JPH01319702A - Color filter - Google Patents

Abstract

PURPOSE:To prevent a colored coated film from discoloration in the absence of oxygen by providing a colored layer contg. a water-soluble phthalocyanine compd. expressed in a form of free acid by a specified formula and a compd. expressed also in a form of free acid by another specified formula to the colored coated film. CONSTITUTION:Discoloration of a colored film in the absence of oxygen is prevented by providing a colored layer contg. a water-soluble phthalocyanine compd. expressed by the formula I in a form of free acid and a compd. expressed also in a form of free acid and expressed by the formula II to the colored film. In the formula I, Pc is a metal-not-contg. phthalocyanine residue or a metal-contg. phthalocyanine residue; A is a group expressed by OH, NH2 or NHCOOH; B is OH, NH2, NHCH2COOH, etc.; alpha is 1 to 3; beta is zero to 2; gammais 1 to 4, wherein alpha+beta+gamma<=4. In the formula II, Ar is stilbene, naphthalene, or anthraquionone residue; x is an integer 1 or 2; y is an interger 1 to 3.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to color filters. More specifically, it relates to specific dyes and methods for coloring substrate surface films.

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

Conventional technology Transparent substrates such as glass and plastics are colored and used for sunglasses, shop windows, and various displays.More recently, these colored substrates have been used for liquid crystal devices, color television cameras, etc. It is used as a member of color separation devices. However, it cannot be said that a method for coloring substrates suitable for the purpose of use in such fields of use has been established. In other words, conventionally, in order to color glass, plastic, etc., a coloring agent is added in the process prior to molding it into a predetermined shape, then a coloring agent is added after molding, and then a coloring agent is added after molding. The method of obtaining is applied as the easiest method, but
Although this method is suitable for the purpose of obtaining a large amount of colored molded products with the same color tone at once, it is not suitable for the purpose of obtaining colored products on a small scale, and depending on this method, different color tones can be obtained. It is not possible to provide two parts on the same molded product. Therefore, for this purpose, a thin transparent synthetic resin layer or a film of a protein-based natural polymer material such as gelatin, casein, or glue is provided on the surface of the substrate, and this is colored (or The method of staining) is convenient. By the way, protein-based natural polymer substances such as gelatin, casein, and glue retain cationic groups and can generally be dyed with anionic dyes.

A method is adopted in which the dyes are applied from the same dye bath or from separate baths. However, this method has the disadvantage that the desired green tone may not be obtained or the reproducibility may not be sufficient because the affinity of the anionic dye for the protein-based natural polymer substance varies depending on the dye used.

Another disadvantage is that the quality of the obtained protein-based natural polymer substances such as gelatin, casein, and glue varies depending on the raw material source, making it difficult to obtain a stable color.

On the other hand, color filters are also being developed as devices for LCD color televisions. Color filters can be roughly divided into three primary colors, i.e., red, green, and blue, and complementary colors, i.e., cyan, yellow, magenta, or two of them.
There are filters that consist of a color and a transparent layer, but in either case, the spectral characteristics of the color filter determine the quality of color reproducibility of color solid-state imaging devices, color televisions, etc. Needless to say, attempts have been made to color with various dyes or combinations thereof. However, it is difficult to find a dye with good spectral properties for the complementary color cyan, and it is also difficult to find a dye with good spectral properties for the primary color green. Furthermore, recently, from the viewpoint of using liquid crystal color televisions outdoors, the fastness of color filters, particularly light resistance, has become a problem. With such excellent spectral properties,
The use of phthalocyanine dyes as cyan (complementary color) and green (primary color) dyes with good light resistance has been proposed.

Problems to be Solved by the Invention The compound represented by the formula (1) described below is a compound that contains protein-based natural polymers such as gelatin, casein, and glue, or cationic groups, which are often used as coatings to be colored in the production of color filters. The colored (dyed) coating film has excellent spectral properties and light fastness in the presence of oxygen, and has good dyeability for the synthetic resin. However, it has the disadvantage of causing discoloration in a light fastness test under oxygen cut conditions.

Means for Solving the Problems The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result they have arrived at the present invention. That is, the present invention provides a free acid form of the formula (1) (in formula (1), PC is a metal-free or metal-containing phthalocyanine residue, A is a group represented by OH, NR2, or NHCOOH, and B is a group represented by OH , NR2, NHCH2C0OH or NHCOCH3, NHCONH2, halogen or C1~
Al of C3 (R3, R4 are H, OH, Co OH, CH
3SC'2, CHa C0NH, NR2゜CI~C
3 alkyl group, C1 to C3 alkoxy group or halogen, m represents 0, 1 or 2, respectively)
(represents C2H5, COOH or N R2, respectively);
is the alkyl group of CI-4, +CHr+qCOOH (C
I represents 1 respectively); e(SO3H)m (
m represents the above-mentioned binding meaning), and n represents 0 or 1, respectively. ] respectively. Further, α represents a number from 1 to 3, β represents a number from O to 2, and γ represents a number from 1 to 4, respectively, but α+β10γ≦
It is 4. Furthermore, each of 5O3H, 5O2A, and 5O2B bonded to PC is assumed to be bonded to a benzene ring that is not the same as the phthalocyanine residue, and when Pc contains a metal, the metal is copper, zinc, aluminum, or nickel. Formula (2) % formula % (21 (In formula (2), Ar is stilbene, naphthalene or anthraquinone, X is 1 to 2, y is 1 ~ represents an integer of 3)
Provided is a color filter characterized by having a colored layer containing a compound represented by:

