JP4808587B2 - Photosensitive coloring composition and optical member using the same - Google Patents

Description

 The present invention is used for optical members such as color filters used in liquid crystal displays, video cameras, car navigation systems, mobile phones, and the like, and a photosensitive coloring composition containing an organic pigment having excellent heat resistance and light resistance, and the same The present invention relates to an optical member using.

Color filters used in color filters for liquid crystal displays, video cameras, car navigation systems, mobile phones, etc. are generally a transparent substrate, a black matrix, three primary color pixels, a pixel protective film, and a working electrode that are sequentially laminated on the transparent substrate. And a transparent conductive film.
The color filter colors white light incident on the coating in the color of the coating. The color filter uses light from a built-in light source, external light incident on a display screen, external light incident on a camera from a subject, and the like, and enables color display.

In such a color filter, the wavelength of light included in the visible region is divided into a plurality of regions, and among these regions, light included in a specific region is completely transmitted and light in other wavelength regions is completely transmitted. It is considered ideal to shut off. That is, by completely blocking light in other wavelength regions, it is possible to perform color separation and color display with excellent hue, brightness, and saturation (see, for example, Patent Document 1).
As a method for producing a color filter, a known ink jet method, printing method, photoresist method, etching method or the like is used (for example, see Patent Document 2).
However, in consideration of high definition, control of spectral characteristics and reproducibility, the following photoresist method is preferable. In this photoresist method, a dye or pigment is dispersed in a transparent resin together with a photopolymerization initiator and a polymerizable monomer in a solvent to prepare a colored composition, and this colored composition is applied onto a transparent substrate to form a colored layer. Then, a color filter is formed by repeating a series of processes for forming one color pixel for each color by pattern exposure and development of the colored layer.
JP 2001-042521 A JP 2004-307853 A

Conventionally, in the three primary color pixels, a dye is used as a coloring composition because of excellent transparency and contrast and abundant spectral variations. However, in order to enhance heat resistance and light resistance, the manufacturing method using a pigment as a coloring composition is currently shifted, and production by a manufacturing method using a dye method is very small.
Further, it is disclosed that the heat resistance and light resistance of a dye are improved by coating the dye with inorganic fine particles to make the particles fine. However, this dye does not provide characteristics that surpass the pigment.
On the other hand, the use of pigments has improved heat resistance and light resistance, but pigment particles have a large particle size, which causes problems such as a decrease in transmittance and a decrease in contrast due to light scattering. . Research on the reduction in the diameter of pigment particles is ongoing, but pigment particles aggregate due to an increase in surface energy as the diameter decreases, resulting in a decrease in transmittance and a decrease in contrast due to light scattering. Problem arises.

By the way, in the past, when trying to combine inorganic oxide particles and organic pigments in a hydrophobic resin, the surface of the inorganic oxide particles is hydrophilic, so that both are separated or not separated. There was a risk of problems such as devitrification. Therefore, there has been a problem that it is difficult to combine the inorganic oxide particles and the organic pigment while maintaining the transparency of the resin.
Therefore, as a general solution, in order to hydrophobize the surface of the inorganic oxide particles, the surface of the inorganic oxide particles is modified with a surface modifier such as an organic polymer dispersing agent to thereby form a resin and an inorganic oxide. The device which raises the compatibility with particles is made. However, since the particle size of the inorganic oxide particles exceeds 20 nm, there is a problem in that the transparency is lowered and devitrification occurs in some cases.

 The present invention has been made in view of the above circumstances, and is a photosensitive coloring composition capable of realizing an optical member excellent in transparency, heat resistance, and light resistance by coating an organic pigment with inorganic oxide fine particles. An object is to provide an object and an optical member using the same.

 As a result of intensive studies to solve the above problems, the present inventors have coated an organic pigment with inorganic oxide fine particles, and dispersed the organic pigment in a dispersion to obtain a photosensitive coloring composition. When compounded with a resin, the present inventors have found that mechanical properties can be improved while maintaining the transparency of the complex, and the present invention has been completed.

