JP2534896B2 - Color filter - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color filter. More specifically, it relates to a color filter having a surface film containing a specific dye and a specific compound.

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. By the way, since protein type natural high molecular weight substances such as gelatin, casein and glue have a cationic group, they can generally be dyed (colored) 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. or,
There is also a drawback in that the quality of 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, and A is B is OH, NH ₂ or [R ₁ and R ₂ are H, CH ₃ , COOH, NHCOCH ₃ , NHCONH ₂ , halogen or C
_1-3 alkoxy, C is (R ₃ and R ₄ are H, OH, COOH, CH ₃ SO ₂ , CH ₃ CONH, NH ₂ , C _1-3 alkyl, C _1-3 alkoxy or halogen, and m is 0,
1 or 2 respectively) or (P represents 0, 1, 2 or 3), Z represents CH ₃ , C ₂ H ₅ , COOH or
NH ₂ ); (R ₅ is CONH ₂ , CH ₂ SO ₃ H or CN, R ₆ is C _1-4 alkyl, CH _{2 q} COOH (q represents 1, 2 or 3), CH _{2 q} S
O ₃ H (q represents the same meaning as described above) or C _1-3 hydroxyalkyl, 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 represents a number of 1 to 3, β represents a number of 1 to 2, and γ represents a number of 0 to 4, respectively, and α + β + γ ≦ 4. Each of SO ₃ H, SO ₂ A and SO ₂ B bound to Pc is bound to a non-identical benzene ring of a phthalocyanine residue, and when Pc contains a metal, the metal is copper, Zinc, aluminum or nickel. } (2) (O ₂ N _x Av- (SO ₃ H) _y (2) as a water-soluble phthalocyanine compound represented by the formula (2) (Av in the formula (2) is stilbene, naphthalene, naphthalene formalin condensate or Anthraquinone x is 1 to 11,
y represents 1 to 11), and a color filter is provided.

The water-soluble phthalocyanine compound represented by the formula (1) is produced, for example, by the following method. That is, formula (3) (In the formula (3), α, β and γ represent the same meanings as described above) and a sulfonic acid chloride compound represented by the formula (4) HA (4) (A in the formula (4) has the same meaning as described above. Or a compound represented by formula (4) and formula (5) (In the formula (5), C, R ₁ , R ₂ and n have the same meanings as described above) and can be obtained by condensation.

Condensation reaction between the compound represented by formula (3) and the compound represented by formula (4), or condensation between the compound represented by formula (3) and the compounds represented by formula (4) and formula (5) The reaction is carried out in water, in an aqueous organic solvent or in an organic solvent at a temperature of 0 to 100 ° C
Values 2-12 are carried out in the presence of acid binders.

As the acid binder in these condensation reactions, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are used. In order to separate the thus obtained target substance from the reaction solution, an ordinary separation method such as an acid precipitation method or a salting out method is applied.

Specific examples of the compound represented by the formula (4) include the followings. (In the examples, sulfonic acid groups and carboxyl groups are represented in a free form. The same applies hereinafter.) Next, the following are mentioned as a specific example of the compound represented by Formula (5).

Specific examples of the compound represented by the formula (2) include the followings. (The sulfonic acid group is represented as a free acid) Next, a protein-based natural polymer such as gelatin or casein used as a film provided on a 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 it with water. Yes, while casein is a phosphoprotein that is the main constituent 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 or the like in which a compound (E) having two or more unsaturated groups capable of photoreacting in one molecule is further added to the base material surface, and then the active light ray is irradiated,
The reaction is performed 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 -Homopolymers or copolymers 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- It is obtained by reacting with an unsaturated compound having an active halogen atom such as 2-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 as long as it can dissolve the polymer (A), the photoreaction initiator (B) and the compound (E), for example, 2
-Methoxyethanol, 2-ethoxyethanol, toluene, xylene and the like are 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" means "parts by weight", and sulfonic acid groups and carboxyl groups are shown in the form of free acids.