The color filter of the present invention will be explained in detail.

The phthalocyanine compound (dye) represented by formula (1) is produced, for example, according to the method described in Japanese Patent Application No. 102489/1989. That is, a sulfonic acid chloride compound of PC represented by formula (a) (in formula (a), PC9α, β and γ represent the same meanings as above) and a formula (
A compound represented by bl and a compound represented by formula (cl R1 (in formula (C), R++ R2+ n and C represent the same meanings as above) are reacted or a compound represented by formula (
It is obtained by reacting the compound of a) with the compound of formula (cl).

Further, specific examples of the compound represented by formula (2) used in the present invention include the following.

(Indicated as a free acid) n represents 1 to 10 Further, protein-based natural polymers such as vine gelatin and casein used as a film provided on a substrate in the present invention will be explained. Among these, gelatin is an animal protein that is irreversibly made water-soluble by boiling collagen with water.It is extracted from animal bones, skin, oboro, etc. by boiling it with water. Casein is a phosphorus protein that is the main component of milk.

Add a few percent of dichromate such as ammonium dichromate to an aqueous solution of these natural proteins, apply it uniformly onto the substrate using a method such as a spin code, and then completely cure when exposed to ultraviolet rays, making it water-insoluble. A film is formed.

Since the raw material source is an animal, the mechanical properties and dyeability of the film vary depending on the type, habitat, site, etc. of the animal, but these differences do not pose a problem for the film used in the present invention.

Examples of synthetic resin films containing cationic groups that can be used in the present invention include the following.

A polymer prisoner having a photoreactive unsaturated group and a quaternary ammonium base in its side chain, a photopolymerization initiator (Bl and a solvent (
Using a photoreactive resin composition consisting of C), or a photoreactive resin composition in which a compound (2) having two or more photoreactive unsaturated groups in one molecule is further added to this resin composition, After it is applied to the surface, it is irradiated with actinic rays to cause a reaction and form a film. Examples of polymer particles having a photoreactive unsaturated group and a 4R ammonium base in the side chain include (N,N-dimethylamino)ethyl acrylate,
(N,N-diethylamino)ethyl acrylate, (N
, N-dimethylamino)propylacrylamide, etc.
Active polymers such as allyl bromide, 3-chloro-2-methylpropene, p-chloromethylstyrene, and 3-chloro-2-hydroxypropyl methacrylate are added to the homopolymer or copolymer obtained by polymerizing monomers having a class amine group. - Obtained by reacting with an unsaturated compound having a rogene atom.

Examples of the compound (E) having two or more photoreactive unsaturated groups in one molecule include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, and trimethylolpronochloride. Examples include methacrylate.

As the photoreaction initiator CB+, 2-ethylanthraquinone, benzophenone, etc. can be used. The solvent FC+ may be any solvent that can dissolve the polymer (2), the photoreaction initiator (B), and the compound (El) well, for example, 2
-Methoxyethanol, 2-ethoxyethanol, toluene, xylene, etc. 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 to be applied is desirably one that has transmission characteristics over the entire wavelength range of visible light (generally optical glass is used, but methyl methacrylate resin,
Plastic plates such as polystyrene resin and polycarbonate resin are also used.

In order to incorporate the compound represented by formula (1) and the compound represented by formula (2) into the film, for example, a dipping method or a printing method is used, and a dipping dyeing method using an aqueous solution is particularly convenient. It is. In this case, formula (1) for 01 to 30g
and 0.1 to 30 g of the compound of formula (2) in water 1
After immersing the base material provided with the above-mentioned film in a dye bath at 10 to 100° C. in which the above-described film was dissolved in No. 2 for 10 seconds or more, it was taken out and dried.

The blue to green colored film thus obtained not only exhibits favorable transmission spectral characteristics, but also has excellent resistance to light, and is characterized by no discoloration, especially under oxygen cut conditions.

Note that the compounds of formula (1) and formula (2) may be used alone, but two or more of each may be used in combination.

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

Example The present invention will be explained in more detail by way of examples.

