained. On the other hand, when the content of benzyl methacrylate is lower than 30% by weight, the effect of improving the light resistance is not sufficient, and when it exceeds 80% by weight, the pattern linearity is poor and the chemical resistance is poor. Further, when the ratio of the photopolymerizable monomer in the solid content is less than 20%, the exposure sensitivity is lowered, and when it exceeds 50%, the pattern shape is overhanged, making it difficult to produce a color filter substrate. From the above, the products of the present invention of Examples 1 to 4 were all better than the comparative products of Comparative Examples 1 to 7.

  By using a dye, the transmittance is high, that is, the efficiency at the time of color display is high and the light resistance is excellent. Therefore, a color display device having a low-power consumption, a long life, and a bright and clear color image can be obtained.

1. Color filter 2. Liquid crystal
3 ... TFT array 4 ... Backlight 5 ... Transparent substrate 6a ... Red colored layer
6b: Green colored layer 6c: Blue colored layer 7: Black matrix 8: Overcoat layer 9: TFT
10: Transparent electrode 11: Deflection plate 12: Organic EL element
13 …… Barrier layer
14a... Red light emitting layer 14b... Green light emitting layer 14c... Blue light emitting layer 15.

Claims (6)

  In the photosensitive composition containing at least (A) transparent resin, (B) photopolymerizable monomer, (C) dye, (D) photoinitiator, and (E) solvent, the (A) transparent resin is copolymerized. A photosensitive composition comprising 30 to 80% by weight of benzyl methacrylate as a component and 3 to 10% by weight of (C) dye in the total solid content.   2. The photosensitive composition according to claim 1, wherein the (B) photopolymerizable monomer is 20 wt% to 50 wt% in the total solid content.   The photosensitive composition according to claim 1, wherein the (C) dye is a triarylmethane dye.   A color filter comprising the dye-containing photosensitive composition according to claim 1.   A liquid crystal display comprising the color filter according to claim 4.   An organic EL display comprising the color filter according to claim 4.