JP2579525B2 - Water-soluble phthalocyanine compound and method for coloring substrate surface film using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a water-soluble phthalocyanine compound and a method for coloring a substrate surface film using the same.

2. Description of the Related Art Transparent substrates such as glass and plastic are colored and used for sunglasses, show windows and various displays. Recently, these colored substrates are used for color separation of liquid crystal devices and color television cameras. It is used as a member of a device. 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, plastics, and the like, a method of adding a coloring agent in a process prior to molding into a predetermined shape, and then obtaining a colored product by molding is applied as the simplest method. Although this method is suitable for the purpose of obtaining a large amount of colored moldings of the same color at a time, it is not suitable for the purpose of obtaining small-scaled colored products, and this method It is not possible to provide parts having different color tones on the same molding. Therefore, for such purposes, a thin film of a transparent synthetic resin or gelatin, casein, glue or other protein-based natural high molecular weight material is provided on the substrate surface,
A method of coloring (or dyeing) this with a dye 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. In order to obtain a green colored film of a protein-based natural high molecular substance, particularly, a method of applying a yellow anionic dye and a blue anionic dye from the same dyeing bath or another bath is adopted. However, in this method, the desired green color is not obtained because the affinity of the anionic dye for the protein-based natural polymer substance differs depending on the dye used,
It has the disadvantage that reproducibility is not sufficient. Further, there is a disadvantage that the quality of the obtained protein-based natural high molecular substances such as gelatin, casein, glue and the like easily varies depending on the raw material source, and it is difficult to obtain a stable color.

On the other hand, color filters for LCD color television devices are also being developed. Color filters are roughly classified into three primary colors, that is, those composed of red, green, and blue, and those of complementary colors, that is, those composed of cyan, yellow, magenta, or two of them, and a transparent layer. Needless to say that the spectral characteristics of the filter determine the quality of color reproducibility of color solid-state imaging devices, color televisions, and the like, coloring with various dyes or a combination thereof has been attempted. However, cyan in the case of a complementary color system is particularly difficult to select, and it is difficult to find a dye having good spectral characteristics. Regarding the primary color green, it is difficult to find a dye having good spectral characteristics.

More recently, color filters have become more problematic in terms of robustness, especially light fastness, in view of outdoor use of liquid crystal color televisions.

Problems to be Solved by the Invention Gelatin used as a substrate film, casein, shows good dyeing properties to protein-based natural polymers such as glue or synthetic resins having a cationic group, and has good spectral characteristics and The development of blue-green anionic dyes having good light fastness has been desired.

Means for Solving the Problems The present inventors have made intensive efforts to develop a dye having the above-mentioned properties, and as a result, have reached the present invention.

That is, the present invention provides a compound of the formula (1) に お い て In the formula (1), Pc represents a metal-free or metal-containing phthalocyanine residue, 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), 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} SO ₃ H
(Q represents the same meaning as described above) or C _1-3 hydroxylalkyl, 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 from 1 to 3, β represents a number from 0 to 2 (excluding 0), and γ represents a number from 1 to 4, and α + β
+ Γ ≦ 4. SO ₃ H, SO ₂ A and SO ₂ bound to Pc
Each of B 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. A method for coloring a surface film of a substrate, characterized by using the water-soluble phthalocyanine compound represented by the formula (1) and the water-soluble phthalocyanine compound represented by the formula (1) in the form of a free acid.

The water-soluble phthalocyanine compound represented by the formula (1) is produced, for example, by the following method. That is, equation (2) (In formula (2), Pc, α, β, and γ represent the same meaning as described above) and a sulfonic acid chloride compound represented by the following formula (3) (where A represents the same meaning as described above): Or a compound of formula (2) and a compound of formula (3) and a compound of formula (4) (In the formula (4), C, R ₁ , R ₂ and n have the same meanings as described above).

Condensation reaction of the compound represented by the formula (2) with the compound represented by the formula (3), or condensation of the compound represented by the formula (2) with the compound represented by the formula (3) or the formula (4) 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. pH 2
~ 12 in the presence of an acid binder.

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. A usual separation method such as an acid precipitation method or a salting out method is applied for separating the target substance from the reaction solution thus obtained.

Specific examples of the compound represented by the formula (3) include the following. (In the examples, sulfonic acid groups and carboxyl groups are represented in a free form. The same applies hereinafter.) Next, specific examples of the compound represented by the formula (4) include the following.