In the examples, parts indicate 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 azoin butyronitrile
... 1 part A mixture having the above composition is stirred at 80° C. for 8 hours in a nitrogen atmosphere to obtain 100 parts of a toluene solution containing poly(N,N-dimethylamino)ethyl methacrylate and azoisobutyronitrile.

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 Irgacure 651 (
16 parts of photopolymerization initiator (manufactured by Ciba Geigy) were added and dissolved to obtain a cationic group-containing photosensitive resin composition. On the other hand, the surface of the optical glass (glass plate with excellent light transmittance) was cleaned with acetone, dried, and then coated with a 10% ethanol solution of KBM503 (silane coupling agent, Shin-Etsu Chemical ff), air-dried, and heated at 110°C for 5 minutes. After heating and drying, the surface was further washed with acetone and dried to obtain a base material for coating. The above photosensitive resin composition was applied to the surface of this coating substrate to a thickness of about 1 micron by a spin code method, and the coating film was cured by irradiating ultraviolet light at 80 wait/cm for 4 seconds with a high-pressure mercury lamp.

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

After adjusting this aqueous solution to pH 5.5 with acetic acid,
The temperature was raised to C. The optical glass on which the cured coating film was formed was immersed in this solution for 20 minutes, then washed with water and dried, showing a maximum transmission wavelength (λmax) of 528 nm.
An optical glass plate (color filter) having a film colored in clear green was obtained. (Coloring treatment) This product had good not only spectral properties but also light fastness under oxygen cut.

The light resistance test under oxygen cut was conducted as follows.

(Similarly in the following examples) The optical glass plate having the green film obtained above and another transparent glass plate were
After screen-printing an epoxy adhesive containing a μm spacer, they were glued together and cured to create an empty cell with a gap of approximately 8 μm.Then, liquid crystal was injected under vacuum, and the injection port was sealed with adhesive. Fabricate a liquid crystal cell with a color filter inside. This product was subjected to an exposure test using a carbon arc fade meter, and the change in transmittance at the thickest transmitted wavelength before and after exposure was calculated as the transmitted light retention rate using the following formula.

Transmitted light retention Example 1 91% Comparative example 1 75% Comparative example 1 is the same as Example 1 except that the compound of formula (4) is not added.
The effect of adding the compound of formula (4) is clear.

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

pH 8 containing 9.5 parts of the amine compound represented by formula (5)
19.4 parts of copper phthalocyanine-tetrasulfonic acid chloride is added as an aqueous paste to 100 parts of an aqueous solution adjusted to 100 parts under stirring at a temperature below 10'C. Then, at around 10°C, the pH value was adjusted to 9.0 to 9.5 by adding an aqueous solution of caustic soda.
The reaction was carried out for 6 hours while maintaining the temperature.

The temperature was then raised to 70°C, and the reaction was continued at this temperature for an additional 2 hours. Thereafter, the pH value was adjusted to 6.5 to 7.0 with dilute hydrochloric acid, and salting out was carried out with sodium chloride. The precipitated crystals were filtered and dried at 60°C to obtain 26.0 parts of the compound of formula (3).

The amine compound shown in Bunbu (5) is obtained by coupling 4-acetylamino-2-amine benzenesulfonic acid in water at 5°C or below with a pyridone compound represented by diazo in a hydrochloric acid/sodium nitrite system by a conventional method. It is obtained by thermal hydrolysis (deacetylation) in the state.

Examples 2 to 13゜Using the compounds of formula (1) and formula (2) shown in Table 1,
Optical glass having a coating film prepared according to Example 1 (
Color filter) was subjected to coloring treatment in the same manner as in Example 1. Table 1 shows the structural formulas of the compounds represented by formulas (1) and (2), the hue of the colored film, and the transmitted light retention rate of the leaked colored optical glass.

Example 14 A 10% aqueous gelatin solution containing 0.5% ammonium dichromate was uniformly applied onto an optical glass substrate using a spin code method, dried, cured by irradiation with ultraviolet rays, and then washed with warm water at 40°C. After drying, a photocrosslinked gelatin film was formed on an optical glass plate.

On the other hand, 02 parts of the compound represented by the following formula (6), the above formula (4)
) is dissolved in 100 parts of water to prepare an aqueous solution.

This aqueous solution was adjusted to pH 4 with acetic acid and then heated to 60°C. When the above-mentioned optical glass having a hardened gelatin film was immersed in this solution for 20 minutes, washed with water and dried, the result was 535.
An optical glass substrate (color filter) having a green colored film with maximum transmittance in nm was obtained. A liquid crystal cell was prepared using the colored substrate, and a light resistance test was conducted under oxygen cut conditions, and the light resistance of this cell was found to be good. The transmitted light retention rate of this product was 85%.

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

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 to 100 parts of an aqueous solution adjusted to 100 parts under stirring at 10°C or less.

