JPH0411672B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a method for coloring a substrate surface film using a water-soluble phthalocyanine compound. ``Prior art'' Transparent substrates such as glass and plastic are colored and used in sunglasses, shop windows, and various displays, and recently these colored substrates have been used in liquid crystal devices, color television cameras, etc. It also came to be used as a component of color separation devices. However, it cannot be said that a method for coloring substrates suitable for the purpose of use in such recent fields of use has been established. In other words, conventionally, in order to color glass, plastic, etc., in the process prior to molding it into a predetermined shape,
The easiest method is to add a coloring agent and then mold it to obtain a colored product, but this method is not suitable for the purpose of obtaining a large amount of colored molded products of the same color at once. However, this method is not suitable for the purpose of obtaining colored products on a small scale, and it is not possible to provide parts with different color tones on the same molded product using this method. Therefore, for this purpose, a thin film of transparent synthetic resin or protein-based natural polymer substances such as gelatin, casein, or glue is provided on the surface of the substrate, and this is colored (or dyed) using a dye. ) is convenient. By the way, protein-based natural polymer substances such as gelatin, casein, and glue retain cationic groups and can therefore be dyed with anionic dyes. In order to obtain a particularly green colored film of protein-based natural polymer substances, a method has been adopted in which a yellow anionic dye and a blue anionic dye are applied from the same dye bath or from separate baths. However, this method may not produce the desired green tone because the affinity of the anionic dye for protein-based natural polymer substances differs depending on the dye used.
The conclusion is that the reproducibility is not sufficient. Another drawback 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, methods using synthetic resin base materials with cationic groups in place of protein-based natural polymers such as gelatin, casein, and glue have been carried out, but these base materials can be colored green with the desired optical properties. Anionic dyes that provide color cannot be found among existing dyes. ``Problems to be Solved by the Invention'' A green anionic dye that exhibits good dyeing properties for protein-based natural polymers such as gelatin, casein, and glue or synthetic resins having cationic groups used as a base film. Development is desired. "Means for Solving the Problems" The present inventors have made earnest efforts to develop a dye having the above-mentioned properties, and as a result, have arrived at the present invention. That is, the present invention provides the formula () in the form of a free acid. [In formula (), Pc is a metal-containing phthalocyanine residue, A is NH ₂ , R ₁ and R ₂ are H, CH ₃ , COOH,
_NHCOCH3 , _NHCONH2 , chloro _atom or _C1-3
an alkoxy group, n is 0 or 1, B is (In the above formula _, X is an alkyl ( _C1-8 ) amino group, a phenyl-substituted alkyl ( _C1 - _C3 ) amino group,
Hydroxyalkyl ₍ C _1-5 ) amino group, alkoxy (C _{1-3 )} alkyl (C _2-4 ) amino group _{, phenoxyalkyl (C 1-3 )} amino group, cyclohexylamino group, _morpholino group, substituent (a methoxy group, a carboxyl group, a sulfonic acid group, a methyl group, or a chloro atom) or a naphthylamino group substituted with 1 or 2 sulfonic acid groups. ); (In the above formula, X has the same meaning as above, or m represents 1 or 2.); (In the above formula, X represents the same meaning as above, and n
represents 0 or 1); (In the above formula, n represents 0 or 1.) or -NH-, and further C is (In the above formula, Y is H, (R ₃ and R ₄ are H, OH, COOH, CH ₃ SO ₂ ,
CH ₃ CONH, represents a methyl group, a C ₁ to ₃ alkoxy group, or a chloro atom; represents 0 or 1) or (p represents an integer from 1 to 3); Z represents CH ₃ , C ₂ H ₅ , COOH or NH ₂ ); (In the above formula, R ₅ is CONH ₂ , CH ₂ SC ₃ H or
CN, _R6 is _C2H5 , _{C3H7 , C4H9} , _{( -CH2 ) -q}
COOH (q represents an integer from 1 to 5), (−CH ₂ ) − _r
SO ₃ H (r represents an integer of 1 to 3), represents a C ₁ to ₅ hydroxyalkyl group. ); (l' means 1) or (P' represents an integer from 1 to 3). α represents a number from 0 to 3, β represents a number from 1 to 2, and γ represents a number from 1 to 4, but α+β+γ
