JP2534892B2 - Color filter - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color filter. More specifically, it relates to a specific dye and a method for coloring a surface film of a substrate.

The present invention relates to a color filter having a colored layer containing an additive.

BACKGROUND ART Transparent substrates such as glass and plastic are colored and used for sunglasses, show windows, various displays, etc., and recently, these colored substrates are
It is used as a member of liquid crystal devices and color separation devices for color TV cameras. However, it is difficult to say that a method for coloring a substrate suitable for the purpose of use in such a field of use has been established. That is, in order to color conventional glass, plastic, etc., a coloring agent is added in a step prior to molding into a predetermined shape, and then molding and coloring are added, and then molding and coloring are carried out. Although the method of obtaining is applied as the easiest method, this method is suitable for the purpose of obtaining a large amount of colored moldings of the same color at a time, but for the purpose of obtaining a small-scale colored product. Is unsuitable, and by this method, it is not possible to provide portions having different color tones on the same molded product. Therefore, for such purpose, a transparent synthetic resin layer on a thin film or a film of a protein-based natural polymer substance such as gelatin, casein, or glue is provided on the surface of a substrate, and this is colored with a dye (or The method of dyeing) is convenient. Incidentally, protein-based natural high-molecular substances such as gelatin, casein, and glue have a cationic group, and thus can be generally dyed with an anionic dye. A method of applying a yellow anionic dye and a blue anionic dye from the same dye bath or a separate bath has been adopted to obtain a particularly green colored film of a protein-based natural polymer substance. However, this method has the drawback that the desired green color tone is not obtained and the reproducibility is not sufficient because the affinity of the anionic dye for the protein-based natural polymer substance varies depending on the dye used.

There is also a drawback that the quality of the protein-based natural high molecular weight substances such as gelatin, casein and glue to be obtained varies depending on the raw material source and it is difficult to obtain a stable color.

On the other hand, color filters for liquid crystal color television devices are also being developed. Color filters are roughly classified into three primary colors, that is, red, green, and blue, and complementary colors, that is, cyan, yellow, and magenta, or two of them and a transparent layer. In either case, Needless to say, the spectral characteristics of the color filter determine whether or not the color reproducibility of a solid-state image sensor for color, a color television, etc. is determined, and coloring with various dyes or combinations thereof has been tried. . However, in the case of the complementary color system, it is difficult to find a dye having a good spectral characteristic for cyan, and it is difficult to find a dye having a good spectral characteristic for the primary color green as well. More recently, from the viewpoint of outdoor use of liquid crystal color televisions, the robustness of color filters, particularly the light resistance, has become a problem. It has been proposed to use phthalocyanine dyes as cyan (complementary color) and green (primary color) dyes having such excellent spectral characteristics and excellent light resistance.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The compound represented by the formula (1) described below contains a protein-based natural polymer such as gelatin, casein, and glue, or a cationic group, which is often used as a coating film to be colored in producing a color filter. It has excellent spectral characteristics of a colored (dyeing) coating film that has been shown to have good dyeing properties with respect to the synthetic resin, and has excellent light fastness in the presence of oxygen. However, it has a drawback that it causes discoloration in a light resistance test under oxygen cutting.