Then, at around 10°C, the pH was adjusted by adding an aqueous solution of caustic soda.
The reaction was carried out for 6 hours while maintaining the value between 9.0 and 9.5.

The temperature was then raised to 70°C, and the reaction was continued at this temperature for an additional 2 hours. Thereafter, the pH value was adjusted to 6.5 to 7.0 with dilute hydrochloric acid, and salting out was carried out with sodium chloride.

The precipitated crystals were filtered and dried at 60°C to give the formula (6
) was obtained.

Examples 15 to 26 Gelatin-coated optical glass prepared according to Example 14 was similarly dyed, resulting in gelatin-coated optical glass (color filter) having a good greenish hue.

Table 2 shows the structural formulas of the compounds represented by formula (1) and formula (2), the hue of the colored film, and the transmitted light retention rate of the colored optical glass.

Example 27゜ Gelatin-coated optical glass prepared according to Example 14 was dissolved in 0.1 part of the compound represented by formula (7) and 0.1 part of the compound represented by formula (4) above in 100 parts of water. and adjust the pH with acetic acid.
After adjusting the temperature to 5.5, it was immersed in a dyeing solution heated to 60°C for 20 minutes, washed with water, and dried. )was gotten. The transmitted light retention rate of this product was 85%.

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

Aqueous solution 2 in which 1.7 parts of glycine was completely dissolved at pH 10
Zinc phthalocyanine-
17 parts of trisulfonic acid chloride are added as a wet base. The reaction was then carried out at 10-15° C. for 15 hours while maintaining the pH value at 10.0-11.0 by addition of IO% liquid caustic aqueous solution. Then, the temperature was raised to 50°C, and the reaction was carried out at this temperature for 3 hours. After that, dilute hydrochloric acid p)(
(adjust the value to 3 and chloride) Salting out with IJum was performed, and the obtained crystals were filtered off and dried at 80°C to obtain 16 parts of the compound of formula (7).

Examples 28 to 33゜ Gelatin-coated optical glass was dyed according to Example 27 using the compounds represented by formulas (1) and (2) shown in Table 3 to produce a blue colored glass substrate (color filter). ) was obtained. Table 3 shows the structural formulas of the compounds represented by formula (1) and formula (2), the hue of the colored film, and the transmitted light retention rate of the colored glass substrate.

Examples 34 to 39 According to Example 1, acrylic photosensitive resin-coated optical glass was dyed using compounds represented by formulas (11 and (2)) shown in Table 4, and a good green color was obtained. A colored glass substrate (color filter) having a hue was obtained.Table 4 shows the formula (1).
) and the structural formula of the compound represented by formula (2), the hue of the colored film, and the transmitted light retention rate of the colored glass substrate are shown.

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

Claims (1)

[Claims] 1. Formula (1) in the form of a free acid ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) {In formula (1), Pc represents a metal-free or metal-containing phthalocyanine residue, A is a group represented by OH, NH_2 or NHCOOH, B is OH, NH_2, NHCH_2COO
H or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R_1, R
_2 is H, CH_3, COOH, NHCOCH_3, N
HCONH_2, halogen or alkoxy group of C_1 to C_3, C is ▲There are numerical formulas, chemical formulas, tables, etc.▼(Y
is H, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_3, R_4 are H, OH, COOH, CH_3SO_2, CH_3CO
NH, NH_2, C_1 to C_3 alkyl group, C_1
~ C_3 alkoxy group or halogen, m represents 0, 1 or 2 respectively) or ▲ Numerical formula, chemical formula, table, etc. ▼ (p represents an integer from 0 to 3), Z is CH_3, C_2H_5
, COOH or NH_2 respectively); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_5 is CONH_2, CH_2SO_3H or CN, R_6 is an alkyl group of C_1_-_4, ▲There are mathematical formulas, chemical formulas, tables, etc.) (q represents an integer from 1 to 3), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (q represents the same meaning as above) or C_1_ to_3 hydroxyalkyl groups, respectively); ▲ Numerical formulas, chemical formulas, There are tables, etc. ▼ (m represents the same meaning as above) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (p represents the same meaning as above), and n represents 0 or 1, respectively. ] respectively. Further, α represents a number from 1 to 3, β represents a number from 0 to 2, and γ represents a number from 1 to 4, respectively, and α+β+γ≦4. Also, each of SO_3H, SO_2A and SO_2B bonded to Pc is assumed to be bonded to a different benzene ring of a phthalocyanine residue, and when Pc contains a metal, the metal is copper, zinc, aluminum or It is nickel. } As a water-soluble phthalocyanine compound and free acid represented by formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In formula (2), Ar is still pen, naphthalene or anthraquinone, and x is 1 ~2, y represents an integer of 1 to 3) A color filter characterized by having a colored layer containing a compound represented by