In the formula (1), the compound in which B is NH ₂ is obtained by condensing a sulfonic acid chloride compound of the formula (2) with a compound of the formula (3) and a compound releasing ammonia such as ammonia or ammonium chloride or ammonium acetate. It is obtained by things. Further, for the compound in which B is OH in the formula (1), the sulfonic acid chloride compound of the formula (2) and the compound of the formula (3) are condensed and then subjected to heat treatment in an aqueous medium to hydrolyze the sulfonyl chloride group. Can be obtained by

Next, a protein-based natural polymer film such as gelatin, casein, and glue that can be used as a film in the present invention will be described. Gelatin is an animal protein in which collagen is irreversibly converted to water-soluble by boiling collagen, and is extracted by boiling with water using animal bones, skins, tendons and the like as raw materials. Casein is a phosphoprotein that is the main component of milk.

A few percent of a dichromate such as ammonium bichromate is added to an aqueous solution of these natural proteins, and the solution is uniformly applied on a flat substrate by a method such as spin coating. An insoluble film is formed.

Since the raw material source is animal,
Although it depends on the type, habitat, site, etc. of the animal, the difference does 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 and a quaternary ammonium base in a side chain, a photopolymerization initiator (B) and a solvent (C), or this resin composition Is further coated on the substrate surface using a photoreactive resin composition to which a compound (E) having two or more photoreactive unsaturated groups in one molecule is added, and then irradiated with actinic light to cause a reaction. To form a film. Polymer (A) having a photoreactive unsaturated group in its side chain and a quaternary ammonium base is (N, N-dimethylamino) ethyl acrylate, (N, N-diethylamino) ethyl acrylate,
A homopolymer or copolymer obtained by polymerizing a monomer having a tertiary amino group such as (N, N-dimethylamino) propylacrylamide is added to allylpromide,
It is obtained by reacting with an unsaturated compound having an active halogen atom such as chloro-2-methylpropene, p-chloromethylstyrene, and 3-chloro-2-hydroxypropyl methacrylate.

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 trimethylolpropane trimethacrylate. And the like.

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 natural or synthetic photoreactive resin composition is applied to the surface of a substrate and cured by irradiation with actinic light to obtain a film. The thickness of the coating is usually 0.5 to 1 micron. As the substrate, those having excellent transmission characteristics over the entire wavelength range of visible light are desirable. Generally, optical glass is used, but methyl methacrylate resin is used. Also, a plastic plate of a polystyrene resin, a polycarbonate resin or the like is used.

In order to color the film by using the compound represented by the formula (1), for example, an immersion method or a printing method is used, and particularly, an immersion dyeing method using an aqueous solution is convenient. in this case
0.1 to 30 g of the compound of formula (1) dissolved in water 1
The substrate provided with the film is immersed in a dye bath at 0 ° C. for 10 seconds or more, and then taken out and dried. The blue color thus obtained ~
The film colored in green not only exhibits favorable transmission spectral characteristics, but also has excellent resistance to light and also has characteristics that are not easily discolored.

The compounds of the present invention may be used alone or as a mixture of two or more.

The colored film obtained by the present invention is particularly useful as a color separation device for a color television camera and as a color filter for a liquid crystal color television device. To give a vivid hue color filter.

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. Cu ・ Pc ＝ Copper phthalocyanine skeleton Following structure Aqueous solution 1 adjusted to pH 7.5 containing 9.46 parts of the amino compound
To 10 parts, 19.4 parts of copper phthalocyanine-tetrasulfonic acid chloride is added as a wet paste under stirring at 10 ° C. or lower.
Then, 50 parts of an aqueous solution obtained by completely dissolving 2.78 parts of p-nitrophenol in an alkaline solution are added.

Then at 10-20 ° C. by addition of a 10% liquid caustic aqueous solution,
The reaction was carried out for 12 hours while maintaining the pH value at 9.0 to 10.0. Then, the temperature was raised to 70 ° C., and the reaction was carried out at this temperature for 2 hours. Thereafter, the pH was adjusted to 6.0 with dilute hydrochloric acid, and the crystals obtained by salting out with sodium chloride were filtered off and dried at 60 ° C. to obtain 26.0 parts of a compound of the formula (5). The wavelength indicating the maximum transmittance of the obtained compound in water (the same applies to λ _Tmax or less) is 526 n.
m, and the maximum absorption wavelength (λ _max ) was 425 nm and 667 nm.

Example 2. The liquid of the above composition is treated in a nitrogen atmosphere at 80 ° C. for 8 hours,
100 parts of a poly (N, N-dimethylamino) ethyl methacrylate solution are obtained. Chloromethylstyrene 1 was added to 50 parts of this solution.
After adding 5 parts at room temperature and reacting for 16 hours, this was added to 2-
It was dissolved in 260 parts of ethoxyethanol, and 16 parts of Irgacure 651 (a photopolymerization initiator manufactured by Ciba-Geigy) was added and dissolved to obtain a cationic group-containing photosensitive resin composition. Next, the surface of the optical glass (a high-purity glass plate excellent in light transmittance) is washed with acetone, dried, coated with a 10% ethanol solution of KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.), air-dried, and dried. This was dried by heating at 5 ° C. for 5 minutes, and the surface was further washed with acetone and dried to obtain a coating substrate.
The photosensitive resin composition was applied to a thickness of about 1 micron on the surface of the coating substrate by spin coating, and irradiated with ultraviolet light at 80 watt / cm for 4 seconds from a high-pressure mercury lamp to cure the coating. Next, the compound of Example 1 was dissolved in water adjusted to pH 4 with acetic acid so as to be a 0.1% aqueous solution, and the temperature was raised to 80 ° 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 having a λ _{Tmax of} 526 nm and having a clear green colored film was obtained.

Examples 3 to 16 The compounds were synthesized according to Example 1, and then the coating on the optical glass prepared according to Example 2 was subjected to the same dyeing operation as in Example 2, resulting in a good green hue. An optical glass having a coated film was obtained. Table 1 shows the structure of the compound, the hue of the colored film, and the λ _Tmax (nm) of the compound in water.

The substrates colored in Examples 2 to 24 were subjected to a light fastness test, and all showed good light fastness.

In the table, Zn · Pc, Ni · Pc and Al · Pc represent a zinc phthalocyanine skeleton, a nickel phthalocyanine skeleton and an aluminum phthalocyanine skeleton, respectively. Example 25. Under stirring, 17.4 parts of zinc phthalocyanine-trisulfonic acid chloride is added as a wet paste to 200 parts of an aqueous solution in which 3.68 parts of 2,4-dinitrophenol are completely dissolved at pH 10 at 10 ° C. or less.

Then at 10-15 ° C, by adding 10% liquid caustic aqueous solution
The reaction was carried out for 15 hours while maintaining the pH value at 10.0 to 11.0. Then, the temperature was raised to 50 ° 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, salted out with sodium chloride, and the obtained crystals were separated by filtration and dried at 80 ° C. to obtain 19.5 parts of a compound of the formula (6). (Λ _Tmax 498 nm) Example 26. The compound of Example 25 was dissolved in acetic acid (pH 4) water to a concentration of 0.05%, and the solution was heated to 90 ° C. An optical glass having a cured coating film on the surface obtained in the same manner as in Example 2 was immersed in this dye solution for 20 minutes.

An optical glass having λ _Tmax at 498 nm and having a clear blue colored film was obtained.

Examples 27 to 36. Compounds were synthesized according to Example 25, and then the same coloring operation as in Example 2 was performed on an optical glass having a coating film manufactured according to Example 2.

Table 2 shows the structural formula of the compound, the hue of the colored film, and λ _Tmax (nm) in water.

The substrates colored in Examples 26 to 36 were subjected to a light fastness test, and all showed good light fastness.

Example 37. A 10% aqueous gelatin solution containing 0.5% ammonium dichromate was uniformly applied on an optical glass substrate by spin coating, dried, cured by irradiating ultraviolet rays, and then cured.
After washing with warm water at 40 ° C. and drying, a photocrosslinked gelatin film was formed on an optical glass plate. A 0.5% aqueous solution of the compound of Example 1 was adjusted to pH 4 with acetic acid, and the optical glass having the above gelatin film was immersed in a dye bath heated to 60 ° C. for 20 minutes and washed with water.
When dried, an optical glass substrate having a green colored film having λ _Tmax at 526 nm was obtained.

A lightfastness test was performed on the colored substrates, which showed excellent lightfastness.

Examples 38 to 51. Compounds were synthesized according to Example 1, and then a coating on an optical glass prepared according to Example 37 was subjected to the same dyeing operation as in Example 37. As a result, a good green hue was obtained. An optical glass having a coated film was obtained.

Table 3 shows the structure of the compound, the hue of the colored film, and λ _Tmax (nm) of the compound in water.

The substrates colored in Examples 38 to 51 were subjected to a light resistance test, and all showed good light fastness.

Effect of the Invention A base film made of a protein-based natural polymer such as casein, gelatin, glue or a synthetic resin having a cationic group provided on a substrate such as glass or plastic, or a blue-green hue having excellent optical properties. (Color). The substrate having the colored film is excellent in optical properties and light fastness as a member of a color separation device.

Claims (2)

(57) [Claims] 1. Formula (1) in the form of the free acid に お い て In the formula (1), Pc represents a metal-free or metal-containing phthalocyanine residue, 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 of alkoxy, (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} SO ₃ H
(Q represents the same meaning as described above) or C _1-3 hydroxylalkyl, 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, α1 to 3 and β are 0 to 2 (however, 0
), Γ represents a number from 1 to 4, and α + β
+ Γ ≦ 4. SO ₃ H, SO ₂ A and SO ₂ bound to Pc
Each of B 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. A water-soluble phthalocyanine compound represented by｝ 2. A method for coloring a surface film of a substrate, comprising using a water-soluble phthalocyanine compound represented by the formula (1) in the form of a free acid.