Means for Solving the Problems The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides a compound of the formula (1) {In the formula (1), Pc is a metal-free or metal-containing phthalocyanine residue, A is a group represented by OH, NH ₂ or NHCOOH, and B is
OH, NH ₂ , NHCH ₂ COOH or (R ₁ and R ₂ are H, CH ₃ , COOH, NHCOCH ₃ , NHCONH ₂ , halogen or C ₁
~ C ₃ alkoxy group, C is (Y is H, (R ₃ and R ₄ are H, OH, COOH, CH ₃ SO ₂ , CH ₃ CONH, NH ₂ , C _{1 to} C ₃ alkyl group, C _{1 to} C ₃ alkoxy group or halogen, and m is 0,
1 or 2 respectively) or (P represents an integer of 0 to 3), Z is CH ₃ , C ₂ H ₅ , COOH
Or NH ₂ respectively); (In the formula, R ₅ is CONH ₂ , CH ₂ SO ₃ H or CN, R ₆ is an alkyl group of C ₁ to ₄ , CH _{2 q} COOH (q represents an integer of 1 to 3), CH _{2 q} SO ₃ H (p represents the same meaning as described above) or a C _1-3 hydroxyalkyl group, respectively; (M represents the same meaning as described above) or (P represents the same meaning as described above), and n represents 0 or 1. ], Respectively. Further, α is a number of 1 to 3, β is a number of 0 to 2, and γ is a number of 1 to 4, respectively, α + β +
γ ≦ 4. Also, SO ₃ H, SO ₂ A and SO ₂ B bound to Pc
Each of which is bonded to a non-identical benzene ring of a phthalocyanine residue, and when Pc contains a metal, the metal is copper, zinc, aluminum or nickel}. wherein as the free acid _{(2) (O 2 N)} x-Ar- (SO 3 H) y (2) ( equation (2), Ar is stilbene, naphthalene or anthraquinone, x is 1 to 2, y is The present invention provides a color filter having a colored layer containing a compound represented by (representing an integer of 1 to 3).

The color filter of the present invention will be described in detail. The phthalocyanine compound (dye) represented by the formula (1) is produced, for example, according to the production method described in Japanese Patent Application No. 63-102489.
That is, formula (a) (In the formula (a), Pc, α, β and γ have the same meanings as described above), and the sulfonic acid chloride compound of Pc and the formula (b) HA (b) (wherein A is the formula (b) is And a compound represented by the formula (c) (In the formula (c), R ₁ , R ₂ , n and C have the same meanings as described above) or by reacting the compound of the formula (a) with the compound of the formula (c) can get.

Specific examples of the compound represented by the formula (2) used in the present invention include the following. (Shown as free acid) n represents 1 to 10. Further, protein type natural polymers such as gelatin and casein which can be used as a film provided on the substrate in the present invention will be described. Of these, gelatin is an animal protein that is irreversibly converted into water-soluble collagen by boiling it with water.It is extracted from animal bones, skin, tendons, etc. by boiling with water. Ari casein is a phosphoprotein that is the main component of milk.

A few percent of a dichromate such as ammonium dichromate is added to an aqueous solution of these natural proteins, which is applied evenly on a substrate by a method such as spin coating, and then irradiated with ultraviolet rays to be completely cured and water insoluble. A film is formed.

The mechanical properties and dyeability of the film vary depending on the type of animal, habitat, site, etc. because the raw material source is animal.
These differences do not hinder the film used in the present invention.

Examples of the synthetic resin film having a cationic group that can be used in the present invention are as follows.

A photoreactive resin composition comprising a polymer (A) having a photoreactive unsaturated group in the side chain and a quaternary ammonium salt group, a photopolymerization initiator (B) and a solvent (C), or a resin composition thereof. Further, a photoreactive resin composition containing a compound (E) having two or more unsaturated groups capable of photoreacting in one molecule is applied to the surface of the base material, and then irradiated with an actinic ray to react. To form a film. The polymer (A) having a photoreactive unsaturated group in the side chain and a quaternary ammonium base is, for example, (N, N-dimethylamino) ethyl acrylate, (N, N-diethylamino) ethyl acrylate, (N, N -Homopolymer or copolymer obtained by polymerizing a monomer having a tertiary amino group such as dimethylamino) propylacrylamide and the like, allyl bromide, 3-chloro-2-methylpropene, p-chloromethylstyrene, 3-chloro-2 -It is obtained by reacting with an unsaturated compound having an active halogen atom such as hydroxypropyl methacrylate. Examples of the compound (E) having two or more unsaturated groups capable of photoreacting in one molecule include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate. Etc.

As the photoreaction initiator (B), 2-ethylanthraquinone, benzophenone and the like can be used. The solvent (C) may be any solvent that can dissolve the polymer (A), the photoreaction initiator (B) and the compound (E) well, and examples thereof include 2-methoxyethanol, 2-ethoxyethanol, toluene, and xylene. Is used.