 That is, the photosensitive coloring composition of the present invention is a photosensitive coloring composition mainly composed of a photosensitive resin and an organic pigment, and the organic pigment is coated with inorganic oxide fine particles.

The dispersed particle diameter of the inorganic oxide fine particles is preferably 20 nm or less.
The inorganic oxide fine particles are preferably modified on the surface with a surface modifier.
The surface modifier preferably has at least one reactive functional group.
The surface modifier is preferably one or more selected from the group of silane coupling agents and surfactants.
The weight ratio of the modified portion on the surface is preferably 5% by weight or more and 200% by weight or less of the inorganic oxide fine particles.
The dispersed particle diameter of the organic pigment coated with the inorganic oxide fine particles is preferably 100 nm or less.
The weight ratio of the inorganic oxide fine particles is preferably 1% by weight or more and 70% by weight or less of the organic pigment.

 The optical member of the present invention is characterized by using the photosensitive coloring composition of the present invention.

 The photosensitive coloring composition of the present invention is a photosensitive coloring composition mainly composed of a photosensitive resin and an organic pigment, and the organic pigment is coated with inorganic oxide fine particles, so that it has excellent dispersion stability. It becomes a photosensitive coloring composition for a color filter excellent in transparency, heat resistance, and weather resistance.

 Since the optical member of the present invention uses the photosensitive coloring composition of the present invention, a color filter excellent in transparency, heat resistance, and weather resistance can be formed.

The best mode of the photosensitive coloring composition of the present invention and an optical member using the same will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

"Photosensitive coloring composition"
The photosensitive coloring composition of the present invention is a photosensitive coloring composition mainly composed of a photosensitive resin and an organic pigment, and is a composition in which an organic pigment is coated with inorganic oxide fine particles.

Transparent resin is mentioned as resin used for the coloring composition of this invention. As this transparent resin, a resin having a transmittance of 80% or more in the entire wavelength region of 400 nm to 700 nm is preferable, and a resin of 95% or more is more preferable.
This transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin.
In addition, the transparent resin, if necessary, is a precursor thereof, and is mixed with one or more selected from a polymerizable monomer or a polymerizable oligomer that is cured by irradiation with radiation to produce a transparent resin. Can be used.

Thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, Examples thereof include acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, and polyimide resins.
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 melamine resin, a urea resin, and a phenol resin.

  As the photosensitive resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group, Resins in which photocrosslinkable groups such as (meth) acryloyl groups and styryl groups are introduced into linear polymers by reacting with cinnamic acid; styrene-maleic anhydride copolymers and α-olefin-maleic anhydride copolymers A linear polymer containing acid anhydrides such as those obtained by half-esterification with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate is used.

 Polymerizable monomers and polymerizable oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (Meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tolpropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate , Neopentyl glycol diglycidyl diether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy ( Various acrylic esters and methacrylic esters such as (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxy vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl One or more selected from (meth) acrylamide, N-vinylformamide, acrylonitrile and the like are used.

Although it does not specifically limit as an organic pigment, Well-known C.I. I. One or two or more types selected from Pigment are used. For example, Pigment Red 9, 19, 38, 43, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240; Pigment Blue 15, 16, 22, 29, 60, 64; Pigment Green 7, 36; Pigment Red 20, 24, 81, 83, 86, 93, 108 109, 110, 117, 125, 137, 138, 139, 147, 153, 154, 166, 168, 185; Pigment Orange 36; Pigment Violet 23, and the like.
These organic pigments may be used as a mixture of two or more according to the desired hue.