≦4. However, SO ₃ H, SO ₂ A and each of which is bonded at the 3 or 4 position to the non-identical benzene ring of the phthalocyanine, and the metal contained in Pc is copper, zinc, aluminum or nickel. ] This invention relates to a method for coloring a base film made of a protein-based natural polymer substance or a synthetic resin having a cationic group, which is characterized by using a water-soluble phthalocyanine compound represented by the following. The water-soluble phthalocyanine compound represented by the formula () is produced, for example, by the following method. That is, the expression () [In formula (), A, α, β, and γ represent the same meanings as above, and D is

[Formula] -NH (- CH ₂ CH ₂ ) - _n NH - (where m represents the same meaning as above) or

[Formula] (where n represents the same meaning as above). ] Compounds represented by and formula () [In the formula (), C, R ₁ , R ₂ and n represent the same meanings as above] and then () Q-H () (in the formula (), Q represents the above-mentioned X) amines represented by atoms or groups (representing groups excluding chlorine and hydroxyl groups), or (A, α, β, and γ in formula () have the same meanings as above) and a sulfonic acid chloride compound represented by formula () (C, R ₁ , R ₂ and n in formula () have the same meanings as above) or a compound represented by formula () (In formula (), C, R ₁ , R ₂ and n have the same meanings as above). The condensation reaction between the compound represented by formula () and the compound represented by formula () is carried out in water, an aqueous organic solvent, or an organic solvent at a temperature of 20 to 80°C and a pH value of 4 to 10 in the presence of an acid binder. be exposed. Further, the condensation of the product obtained by condensation of the compound represented by formula () with the compound represented by formula () and the amine represented by formula () is carried out at a temperature of 30 to 100°C and a pH value of 4 to 4.
10 in the presence of an acid binder. Also, a compound represented by formula () and formula () or formula ()
The condensation reaction with the compound represented by
℃, pH value 4-10 and in the presence of an acid binder. The acid binders used in these condensation reactions include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide,
Potassium hydroxide, lithium hydroxide, etc. are used. A conventional separation method such as an acid precipitation method or a salting out method is applied to separate the target product thus obtained from the reaction solution. Specific examples of the compound represented by formula () include the following. (In the examples, sulfonic acid and carboxyl groups are expressed in free form. The same applies hereinafter.) (The sulfonic acid group is bonded to the 2- or 31-position of the benzene nucleus) (The sulfonic acid group is bonded to the 2- or 3-position of the benzene nucleus) In addition, in the above specific examples, the numbers 3 and 4 indicated as Pc(3) and Pc(4) represent the 3- or 4-bond positions of the benzene rings, which are not the same, of the phthalocyanine,
Decimal values for α, β, and γ indicate average compositions. Next, specific examples of the compound represented by formula () include the following. Next, specific examples of the compound represented by formula () include the following. Methylamine, ethylamine, n-propylamine, t-butylamine, hydroxyethylamine, hydroxypropylamine, γ-hydroxyhexylamine, 2-phenylethylamine, 2
-Ethylhexylamine, 2-methoxyethylamine, 3-ethoxypropylamine, phenoxyethylamine, impropoxyethylamine, 2
-ethoxyethylamine, cyclohexylamine, morpholine, aniline, m-chloroaniline, p-chloroaniline, o-chloroaniline,
2-chlorotoluidine, m-toluidine, anthranilic acid, methyl anthranilate, sulfanilic acid, metanilic acid, ortanilic acid, (2-,3-,
or 4-carboxy)aniline, (2-,3-,
or 4-ethyl)aniline, (2-,3-,4-
ethoxy)aniline, (2-,3-,4-ethoxy)aniline

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[Formula] Next, specific examples of the compound represented by the formula () include the following. Furthermore, specific examples of the compound represented by formula () include the following. The protein-based natural polymeric cortex such as gelatin, casein, and glue used in the present invention will be explained. Gelatin is an animal protein made by boiling collagen with water to irreversibly make it water-soluble.