Such a photoreactive resin composition is applied to the surface of a substrate and cured by irradiation with actinic rays to form a film. The substrate on which the film is provided preferably has excellent transmission characteristics over the entire wavelength range of visible light, and optical glass is generally used, but plastics such as methyl methacrylate resin, polystyrene resin, and polycarbonate resin are preferable. Plates are also used.

In order to incorporate the compound represented by the formula (1) and the compound represented by the formula (2) into the film, for example, a dipping method or a printing method is used, and a dip dyeing method using an aqueous solution is particularly convenient. Is. In this case, 0.1 to 30 g of the compound of the formula (1) and 0.1 to 30 g of the compound of the formula (2) are dissolved in water 1 to prepare a substrate having the above coating in a dye bath at 10 to 100 ° C.
After soaking for at least 2 seconds, remove and dry. The blue-green colored film thus obtained not only exhibits favorable transmission spectral characteristics, but also has excellent light resistance and, in particular, is not discolored under oxygen cutting.

The compounds of formula (1) and formula (2) may be used alone or in combination of two or more.

The color filter obtained by the present invention is useful for cameras for color televisions, liquid crystal color televisions, and the like.

Examples The present invention will be described in more detail with reference to examples. In the examples, parts are parts by weight, and sulfonic acid groups and carboxyl groups are expressed in the form of free acids.

Example 1. Toluene: 69 parts (N, N dimethylamino) ethyl methacrylate: 30 parts Azoisobutyronitrile: 1 part The mixture having the above composition was stirred in a nitrogen atmosphere at 80 ° C. for 8 hours to obtain poly (N, N-dimethyl). Toluene solution containing amino) ethyl methacrylate and azoisobutyronitrile 100
Get the part.

To 50 parts of this solution, 15 parts of chloromethylstyrene was added at room temperature, and after reacting for 16 hours, this was dissolved in 260 parts of 2-ethoxyethanol and further 16 parts of Irgacure 651 (photopolymerization initiator manufactured by Ciba-Geigy). Was added and dissolved to obtain a cationic group-containing photosensitive resin composition. On the other hand, the surface of optical glass (glass plate with excellent light transmission) was washed with acetone, dried, KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 10% ethanol solution was applied, and air-dried.
After heating and drying at 5 ° C. for 5 minutes, the surface was washed with acetone and dried to obtain a coating substrate. The above-mentioned photosensitive resin composition was applied on the surface of this coating substrate by a spin coating method to a film thickness of about 1 micron, and ultraviolet rays of 80 watt / cm4 were applied by a high pressure mercury lamp.
The coating was cured by irradiation for 2 seconds.

An aqueous solution is prepared by dissolving 0.1 part of the compound represented by the other formula (3) and 0.1 part of the compound represented by the formula (4) in 100 parts of water.

This aqueous solution was adjusted to pH 5.5 with acetic acid and then heated to 60 ° C. The optical glass on which the above-mentioned cured coating film has been formed is immersed in this solution for 20 minutes, then washed with water and dried to show a maximum transmission wavelength (λmax) of 528 nm, and an optical glass plate having a film colored vivid green ( A color filter) was obtained. (Coloring treatment) This product was excellent not only in spectral characteristics but also in light fastness under oxygen cutting.

The light resistance test under oxygen cutting was performed as follows.
(Similarly in the following examples) The optical glass plate having the green film obtained above and another transparent glass plate 8
After screen-printing epoxy adhesive containing μm spacers, glue them together and cure to create empty cells with about 8 μm voids, then inject liquid crystal in vacuum, seal the inlet with adhesive, and green A liquid crystal cell having a color filter inside is produced. This was subjected to an exposure test with a carbon arc fade meter, and the change in the transmittance at the maximum transmission wavelength before and after exposure was calculated as the transmitted light retention rate by the following formula.

Transmitted light retention rate Example 1 91% Comparative example 1 75% Comparative example 1 was carried out according to Example 1 except that the compound of formula (4) was not added, and the effect of adding the compound of formula (4) Is clear.