Example 1. Toluene ...... 69 parts (N, N-dimethylamino) ethyl methacrylate ...... 30
Part Azoisobutyronitrile ...... 1 part The liquid of the above composition is treated in a nitrogen atmosphere at 80 ° C for 8 hours, poly (N, N-dimethylamino) ethyl methacrylate solution 1
Get 00 copies.

Chloromethylstyrene (15 parts) was added to this solution (50 parts) at room temperature and reacted for 16 hours. This was dissolved in 2-ethoxyethanol (260 parts) and further Irgacure 651 (Ciba-Geigy photopolymerization initiator) (16 parts). Was added and dissolved to obtain a cationic group-containing photosensitive resin composition. Next, wash the surface of the optical glass (high-purity glass plate with excellent light transmission) with acetone, dry it, and then use KBM503 (silane coupling agent,
A 10% ethanol solution (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied, air-dried, and then heated and dried at 110 ° C. for 5 minutes, and the surface was washed with acetone and dried to obtain a coating substrate. The photosensitive resin composition was applied to the surface of the coating substrate by a spin coating method to a film thickness of about 1 micron, and ultraviolet rays of 80 wa were applied by a high pressure mercury lamp.
The coating film was cured by irradiation at tt / cm4 for 4 seconds. Next, 0.3 part of the compound represented by the formula (6) and 0.2 part of the compound represented by the formula (7) are added to water.
Prepare an aqueous solution dissolved in 100 parts.

This aqueous solution was adjusted to pH 5.5 with acetic acid and then heated to 60 ° C. When the optical glass on which the above-mentioned cured coating film was formed was immersed in this solution for 20 minutes, an optical glass plate (color filter) having a clear green-colored film having a maximum transmission wavelength of 528 nm was obtained. As a green for a color filter, this product was excellent not only in spectral characteristics but also in light fastness under oxygen cut.

The light resistance test under oxygen cutting was performed as follows. Screen printing an epoxy adhesive containing 8 μm spacers on an optical glass plate with a colored film and another transparent glass plate without a film, and then laminating them together to cure them and curing them Then, a liquid crystal is injected in a vacuum and the injection port is sealed with an adhesive to prepare a liquid crystal cell having a green color filter inside. Exposure test this with a carbon arc fade meter,
The change in the transmittance at the maximum transmission wavelength before and after the exposure was represented as the transmitted light retention by the value defined by the following formula.

Example 1 91% Comparative Example 1 87% Comparative Example 1 was carried out according to Example 1 except that the compound of formula (7) was not added, and the effect of the compound of formula (7) is clear. .

The compound represented by the formula (6) was synthesized as follows.

To 100 parts of an aqueous solution containing 9.5 parts of the amino compound represented by the formula (8) and adjusted to pH 7.5, 19.4 parts of copper phthalocyanine-tetrasulfonic acid chloride is added as a wet paste at 10 ° C. or lower with stirring. Then 2,4-dinitrophenol 3.7
50 parts of an aqueous solution in which all parts are completely dissolved is added. Then, the reaction was carried out for 12 hours while maintaining the pH value at 9.0 to 10.0 by adding 10% liquid caustic aqueous solution at 10 to 20 ° C. After that, the pH value was adjusted to 6.0 with dilute hydrochloric acid and salted out with sodium chloride, and the obtained crystals were separated by filtration and dried at 60 ° C. to obtain the formula (6).
26.2 parts of a compound of

Examples 2 to 21. The same dyeing operation as in Example 1 was performed using the compounds shown in Table 1 on the optical glass having a resin film produced according to Example 1. In the table, the phthalocyanine compound of formula (1), the structural formula of the compound of formula (2), the hue of the colored film,
The maximum transmission wavelength λmax (nm) and the transmitted light retention rate (%) are shown.

When the light resistance test of the colored substrates obtained in Examples 2 to 21 was carried out, they all had excellent light resistance.