The inorganic oxide fine particles are not particularly limited, but zirconia (Zr), titanium (Ti), silicon (Si), aluminum (Al), iron (Fe), copper (Cu), zinc (Zn), yttrium (Y ), Niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), tantalum (Ta), tungsten (W), lead (Pb), bismuth (Bi), cerium (Ce), antimony (Sb) ), Germanium (Ge), lanthanum (La), ruthenium (Ru), and the like.
Examples of oxides of these elements include zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ , FeO). , Fe ₃ O ₄ ), copper oxide (CuO, Cu ₂ O), zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ), indium oxide (In ₂ O ₃ , In ₂ O), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₅ , Sb ₂ O ₅ ), germanium oxide (GeO ₂ , GeO ), Lanthanum oxide (La ₂ O ₃ ), ruthenium oxide (RuO ₂ ), and the like.
Further, composite oxides in which a plurality of these inorganic oxide fine particles are combined, for example, tin-added indium oxide (ITO), antimony-added tin oxide (ATO), aluminum zinc oxide (ZnO.Al ₂ O ₃ ), etc. are also used. .

The dispersed particle diameter of the inorganic oxide fine particles is preferably 20 nm or less, and more preferably 10 nm or less. When the dispersed particle diameter of the inorganic oxide fine particles exceeds 20 nm, the dispersed particle diameter of the organic pigment coated with the inorganic oxide fine particles becomes 100 nm or more, light scattering occurs, and the transmittance decreases.
As described above, since the inorganic oxide particles are nano-sized particles, even if the inorganic oxide particles are mixed with an organic pigment to form a composite, light scattering is small and the transparency of the composite can be maintained. Is possible.

Moreover, it is preferable that the surface of the inorganic oxide fine particles is modified with a surface modifier.
As the surface modifier, one having at least one reactive functional group is used. Examples of the reactive functional group include a carbon-carbon double bond or a silicon-hydrogen bond. Such reactive functional groups are preferably one or more selected from the group of alkoxyl groups, hydroxyl groups, vinyl groups, styryl groups, acrylic groups, methacrylic groups, acryloyl groups, and epoxy groups.
Among such surface modifiers, one or more selected from the group of silane coupling agents and surfactants are preferred.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriphenoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltriphenoxysilane, and 3-acryloxypropyl. Trimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltriphenoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriphenoxysilane, 3 -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, Rutriphenoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxy Silane, n-decyltrimethoxysilane, etc. are mentioned.

  Examples of the silane coupling agent include phenyltrimethoxysilane, diphenyldimethoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldichlorosilane, vinylethyldiphenoxysilane, and 3-glycidoxypropylethyl. Dimethoxysilane, 3-glycidoxypropyltriethyldiethoxysilane, 3-glycidoxypropylethyldichlorosilane, 3-glycidoxypropylethyldiphenoxysilane, p-styrylethyldimethoxysilane, p-styrylethyldiethoxysilane P-styryltriethyldichlorosilane, p-styrylethyldiphenoxysilane, 3-acryloxypropylethyldimethoxysilane, 3-acryloxypropylethyldiethoxysilane, 3- Acryloxypropylethyldichlorosilane, 3-acryloxypropylethyldiphenoxysilane, 3-methacryloxypropylethyldimethoxysilane, 3-methacryloxypropylethyldiethoxysilane, 3-methacryloxypropylethyldichlorosilane, 3-methacrylic Examples include loxypropylethyldiphenoxysilane, allylethyldimethoxysilane, allylethyldiethoxysilane, allylethyldichlorosilane, and allylethyldiphenoxysilane.

  Examples of the silane coupling agent include vinyldiethylmethoxysilane, vinyldiethylethoxysilane, vinyldiethylchlorosilane, vinyldiethylphenoxysilane, 3-glycidoxypropyldiethylmethoxysilane, and 3-glycidoxypropyldiethylethoxysilane. 3-glycidoxypropyldiethylchlorosilane, 3-glycidoxypropyldiethylphenoxysilane, p-styryldiethylmethoxysilane, p-styryldiethylethoxysilane, p-styryldiethylchlorosilane, p-styryldiethylphenoxysilane, 3-acryloxypropyldiethylmethoxysilane, 3-acryloxypropyldiethylethoxysilane, 3-acryloxypropyldiethylchlorosilane, 3-acryloxypropiyl Diethylphenoxysilane, 3-methacryloxypropyldiethylmethoxysilane, 3-methacryloxypropyldiethylethoxysilane, 3-methacryloxypropyldiethylchlorosilane, 3-methacryloxypropyldiethylphenoxysilane, allyldiethylmethoxysilane, allyldiethylethoxysilane, Examples include allyl diethyl chlorosilane and allyl diethyl phenoxy silane.