The compound represented by the formula (3) was synthesized as follows.

19.4 parts of copper phthalocyanine-tetrasulfonic acid chloride was added as an aqueous paste to 100 parts of an aqueous solution containing 9.5 parts of the amino compound represented by the formula (5) and adjusted to pH 8 at 10 ° C. or lower with stirring. Then, the mixture was reacted at about 10 ° C. for 6 hours while maintaining the pH value at 9.0 to 9.5 by adding a caustic soda aqueous solution. Then, the temperature was raised to 70 ° C., and the reaction was continued at this temperature for 2 hours. After that, the pH value was adjusted to 6.5 to 7.0 with dilute hydrochloric acid, and salting out was performed with sodium chloride. The precipitated crystals are filtered off and 60
After drying at 0 ° C., 26.0 parts of the compound of the above formula (3) was obtained.

Further, the amino compound represented by the formula (5) is diazotized with 4-acetylamino-2-aminobenzenesulfonic acid in a system of hydrochloric acid / sodium nitrite at 5 ° C. or lower in water by a conventional method, It is obtained by coupling with a pyridone compound represented by and then heating hydrolysis (deacetylation) in an alkaline state.

Examples 2 to 13. Optical glass (color filter) having a coating film prepared according to Example 1 using the compounds of formula (1) and formula (2) shown in Table 1 was the same as in Example 1. And colored. Table 1 shows the structural formulas of the compounds represented by the formulas (1) and (2), the hue of the colored film and the transmitted light retention rate of the obtained colored optical glass.

Example 14. An optical glass substrate was uniformly coated with a 10% aqueous gelatin solution containing 0.5% ammonium dichromate by a spin coating method, dried and then irradiated with ultraviolet rays to be cured.
It was washed and dried with warm water at ℃ and a photocrosslinked gelatin film was formed on an optical glass plate.

On the other hand, an aqueous solution is prepared by dissolving 0.2 part of the compound represented by the following formula (6) and 0.2 part of the compound represented by the above formula (4) in 100 parts of water.

This aqueous solution was adjusted to pH 4 with acetic acid and then heated to 60 ° C. The optical glass having the above-mentioned gelatin hardened film was immersed in this solution for 20 minutes, washed with water and dried to obtain an optical glass substrate (color filter) having a film colored in green with a maximum transmittance at 535 nm. When a liquid crystal cell was produced using the colored substrate and a light resistance test under oxygen cutting was performed, the light resistance of this product was good. The transmitted light retention of this product was 85%. The compound represented by the formula (6) was synthesized as follows.

To 100 parts of an aqueous solution adjusted to pH 8 containing 9.5 parts of the amino compound represented by formula (5), 17 parts of zinc phthalocyanine-trisulfonic acid chloride is added as an aqueous paste at 10 ° C. or lower with stirring.

Then, the mixture was reacted at about 10 ° C. for 6 hours while maintaining the pH value at 9.0 to 9.5 by adding a caustic soda aqueous solution. Then 70
The temperature was raised to 0 ° C., and the reaction was continued at this temperature for 2 hours. Then, the pH value was adjusted to 6.5 to 7.0 with dilute hydrochloric acid and salting out was performed with sodium chloride. The precipitated crystals are filtered off and dried at 60 ° C,
23.5 parts of the compound of the above formula (6) are obtained.

Examples 15 to 26. The gelatin-coated optical glass produced according to Example 14 was similarly dyed to obtain gelatin-coated optical glass (color filter) having a good green hue.
Table 2 shows the structural formulas of the compounds represented by the formulas (1) and (2), the hue of the colored film, and the transmitted light retention rate of the colored optical glass.

Example 27. 0.1 part of a compound represented by the formula (7) was prepared using a gelatin-coated optical glass produced according to Example 14. When 0.1 part of the compound represented by the formula (4) was dissolved in 100 parts of water, adjusted to pH 5.5 with acetic acid, immersed in a dyeing solution heated to 60 ° C. for 20 minutes, washed with water and dried, An optical glass substrate (color filter) having a blue colored film with a maximum transmittance of 496 nm was obtained. The transmitted light retention of this product was 85%.