It is extracted from skin, tendons, etc. by boiling it with water. Casein is a phosphorus protein 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, and the mixture is applied uniformly onto a flat substrate using a method such as spin coating, and is completely cured when exposed to ultraviolet light.
A water-insoluble film is formed. Since the raw material source is animal, the physical properties and dyeability of the film depend on the type of animal,
Although it varies depending on habitat value, location, etc., these differences do not pose a problem for the coating used in the present invention. Further, examples of the synthetic resin film having a cationic group used in the present invention include the following. Polymer (A) having a photoreactive unsaturated group and a quaternary ammonium base in its side chain and a photopolymerization initiator (B)
and a photoreactive resin composition consisting of a solvent (C), or a photoreactive resin composition in which a compound (E) having two or more photoreactive unsaturated groups in one molecule is further added to this resin composition. After applying it to the base material surface using
A film is formed by irradiating active light and causing a reaction. Polymer (A) having a photoreactive unsaturated group and a quaternary ammonium base in the side chain is (N,
N-dimethylamino)ethyl acrylate, (N,
N-diethylamino)ethyl acrylate, (N,
Allyl bromide, 3-chloro-2-methylpropene, p
- It is obtained by reacting with an unsaturated compound having an active halogen atom such as 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. etc. As the photoreaction initiator (B), 2-
Ethyl anthraquinone, benzophenone, etc. can be used. The solvent (C) may be any solvent that can dissolve the polymer (A), photoinitiator (B), and compound (E) well, such as 2-methoxyethanol, 2-methoxyethanol, and 2-methoxyethanol.
- 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 light to form a film.
It is desirable that the base material has excellent transmission characteristics over the entire wavelength range of visible light, and optical glass is generally used, but plastic plates such as methyl methacrylate resin, polystyrene resin, and polycarbonate resin are also used. used. To color the film using the compound represented by the formula (), for example, a dipping method or a printing method is used, and a dipping method using an aqueous solution is particularly convenient. In this case, the base material provided with the above film is immersed for 10 seconds or more in a dye bath containing 0.1 to 30 g of the compound of formula () dissolved in 1 part of water at a temperature of 10 to 100°C, and then taken out and dried. The green colored film thus obtained not only exhibits favorable transmission properties, but also has excellent light resistance and does not easily fade. "Example" The present invention will be explained in more detail with reference to Examples.
In the examples, parts indicate parts by weight, and sulfonic acid groups and carboxyl groups are expressed in free form. Example 1 A suspension was prepared by adding 3.8 parts of cyanuric chloride to a solution consisting of 40 parts of water, 60 parts of ice, and 0.5 part of a 10% Liponox NA aqueous solution (Lion Oil Co., Ltd., dispersant) with stirring. After stirring for 30 minutes, containing 5.8 parts of methamic acid, PH=
50 parts of an aqueous solution adjusted to a temperature of 7 to 8 was poured into the suspension at 10° C. or lower over 1 hour. Then below 20℃
A 10% aqueous soda ash solution was added dropwise and the reaction was carried out for 4 hours while maintaining the pH value at 4 to 6. Then, the reaction solution was
℃ or less, 4 parts of concentrated hydrochloric acid was added, and after stirring for 30 minutes, 3.8 parts of a 40% sodium nitrite aqueous solution was added dropwise at the same temperature. After stirring at 5° C. or below for 2 hours, excess nitrite ions were removed with sulfamic acid. Contains 6.4 parts of a compound with the following structure, pH = 7~ 50 parts of an aqueous solution adjusted to pH 8 was gradually poured into the diazo liquid and stirred for 4 hours at below 10°C, then the pH was adjusted to 6 with a 10% aqueous soda ash solution and further stirred for 4 hours at room temperature. 16.5 parts of a compound having the following structure was added at once to the reaction solution thus obtained. After stirring at room temperature for 1 hour, the reaction solution was heated to 45° C. and stirred at the same temperature for 24 hours while maintaining the pH value at 4 to 6. After the reaction was completed, the temperature was returned to room temperature and the pH was adjusted to 7. 1.5 parts of morpholine was added to this reaction solution, the temperature was raised to 80°C, and the mixture was stirred at the same temperature for 4 hours. The reaction solution was then cooled to 25°C and salted out with sodium chloride. The crystals were filtered and dried at 60°C to obtain 30.0 parts of the compound of the above formula. λmax520nm (water) Example 2 Toluene...69 parts (N,N-dimethylamino)ethyl methacrylate...30 parts Azoisobutyronitrile...1 part A liquid with the above composition was treated at 80°C in a nitrogen atmosphere for 8 hours. , 100 parts of poly(N,N-dimethylamino)ethyl methacrylate solution are obtained. After adding 15 parts of chloromethylstyrene to 50 parts of this solution at room temperature and reacting for 16 hours, this was mixed with 2-ethoxyethanol.