Example 22 A 10% aqueous gelatin solution containing 0.5% ammonium dichromate was uniformly applied onto an optical glass substrate 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. Next, a compound of the formula (9) 0.
An aqueous solution is prepared by dissolving 3 parts and 0.2 part of the compound represented by the formula (10) in 100 parts of water.

This aqueous solution was adjusted to pH 4 with acetic acid and then heated to 60 ° C. In this solution, the optical glass having the above-mentioned gelatin hardened film was dipped for 20 minutes, washed with water and dried to obtain 535 nm.
An optical glass substrate with a green colored coating with maximum transmission was obtained. A liquid crystal cell was prepared using the colored substrate, and a light resistance test under oxygen cutting was carried out. As a result, the light resistance of this product under oxygen cutting was extremely good, and the transmitted light retention rate was 97%.

The compound represented by the formula (9) was synthesized as follows.

To 100 parts of an aqueous solution containing 9.5 parts of the amino compound represented by the formula (8) and adjusted to pH 7.5, 17 parts of zinc phthalocyanine-trisulfonic acid chloride is added as a wet paste at 10 ° C. or lower with stirring. Then, 50 parts of an aqueous solution in which 3.7 parts of 2,4-dinitrophenol are completely dissolved in an alkaline solution are added. next
At around 10 ℃, pH value of 9.0 ~ by adding caustic soda solution
The reaction was carried out for 6 hours while maintaining 9.5. 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 were separated by filtration and dried at 60 ° C. to obtain 24 parts of the compound of the formula (9).

Examples 23 to 29. As a result of similarly dyeing the gelatin-coated optical glass produced according to Example 22, gelatin-coated optical glass having a favorable greenish to blue hue was obtained.

Table 2 shows the structural formula of the phthalocyanine compound of formula (1) and the compound of formula (2), the hue of the colored film, the maximum transmission wavelength (λmax), and the transmitted light retention rate.

Effects of the Invention A specific phthalocyanine compound and a specific sulfone group are added to a base film made of a protein-based natural polymer such as gelatin, casein, or glue provided on a substrate such as glass or plastic or a synthetic resin having a chaotic group. A substrate (color filter) having a blue to green colored (dyed) film having excellent optical properties was obtained by incorporating the compound having the compound. The substrate (color filter) with this colored film is excellent as a member of the color separation device,
In addition, the light fastness to light under oxygen cutting, which has been a particular problem in the past, has been remarkably improved.

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, and A is B is OH, NH ₂ or [R ₁ and R ₂ are H, CH ₃ , COOH, NHCOCH ₃ , NHCONH ₂ , halogen or C
_1-3 alkoxy, C is (R ₃ and R ₄ are H, OH, COOH, CH ₃ , SO ₂ , CH ₃ CONH, NH ₂ , C _1-3 alkyl, C _1-3 alkoxy or halogen, and m is 0,
Represents 1 or 2, respectively) or (P represents 0, 1, 2 or 3) and Z represents CH ₃ , C ₂ H ₅ , COOH or NH ₂ , respectively; (R ₅ is CONH ₂ , CH ₂ SO ₃ H or CN, R ₆ is C _1-4 alkyl, CH _{2 q} COOH (q represents 1, 2 or 3), CH _{2 q} S
O ₃ H (q represents the same meaning as described above) or C _1-3 hydroxyalkyl, 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 represents a number of 1 to 3, β represents a number of 1 to 2, and γ represents a number of 0 to 4, respectively, and α + β + γ ≦ 4. Each of SO ₃ H, SO ₂ A and SO ₂ B bound to Pc is bound to a non-identical benzene ring of a phthalocyanine residue, and when Pc contains a metal, the metal is copper. ,
Zinc, aluminum or nickel. } As a water-soluble phthalocyanine compound represented by the formula (2) (O ₂ N _x Av- (SO ₃ H) _y (2) (in the formula (2), Av is stilbene, naphthalene, or naphthalene formalin condensate) Or anthraquinone, x is 1 to 11
And y represents 1 to 11). A color filter containing a compound represented by