The compound represented by the formula (7) was synthesized as follows.

17 parts of zinc phthalocyanine-trisulfonic acid chloride is added as a wet paste at a temperature of 10 ° C. or lower to 200 parts of an aqueous solution in which 1.7 parts of glycine is completely dissolved to pH 10. Then
The pH value is adjusted to 1 by adding 10% liquid caustic solution at 10 to 15 ℃.
The reaction was carried out for 15 hours while maintaining 0.0 to 11.0. Then 50
The temperature was raised to 0 ° C. and the reaction was carried out at this temperature for 3 hours. Thereafter, the pH value was adjusted to 3 with dilute hydrochloric acid, salting out was performed with sodium chloride, and the obtained crystals were separated by filtration and dried at 80 ° C. to obtain 16 parts of a compound of the formula (7).

Examples 28 to 33. A gelatin-coated optical glass was subjected to a dyeing treatment in accordance with Example 27 using the compounds represented by the formulas (1) and (2) shown in Table 3 to obtain a blue blue glass substrate (color filter). ) Got. Table 3 shows the structural formulas of the compounds represented by the formulas (1) and (2), the hue of the colored film, and the transmitted light retention rate of the colored glass substrate.

Examples 34 to 39. Acrylic photosensitive resin coated optical glass according to Example 1 was dyed with the compounds represented by the formulas (1) and (2) shown in Table 4 to give a good greenish color. A colored glass substrate (color filter) having a hue was obtained. Table 4 shows the structural formulas of the compounds represented by the formulas (1) and (2), the hue of the colored film, and the transmitted light retention rate of the colored glass substrate.

Effects of the Invention A color filter having a colored film colored with a specific phthalocyanine compound, which does not cause discoloration in the absence of oxygen, was obtained.

Claims (1)

(57) [Claims] 1. Formula (1) in the form of the free acid {In the formula (1), Pc is a metal-free or metal-containing phthalocyanine residue, A is a group represented by OH, NH ₂ or NHCOOH, and B is
OH, NH ₂ , NHCH ₂ COOH or (R ₁ and R ₂ are H, CH ₃ , COOH, NHCOCH ₃ , NHCONH ₂ , halogen or C ₁
~ C ₃ alkoxy group, C is (Y is H, (R ₃ and R ₄ are H, OH, COOH, CH ₃ SO ₂ , CH ₃ CONH, NH ₂ , C _{1 to} C ₃ alkyl group, C _{1 to} C ₃ alkoxy group or halogen, and m is 0,
1 or 2 respectively) or (P represents an integer of 0 to 3), Z is CH ₃ , C ₂ H ₅ , COOH
Or NH ₂ respectively); (In the formula, R ₅ is CONH ₂ , CH ₂ SO ₃ H or CN, R ₆ is an alkyl group of C ₁ to ₄ , CH _{2 q} COOH (q represents an integer of 1 to 3),
CH _{2 q} SO ₃ H (q has the same meaning as above) or C
_{1 to 3} each represent a hydroxyalkyl group); (M represents the same meaning as described above) or (P represents the same meaning as described above), and n represents 0 or 1. ], Respectively. Further, α is a number of 1 to 3, β is a number of 0 to 2, and γ is a number of 1 to 4, respectively, α + β +
γ ≦ 4. Also, SO ₃ H, SO ₂ A and SO ₂ B bound to Pc
Each of which is bonded to a non-identical benzene ring of a phthalocyanine residue, and when Pc contains a metal, the metal is copper, zinc, aluminum or nickel. Wherein the water-soluble phthalocyanine compound and the free acid represented _{by} (2) (O 2 N} ) x-Ar- (SO 3 H) in y (2) (Equation (2), Ar is stilbene, naphthalene or anthraquinone Where x represents an integer of 1 to 2 and y represents an integer of 1 to 3), and a color filter containing a compound represented by