As the surfactant, a nonionic surfactant is preferably used.
Examples of the nonionic surfactant include fatty acid-based polyoxyethylene lanolin fatty acid ester polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, fatty acid alkanolamide, and the like.

Examples of the method for modifying the surface of the inorganic oxide fine particles using the surface modifier include a wet method and a dry method.
The wet method is a method for modifying the surface of the inorganic oxide fine particles by adding and mixing the surface modifier and the inorganic oxide fine particles in a solvent.
The dry method is a method of modifying the surface of the inorganic oxide fine particles by putting the surface modifier and the dried inorganic oxide fine particles into a dry mixer such as a mixer and mixing them.

The weight ratio of the modified portion of the surface-modified inorganic oxide fine particles is preferably 5% by weight or more and 200% by weight or less, more preferably 10% by weight or more and 100% by weight or less, More preferably, it is 20 weight% or more and 100 weight% or less.
Here, the reason for limiting the weight ratio of the modified portion to 5 wt% or more and 200 wt% or less is that if the weight ratio of the modified portion is less than 5 wt%, the inorganic oxide fine particles are difficult to be compatible with the resin. This is because the transparency is lost when compounding with the resin. On the other hand, if the weight ratio of the modified portion exceeds 200% by weight, the effect of the surface treatment agent on the resin properties increases, and the refractive index, etc. This is because the composite properties of the above deteriorate.

Further, the dispersed particle diameter of the organic pigment coated with the inorganic oxide fine particles is preferably 100 nm or less, and more preferably 70 nm or less.
When the dispersed particle diameter of the organic pigment coated with the inorganic oxide fine particles exceeds 100 nm, light scattering occurs and the transmittance decreases.

The weight ratio of the inorganic oxide fine particles is preferably 1% by weight or more and 70% by weight or less of the organic pigment, and more preferably 5% by weight or more and 50% by weight or less.
Here, the reason why the weight ratio of the inorganic oxide fine particles is limited to 1% by weight or more and 70% by weight or less of the organic pigment is that this range is a range in which the inorganic oxide particles are well compatible, If the weight ratio is less than 1% by weight, the coating area of the organic pigment is small, so that the effect is not exhibited. On the other hand, if the weight ratio exceeds 70% by weight, gelation and coagulation precipitation may occur. This is because the properties as a coloring composition are deteriorated.

The photosensitive coloring composition of the present invention is dispersed in a dispersion medium and used as a photosensitive coloring composition dispersion.
The dispersion medium basically contains at least one of water, an organic solvent, a liquid resin monomer, and a liquid resin oligomer.
Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol, butanol, and octanol; ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone. Esters such as diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; acetone, Methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, cyclohexanone Any ketones; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; amides such as dimethylformamide, N, N-dimethylacetoacetamide, and N-methylpyrrolidone are preferably used, and one of these solvents Or 2 or more types can be used.

As the liquid resin monomer, acrylic or methacrylic monomers such as methyl acrylate and methyl methacrylate, and epoxy monomers are preferably used.
Moreover, as said liquid resin oligomer, a urethane acrylate oligomer, an epoxy acrylate oligomer, an acrylate oligomer, etc. are used suitably.

  In addition to the above, this photosensitive coloring composition dispersion may contain other inorganic oxide particles, resin monomers, and the like as long as the characteristics are not impaired.

In addition, a photopolymerization initiator or the like is added to the photosensitive coloring composition of the present invention when the photosensitive coloring composition is cured by ultraviolet irradiation.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethyl Thioxanthone compounds such as thioxanthone; 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-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1) Yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4, trichloro Triazine compounds such as methyl- (piperonyl) -6-triazine and 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine; 1,2-octadione, 1- [4- (phenylthio) -2,2 -(O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, and the like; bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Fin compounds; quinone compounds such as 9,10-phenanthrenequinone, camphor quinone, and ethyl anthraquinone; borate compounds; carbazole compounds; imidazole compounds; one or more selected from titanocene compounds Is used.

The addition amount of the photopolymerization initiator is preferably 0.5% by weight or more and 50% by weight or less, preferably 3% by weight or more and 30% by weight or less, based on the total solid content of the photosensitive coloring composition. It is more preferable that
Here, the reason why the addition amount of the photopolymerization initiator is limited to 0.5% by weight or more and 50% by weight or less with respect to the total solid content of the photosensitive coloring composition is less than 0.5% by weight. This is because no proper reaction can be obtained, and if it exceeds 50% by weight, the properties of the resin as the main component may be impaired.

Moreover, in the photosensitive coloring composition of this invention, you may use a dispersing agent in order to improve dispersion | distribution of the organic pigment to transparent resin.
As the dispersant, nonionic surfactants, ionic surfactants, organic pigment derivatives, polyesters, and the like are used.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether.
Examples of the ionic surfactant include sodium alkylbenzene sulfonate, poly fatty acid salt, fatty acid salt alkyl phosphate, and tetraalkyl ammonium salt.
These dispersants can be used alone or in combination of two or more.

  Furthermore, you may add additives, such as a sensitizer, to the photosensitive coloring composition of this invention in the range which does not impair a characteristic.

"Method for producing photosensitive coloring composition"
In order to produce the photosensitive coloring composition of the present invention, a photosensitive resin, an organic pigment, a dispersant and the like are added to the inorganic oxide transparent dispersion, and the solvent is removed at room temperature under reduced pressure. A colored resin is prepared by sufficiently kneading with a three roll, jet mill or the like.
Next, a photosensitive coloring composition is prepared by adding a polymerizable monomer, a photopolymerization initiator, a solvent and the like to the colored resin and stirring.

 The photosensitive coloring composition of the present invention is excellent in dispersion stability, transparency, heat resistance, and weather resistance because the organic pigment is coated with inorganic oxide fine particles.

The optical member of the present invention is a member formed using the photosensitive coloring composition of the present invention. Among the optical members, the color filter includes a transparent substrate and a colored layer that is arranged in a pattern on the transparent substrate and constitutes a pixel.
In order to form this colored layer, the photosensitive colored composition is spin-coated on a transparent substrate and then dried to form a thin film having a predetermined thickness.
Next, after preheating at 80 ° C. or more and 100 ° C. or less for 1 minute or more and 60 minutes or less, exposure is performed using a mask having a predetermined pixel size.
Next, after development with a sodium carbonate solution, it is washed thoroughly with water, heated at 100 ° C. or more and 300 ° C. or less for 1 minute or more and 60 minutes or less to fix the pattern, form a colored layer, and obtain a color filter.

 Since the optical member of the present invention uses the photosensitive coloring composition of the present invention, a color filter excellent in transparency, heat resistance, and weather resistance can be formed.

 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

"Example 1"
[Preparation of Zirconium Oxide Transparent Dispersion]
To a zirconium salt solution in which 2615 g of zirconium oxychloride octahydrate is dissolved in 40 L (liter) of pure water, dilute ammonia water in which 344 g of 28% ammonia water is dissolved in 20 L of pure water is added with stirring, and the zirconia precursor slurry is added. It was adjusted.
Next, an aqueous sodium sulfate solution in which 300 g of sodium sulfate was dissolved in 5 L of pure water was added to this slurry with stirring. The amount of sodium sulfate added at this time was 30% by weight with respect to the zirconia converted value of zirconium ions in the zirconium salt solution.

Next, this mixture was dried in the air at 130 ° C. for 15 hours using a dryer to obtain a solid.
Next, the solid was pulverized with an automatic mortar or the like and then baked at 500 ° C. for 1 hour in the air using an electric furnace.
Next, the fired product is put into pure water and stirred to form a suspension, followed by washing with a centrifuge to sufficiently remove the added sodium sulfate, and then drying with a dryer. Then, zirconium oxide particles were prepared.

Next, 55 g of toluene as a dispersion medium and 15 g of a silane coupling agent (KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surface modifier are added to and mixed with 30 g of the zirconium oxide particles, and the surface of the zirconium oxide particles is then surface modified. Modified by
Thereafter, dispersion treatment was performed to prepare a zirconium oxide transparent dispersion (Z1) of Example 1.

[Preparation of photosensitive coloring composition]
Next, 15.0 g of this zirconium oxide transparent dispersion (Z1: 30 wt%), 45.0 g of a photosensitive acrylic resin (solid content 20 wt%), and C.I. I. pigment no. 15 (manufactured by Toyo Ink Co., Ltd.) and 0.9 g of Solsperse (manufactured by Zeneca Co., Ltd.) as a dispersant were added, and the solvent was removed at room temperature under reduced pressure. A colored resin was prepared.
Next, 2.8 g of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) as a polymerizable monomer and 2- (4′-methoxy-1′-naphthyl) as a photopolymerization initiator are added to 30.0 g of this blue colored resin. A photosensitive coloring composition was prepared by adding 0.6 g of -4,6-bis (trichloromethyl) -s-triazine and 24.0 g of cyclohexane and stirring.

[Production of color filter]
This photosensitive coloring composition was spin-coated on a substrate and then dried to form a thin film having a thickness of 2 μm.
Next, after preheating at 80 ° C. for 20 minutes, exposure was performed using a mask having a pixel size of 80 μm × 100 μm (exposure amount was 400 mJ / cm ² ).
Next, after development with a sodium carbonate solution, the plate was thoroughly washed with water and heated at 250 ° C. for 30 minutes to fix the pattern, thereby obtaining a color filter.

"Example 2"
A zirconium oxide transparent dispersion (Z2) of Example 2 was prepared in the same manner as in Example 1 except that RC-100 (manufactured by Daiichi Rare Element Co., Ltd.) was used as the zirconium oxide particles.
Subsequently, the photosensitive coloring composition of Example 2 was prepared in the same manner as in Example 1 by using this zirconium oxide transparent dispersion (Z2).
Subsequently, the color filter of Example 2 was produced like this Example 1 using this photosensitive coloring composition.

"Comparative Example 1"
A photosensitive colored composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that zirconium oxide particles were not used.
Subsequently, the color filter of the comparative example 1 was produced like this Example 1 using this photosensitive coloring composition.

"Comparative Example 2"
15.0 g of the above-described zirconium oxide transparent dispersion (Z2: 30 wt%), 45.0 g of acrylic resin (solid content: 20 wt%), 9.0 g of Oil Blue 8B (manufactured by Chuo Gosei Co., Ltd.) as a blue dye, and Then, 0.9 g of Solsperse (manufactured by Zeneca) was added as a dispersant, the solvent was removed at room temperature under reduced pressure, and then kneaded sufficiently with a three-roll mill to prepare a blue colored resin.
Next, 30.0 g of this blue colored resin, 1.2 g of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) as a polymerizable monomer, 1.5 g of piperonyl-s-triazine as a photopolymerization initiator, and cyclohexane 24 0.0 g was added and stirred to prepare a photosensitive coloring composition of Comparative Example 2.
Subsequently, the color filter of the comparative example 2 was produced like this Example 1 using this photosensitive coloring composition.

“Comparative Example 3”
A photosensitive colored composition of Comparative Example 3 was prepared in the same manner as Comparative Example 2 except that zirconium oxide particles were not used.
Subsequently, the color filter of the comparative example 3 was produced like this comparative example 2 using this photosensitive coloring composition.

[Evaluation of zirconium oxide particles]
The dispersed particle diameters of the zirconium oxide particles of Examples 1 and 2 were measured.
The dispersed particle size was adjusted using a dynamic light scattering particle size distribution analyzer (Malvern) so that the content of zirconium oxide particles in the zirconium oxide transparent dispersion was 1% by weight using methyl ethyl ketone. The sample was used as a measurement sample. The data analysis conditions were such that the particle diameter standard was a volume standard, the refractive index of zirconium oxide as a dispersed particle was 2.15, and the refractive index of methyl ethyl ketone as a dispersion medium was 1.38.
The results are shown in Table 1.

[Evaluation of Zirconium Oxide Transparent Dispersion]
The visible light transmittance of the zirconium oxide transparent dispersions of Examples 1 and 2 was measured.
Visible light transmittance of the zirconium oxide transparent dispersion was adjusted by using methyl ethyl ketone so that the content of zirconium oxide particles in the zirconium oxide transparent dispersion was 5% by weight in a quartz cell (10 mm × 10 mm). The visible light transmittance when the optical path length of this sample was 10 mm was measured using a spectrophotometer (manufactured by JASCO Corporation).
The results are shown in Table 1.

[Evaluation of color filter]
The color filters of Examples 1 and 2 and Comparative Examples 1 to 3 were evaluated for heat resistance and light resistance by the following apparatuses and methods.
(1) Evaluation of color difference before and after heating (evaluation of heat resistance)
The color difference before and after heating of the color filter was measured using a microspectroscopic system (manufactured by Olympus).
The results are shown in Table 2.

(2) Evaluation of transmittance after heating (evaluation of heat resistance)
The transmittance (wavelength 450 nm and wavelength 600 nm) of the color filter after heating was measured using a spectrophotometer (manufactured by JASCO Corporation).
The results are shown in Table 3.

(3) Evaluation of weather resistance The color filter was exposed to a xenon lamp (100,000 lux), and the time until the color difference from the start was 5 or more was measured.
The results are shown in Table 4.

From the results of Tables 2 and 3, it was found that the color filters of Examples 1 and 2 were excellent in heat resistance. On the other hand, it was found that the color filters of Comparative Examples 1 to 3 were inferior in heat resistance to Examples 1 and 2.
From the results in Table 4, it was found that the color filters of Examples 1 and 2 were excellent in weather resistance. On the other hand, it was found that the color filters of Comparative Examples 1 to 3 were inferior in weather resistance to Examples 1 and 2.

The photosensitive coloring composition of the present invention is a photosensitive coloring composition mainly composed of a photosensitive resin and an organic pigment. Since the organic pigment is coated with inorganic oxide fine particles, it has excellent dispersion stability and is transparent. Because it is a photosensitive coloring composition for color filters that excels in heat resistance, heat resistance, and weather resistance, not to mention color filters used in color filters for liquid crystal displays, video cameras, car navigation systems, mobile phones, etc. The effect is also great in various other industrial fields.

Claims (9)

A photosensitive coloring composition mainly composed of a photosensitive resin and an organic pigment,
A photosensitive coloring composition, wherein the organic pigment is coated with inorganic oxide fine particles.  The photosensitive coloring composition according to claim 1, wherein the dispersed particle diameter of the inorganic oxide fine particles is 20 nm or less.  The photosensitive coloring composition according to claim 1, wherein the surface of the inorganic oxide fine particles is modified with a surface modifier.  The photosensitive coloring composition according to any one of claims 1 to 3, wherein the surface modifier has at least one reactive functional group.  The photosensitive coloring composition according to any one of claims 1 to 4, wherein the surface modifier is a silane coupling agent and / or a surfactant.  The photosensitive coloring composition according to any one of claims 3 to 5, wherein the weight ratio of the modified portion on the surface is 5% by weight or more and 200% by weight or less of the inorganic oxide fine particles. .  The photosensitive coloring composition according to any one of claims 1 to 6, wherein the dispersed particle diameter of the organic pigment coated with the inorganic oxide fine particles is 100 nm or less.  8. The photosensitive coloring composition according to claim 1, wherein a weight ratio of the inorganic oxide fine particles is 1% by weight or more and 70% by weight or less of the organic pigment. An optical member comprising the photosensitive coloring composition according to any one of claims 1 to 8.