Dissolve in 260 parts and add Irugakiyua 651 (Ciba・
A cationic group-containing photosensitive resin composition was prepared by adding and dissolving 16 parts of photopolymerization initiator (manufactured by Geigy). Next, the surface of the optical glass (a high-purity glass plate with excellent light transmittance) is cleaned with acetone, and after drying,
A 10% ethanol solution of KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied, air-dried, and then heated and dried at 110°C for 5 minutes.The surface was further washed with acetone and dried to provide 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 spin coating, and the coating was cured by irradiating it with ultraviolet light at 80 Watt/cm for 4 seconds using a high-pressure mercury lamp. Next, Example 1 was added to water adjusted to pH 4 with acetic acid.
Dissolve the compound to make a 0.05% aqueous solution 80
The temperature was raised to ℃. When the optical glass on which the cured coating film was formed was immersed in this solution for 20 minutes, an optical glass plate with a clear green colored film was obtained which exhibited a λmax of 520 nm. Examples 3 to 40 Compounds were synthesized according to Example 1, and then a coating on optical glass prepared according to Example 2 was dyed in the same manner as in Example 2. As a result, a good greenish hue was obtained. An optical glass with a film was obtained. Table 1 shows the formula of the compound, the hue of the colored film, and the λmax (nm) of the compound in water.

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[Table] Example 41 Structure below To 100 parts of an aqueous solution containing 10.7 parts of the amino compound and adjusted to pH 7.5, 19.4 parts of copper phthalocyanine-(3)-tetrasulfonic acid chloride is added as a wet paste under stirring at 10°C or less. Next, 0.5 part of pyridine was added, and the mixture was reacted at about 10° C. for 4 hours while maintaining the pH value at 6.5 to 7.0 by adding a 10% aqueous soda ash solution. Then, the temperature was raised to 40°C, and the reaction was continued at this temperature for an additional 10 hours. The crystals obtained by acid salting out with hydrochloric acid and sodium chloride were filtered and dried at 60°C to obtain 28.0 parts of the compound of the above formula. Example 42 The compound of Example 41 was added to acetic acid acidic (PH value 4) water.
It was dissolved to a concentration of 0.1%, and the temperature of this solution was raised to 90°C. In this dye solution, 20 pieces of optical glass having a hardened coating film on the surface obtained in the same manner as in Example 2 was placed.
Soaked for minutes. An optical glass having λmax at 500 nm and a film colored in clear green was obtained. Examples 43 to 82. Compounds were synthesized according to Example 1, and then optical glass having a coating film prepared according to Example 2 was subjected to the same coloring operation as in Example 42. The table shows the structural formula of the compound, the hue of the colored film, and the λmax in water.
(nm).

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[Table] Example 92 A 10% aqueous gelatin solution containing 0.5% ammonium dichromate was applied uniformly on an optical glass substrate by spin coating, dried, cured by irradiation with ultraviolet rays, and then coated with hot water at 40°C. was washed and dried to form a photo-crosslinked gelatin film on an optical glass plate. A 0.5% aqueous solution of the compound of Example 41 was diluted to pH4 with acetic acid.
The optical glass substrate with the above gelatin film was immersed for 20 minutes in a dye bath heated to 60°C, washed with water, and dried, resulting in an optical glass substrate with a green colored film with λmax at 510 nm. Obtained. (Application example) Color filters are used to make full-color LCD active matrix panels.
A color filter is a mosaic pattern made of colored gelatin or casein placed on an optical glass substrate.The three primary colors of red, green, and blue are usually created using photolithography technology, and the light source placed on the back of the panel is used as a color filter. It is designed to pass through a filter and express the color. In order to reproduce colors that feel natural, red, green, and blue each need to have specific optical properties and be balanced with each other, and green in particular is an important element that governs color balance. The panels equipped with color filters colored with Kayanol Milling Red GRN for red, Kayanol Cyanine 6B for blue, and the compound of the present invention for green reproduced natural colors and were vivid. "Effects of the Invention" A base film made of a protein-based natural polymer such as casein, gelatin, or glue or a synthetic resin having a cationic group provided on a substrate such as glass or plastic can be coated with a single film represented by the formula (). Using compounds, it has become possible to color (dye) greenish hues with excellent optical properties. A substrate with this colored film is excellent as a member of a color separation device.

Claims (1)

[Claims] 1 Formula () in the form of free acid [In formula (), Pc is a metal-containing phthalocyanine residue, A is NH ₂ , R ₁ and R ₂ are H, CH ₃ , COOH,
_NHCOCH3 , _NHCONH2 , chloro _atom or _C1-3
an alkoxy group, n is 0 or 1, B is (In the above formula _, X is an alkyl ( _C1-8 ) amino group, a phenyl-substituted alkyl ( _C1 - _C3 ) amino group,
Hydroxyalkyl ₍ C _1-5 ) amino group, alkoxy (C _{1-3 )} alkyl (C _2-4 ) amino group _{, phenoxyalkyl (C 1-3 )} amino group, cyclohexylamino group, _morpholino group, substituent (a methoxy group, a carboxyl group, a sulfonic acid group, a methyl group, or a chloro atom) or a naphthylamino group substituted with 1 or 2 sulfonic acid groups. ); (In the above formula, X has the same meaning as above, or m represents 1 or 2.); (In the above formula, X represents the same meaning as above, and n
represents 0 or 1); (In the above formula, n represents 0 or 1.) or -
NH-, and C is (In the above formula, Y is H, (R ₃ and R ₄ are H, OH, COOH, CH ₃ SO ₂ ,
CH ₃ CONH, methyl group, C ₁ to ₃ alkoxy group or chloro atom, l represents 0 or 1) or (p represents an integer from 1 to 3); Z represents CH ₃ , C ₂ H ₅ , COOH or NH ₂ ); (In the above formula, R ₅ is CONH _2, CH ₂ SO ₃ H or
CN, _R6 is _C2H5 , _{C3H7 , C4H9} , _{( -CH2 ) -q}
COOH (q represents an integer from 1 to 5), (−CH ₂ ) − _r
SO ₃ H (r represents an integer of 1 to 3), represents a C ₁ to ₅ hydroxyalkyl group. ); (l′ means 1) or (p' represents an integer from 1 to 3). α represents a number from 0 to 3, β represents a number from 1 to 2, and γ represents a number from 1 to 4, but α+β+γ
≦4. However, SO ₃ H, SO ₂ A and each of which is bonded at the 3 or 4 position to the non-identical benzene ring of the phthalocyanine, and the metal contained in Pc is copper, zinc, aluminum or nickel. ] A method for coloring a base film made of a protein-based natural polymer substance or a synthetic resin having a cationic group, characterized by using a water-soluble phthalocyanine compound represented by: