JPS6187759A - Water-soluble phthalocyanine compound and method for coloring surface film of substrate by using the same - Google Patents

Abstract

NEW MATERIAL:Water-soluble phthalocyanine compounds in the free form of formula I, wherein Pc is a residue of metal-free or metal phthalocyanine; A is NH2, OH; B is a group of formula II or III (wherein X is OH, Cl, 1-8C alkylamino, cyclohexylamino, morpholino, etc.; R1, R2 are each H, CH3, NHCOCH3, NHCONH2, etc.; n is 0, 1) etc.; alpha is 0-3, beta is 1-2, gamma is 1-4; alpha+beta+gamma<=4; SO3H, SO2A and a group of formula IV are attached to different benzene rings at position 3 or 4; and when Pc is a residue of metal phthalocyanine, the metal is Cu, Zn, Al or Ni. USE:Anion dyes which dye natural proteolytic high-molecular materials and cationic group-contg. synthetic resins green. PREPARATION:A compd. of formula V (wherein D is a group of formula VI, VII or VIII; m is 1, 2) is condensed with a compd. of formula IX. The resulting product is then condensed with an amine of the formula Q-H (wherein Q is a group of X excluding Cl and OH).

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a water-soluble phthalocyanine compound and a method for coloring a substrate surface film using the same.

``Prior Art'' Transparent substrates such as glass and plastics are colored and used in sunglasses, shop windows, and various displays, and recently, these colored substrates are used in liquid crystal devices.

It is now also used as a component of color separation devices for color television cameras. 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. That is, conventionally, glass,
The simplest method for coloring plastics, etc. is to add a coloring agent in the process prior to molding into a predetermined shape, and then mold it to obtain a colored product. , this method is suitable for large amounts of
Although it is suitable for the purpose of obtaining colored molded products,
It is unsuitable for the purpose of obtaining colored materials on a small scale,
Also, depending on this method, parts with different color tones cannot be provided on the same molded product. 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. It is convenient to do so. By the way, protein-based natural polymer substances such as gelatin, casein, and glue retain cationic groups, so they can 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.
It has five drawbacks, including insufficient reproducibility.

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 a compound of formula CI) in the free acid form.

[Formula (11, Pc is metal-free or metal-containing 7 talocyanine residue, A is NHg or OH, B is (in the above formula, X is OH1 chlorine atom, alkyl (Ct ~ 8) amino group, arylalkyl ( C1-Ca) Amino group 5 hydroxyalkyl CC1-5) Amino group, alkoxy (C,
~3) Alkyl (C2-4) amine group, phenoxyalkyl (C1-3) amino group, cyclohexylamino group 1
morpholino group, substituted or unsubstituted arylamino group); (In the above formula, X has the same meaning as above.

Further, m represents 1 or 2. ); (In the above formula, X has the same meaning as above, & , R
2 is H, CHs, C0OH, NHCOCHa, N
HCONH2-represents a norogen or a Ct~3 alkoxy group. and n represents 0 or l); (In the above formula, & , R2 and n represent the same meanings as above) or -NH-, and R, , R, 2 and n represent the meanings as above. Further KC is (SO output) ■ R4 is H, OH, C0OH, CHaSOz, CHaC
ONH, NH2゜Cs~3 alkyl group, C1~3 alkoxy group% C1~4 alkylamino group or halogen, l represents 0, 1 or 2), Z is CHs, CxHs, C0OH or N
) or 96 (In the above formula, R5 represents CONH2, CH25OaH or CN, and R represents C = CaH2-CzHv, ÷CH2
+ q C00H (q represents an integer from 1 to 5), ÷
CH2÷9SOaH (q represents the same meaning as above),
Represents a C, ~5 hydroxyalkyl group. ); represents. 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, respectively, and it is assumed that each of α and β is bonded at a different benzene RK3 or 4 position of the phthalocyanine, and Pc is a metal The metal in the case of containing is copper, zinc, aluminum or nickel. ] A water-soluble phthalocyanine compound represented by is produced and used to color (or dye) a surface film of a substrate made of a protein-based natural polymer such as gelatin, casein, or glue or a synthetic resin having a cationic group. 5.

The water-soluble 7-talocyanine compound represented by the formula (11) can be produced, for example, by the following method.
Here, m represents the same meaning as above) or a meaning). ] A compound represented by the formula (IIT) is condensed with a compound represented by the formula (IIT, in which C, Rt, R2 and n represent the same meanings as above), and then (IV) Q -H
(IV) In formula (IV), Q is condensed with an amine represented by the atom represented by X or a group other than chloro or hydroxyl group, or α, β, and r have the same meanings as above) A sulfonic acid chloride compound represented by the formula (formula (%'
Cr R1* R2* '' in l) has the same meaning as above) or a compound represented by the formula (I C, R11, R2, n in formula CI),
It can be obtained by condensing a compound represented by:

The condensation reaction of the compound represented by formula (III) and the compound represented by formula (III) 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. The condensation of the product obtained by the condensation of the compound represented by Bunmu J with the compound represented by formula (m) and the amine represented by formula (IV) is carried out at a temperature of 30 to 1
00°C, pH value 4-10 and in the presence of an acid binder. In addition, a compound represented by formula (■) and formula (VD or formula (
■) The condensation reaction with the compound represented by
℃, pH value 4-10 and in the presence of an acid binder. - Note that sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are used as acid binders in these condensation reactions.

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 0 include the following.

[In the examples, sulfonic acid and carboxyl groups are expressed in free form. Same below. ] Ho, s (The sulfonic acid group is bonded to the 2-) or 3-position of the benzene nucleus. In the above specific examples, Pc(31, Pc(41) and the number yl 3.4 are the same tenon of the phthalocyanine. represents the 3- or 4-bond position of the benzene ring, α, β, γ
Decimal values indicate average composition.

Next, specific examples of compounds represented by formula (IID) include the following.

1 Specific examples of the compound represented by formula (IV) include the following.

Methylamine, ethylamine, n-propylamine, t
-butylamine, hydroxyethylamine, hydroxypropylamine, γ-hydroxyhexylamine, 2-
Phenylethylamine, 2-ethylhexylamine, 2
-methoxyethylamine, 3-ethoxyethylamine, phenoxyethylamine, isopropoxyethylamine, 2-ethoxyethylamine, cyclohexylamine, mole 7 oline, aniline, m-/loraloline, p-
Chloraniline, 0-chloroaniline, 2-chlorotoluidine, m-)luidine, anthra=kH, methyl anthranilate, sulfanilic acid, metanilic acid, ortanilic acid, C2-.

3-1 or 4-carboxy)aniline, (2131 or 4-methoxy)aniline, (2131 or 4-ethyl)
Aniline, (2-93-,4-,ethoxy)aniline Specific examples of compounds represented by the formula (VD) include the following.

Further, specific examples of compounds represented by the formula (VID) include the following.

HO3S `` OsS し3H7 Tomb HI U2ti5 The protein-based natural polymeric cortex such as gelatin, casein, and glue used in the present invention will be explained. Gelatin is an animal-derived collagen made by boiling collagen with water to irreversibly make it water-soluble. It is a protein that 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. Ammonium dichromate, etc. are added to an aqueous solution of these natural proteins. A few percent of dichromate is added and applied uniformly onto a flat substrate using a method such as a spin code, and then irradiated with ultraviolet rays to completely cure and form a water-insoluble film.The physical properties and dyeing of the film Since the raw material source is an animal, the properties vary depending on the type, habitat, part, etc. of the animal, but these differences do not interfere with the film used in the present invention.

Further, examples of the synthetic resin film having a cationic group used in the present invention include the following.

A polymer matrix having a photoreactive unsaturated group and a quaternary ammonium base in the side chain, a photopolymerization initiator) and a solvent (0
A photoreactive resin composition comprising: After coating, it is irradiated with actinic rays to cause a reaction and form a film. A polymer prisoner having a photoreactive unsaturated group and a quaternary ammonium base in its side chain has (N,
N-dimethylamino)ethyl acrylate, (N.

N-diethylamino)ethyl acrylate.

Allyl bromide, 3
-Chloro-2=obtained by reacting with an unsaturated compound having an active halogen atom such as methylpropene, p-chloromethylstyrene, or 3-chloro-2-hydroxyglobil methacrylate. Compounds having two or more photoreactive unsaturated groups in one molecule (for example, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, etc.) Examples of photoreaction initiators (Bl include 2-ethylanthraquinone,
Benzophenone etc. can be used. Further, any solvent may be used as long as it can sufficiently dissolve the solvent (q for the polymer particles and the photoreaction initiator) and the compound (for example, 2-methoxyethanol, 2-ethoxyethanol, toluene, xylene, etc.).

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 base material is preferably one that has excellent transmission characteristics over the entire wavelength range of visible light, and optical glass is generally used.
Plastic plates such as methyl methacrylate resin, polystyrene resin, and polycarbonate resin are also used.

To color the film using the compound represented by the formula (Tl), for example, a dipping method or a printing method is used, and a dipping dyeing method using an aqueous solution is particularly convenient.
30? The formula (10-
The base material provided with the film is immersed in a dye bath at 100° C. for 10 seconds or more, then taken out and dried. The green colored film thus obtained not only exhibits favorable transmission properties, but also has excellent light resistance and is resistant to fading.

"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 3.8 parts of cyanuric chloride was mixed with 40 parts of water, 60 parts of ice, and 0.0% of a 10% Liponox NA aqueous solution (manufactured by Lion Oil, dispersant).
The mixture was added to a solution consisting of 5 parts under stirring to prepare a suspension.

After stirring for 30 minutes, it contained 5.8 parts of metaminic acid and had a pH of -7.
50 parts of an aqueous solution adjusted to S8 was poured into the suspension at 10'C or below over 1 hour. 10 below 20'C
% soda ash aqueous solution was added dropwise and the reaction was carried out for 4 hours while maintaining the pH value at 4-6. Then, the reaction solution was kept at 5°C or less,
After adding 4 parts of concentrated hydrochloric acid and stirring for 30 minutes, 40%
3.8 parts of aqueous sodium nitrite solution was added dropwise. 2 below 5℃
After stirring for an hour, excess nitrite ions were removed with sulfamic acid. Contains 6.4 parts of a compound with the following structure, pH
50 parts of an aqueous solution adjusted to 7 to 8 was gradually poured into the diazo solution and stirred for 4 hours at 10°C or below, then adjusted to pH 6 with a 10% aqueous soda ash solution, and further stirred for 4 hours at room temperature. Compound 1 having the following structure was present in the reaction solution thus obtained.
6.5 parts were added at once.

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. Add 1.5 parts of morpholine to this reaction solution and
The temperature was raised to 0°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.

λmax 520 nm (Water) Example 2゜Toyae, ... River...
...69 parts (N,N-dimethylamine)ethyl methacrylate ...30 parts azoisobutyronitrile
・・・・・・・・・・・・ 1 part of the liquid with the above composition was treated at 80°C for 8 hours in a nitrogen atmosphere to form poly(N,
N-dimethylamino)ethyl methacrylate solution 100
get the part. Add 15 parts of chloromethylstyrene to 50 parts of this solution.
After boiling at room temperature and reacting for 16 hours, this was dissolved in 260 parts of 2-ethoxyethanol, and 16 parts of Irgacure 651 (manufactured by Ciba Geigy, photopolymerization initiator) was added and dissolved to form a cationic group. A photosensitive resin composition containing

Next, the surface of the optical glass (high-purity glass plate with excellent light transmittance) was washed with acetone, dried, and then coated with a 10% ethanol solution of KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical), air-dried, and heated at 110°C. Heat and dry for 5 minutes,
Further, this surface was 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 it with ultraviolet rays 'i 80 Watt/cm for 4 seconds using a high-pressure mercury lamp.

Next, the compound of Example 1 was dissolved in water adjusted to pH 4 with acetic acid to become a 0.05% aqueous solution, and the temperature was raised to 80°C. When the optical glass on which the cured coating film was formed was immersed in this solution for 20 minutes, λmax was 520 nm.
An optical glass plate having a clear green colored film was obtained.

Examples 3 to 40 A compound was 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 having a coating 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.

Example 41 Wet paste 19.4 parts of copper phthalocyanine-(3)-tetrasulfonic acid chloride to 100 parts of an aqueous solution containing 10.7 parts of an amino compound having the following structure and adjusted to pH 7.5 at 10°C or less while stirring. Add as. Then 065 parts of pyridine was added and p
The reaction was carried out for 4 hours while maintaining the H value at 6.5 to 7.0. 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 compound 28 of the above formula.
．． I got 0 copies.

Example 4 0.0% of the compound of Example 41 was added to water acidified with 2° acetic acid (pH value 4).
It was dissolved to a concentration of 1%, and the temperature of this solution was raised to 90°C. 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. 5
An optical glass having a λmax of 0.00 nm and a film colored in clear green was obtained.

Examples 43-82 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 (nm) in water.

Example 9 A 10% aqueous gelatin solution containing 0.5% ammonium dichromate was uniformly applied onto a 3° optical glass substrate by a spin code method, dried, cured by irradiation with ultraviolet rays, and then heated with 40°C hot water. After washing and drying, a photocrosslinked gelatin film was formed on an optical glass plate.

A 0.5% aqueous solution of the compound of Example 41 was adjusted to pH 4 with acetic acid, and an optical glass having a gelatin film was immersed in a dye bath heated to 60°C for 20 minutes, washed with water, and dried. An optical glass substrate with a green colored film with λmax in nm was obtained.

(Application example) Color filters are used to make full-color active Φ matrix channels of liquid crystals. A color filter is a mosaic pattern made of colored gelatin or casein placed on an optical glass substrate.
The three primary colors of green and blue are created using photolithography technology, and the light from a light source placed on the back of the panel passes through a filter to express the colors.

In order to reproduce colors that feel natural, red, green, and the other colors must each have specific optical properties and be balanced with each other, and green in particular is an important element that governs color balance.

Panels equipped with colored filters reproduced natural colors and were vivid.

"Effect of the invention" Casein provided on a substrate such as glass or plastic,
A base film made of a protein-based natural polymer such as gelatin or glue or a synthetic resin having a cationic group is colored with a green hue with excellent optical properties using a single compound represented by the formula (Step 1). The substrate with this colored film is excellent as a member of a color separation device.

Claims (2)

[Claims] (1) In the form of a free acid, the formula (I) [SO_3H]_α ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula (I), Pc is a metal-free or metal-containing phthalocyanine residue, and A is a metal-free or metal-containing phthalocyanine residue. NH_2 or OH, B is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, X is OH, chlorine atom, alkyl (C_
1_~_8) Amino group, arylalkyl (C_1~C
_3) Amino group, hydroxyalkyl (C_1_-_5
) amino group, alkoxy (C_1_-_3) alkyl (
C_2_~_4) Amino group, phenoxyalkyl (C_
1_-_3) Indicates an amino group, a cyclohexylamino group, a morpholino group, and a substituted or unsubstituted arylamino group. )
;▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, X has the same meaning as above, and m represents 1 or 2.); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, X is Same meaning as above, R_1, R_2 are H, CH_3, COOH, NHCOC
H_3, NHCONH_2, halogen or C_1_~_
3 represents an alkoxy group. and n represents 0 or 1); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R_1, R_2 and n represent the same meanings as above.) Or -NH-, or R_1, R_2 and n represents the same meaning as above. Furthermore, C has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, Y is H, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (R_3, R_4 are H, OH, COOH, CH_
3SO_2, CH_3CONH, NH_2, C_1_~
_3 alkyl group, C_1_-_3 alkoxy group, C
(represents an alkylamino group or halogen of _1_ to _4, l represents 0, 1 or 2) or ▲There are numerical formulas, chemical formulas, tables, etc.▼ (p is 0 to 3
Z represents CH_3, C_2H_5, COOH or NH_2); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R_5 represents CONH_2, CH_2SO
_3H or CN, R_6 is CH_3, C_2H_5,
C_3H_7, -(CH_2)-_qCOOH (q is 1
represents an integer from 5 to 5), -(CH_2)-_qSO_
3H (q represents the same meaning as above) or C_1_～_
5 represents a hydroxyalkyl group. ); ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (l represents the same meaning as above)
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (p has the same meaning as above). 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, and α+β+γ≦4. However, SO_3H, SO_2A and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are each bonded to the benzene ring which is not the same as the phthalocyanine at the 3 or 4 position, and if Pc contains a metal, the metal is copper. , zinc, aluminum or nickel. ] Water-soluble phthalocyanine compound represented by (2) Formula (I) in the form of free acid ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In formula (I), Pc is a metal-free or metal-containing phthalocyanine residue, A is NH_2 or OH , B is ▲ formula,
There are chemical formulas, tables, etc.▼ (In the above formula, X is OH, chlorine atom, alkyl (C_
1_~_8) Amino group, arylalkyl (C_1_~
_C_3) 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,
Indicates a morpholino group, a substituted or unsubstituted arylamino group. ); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, X has the same meaning as above, and m represents 1 or 2.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, X Same meaning as above, R^1, R^2 are H, CH_3, COOH, NHCOC
H_3, NHCONH_2, halogen or C_1_~_
3 represents an alkoxy group. And n represents 0 or 1. ); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R_1, R_2 and n represent the same meanings as above.) Or -NH-, and R_1, R_2 and n represent the same meanings as above. Furthermore, c has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, Y is H, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (R_3, R_4 are H, OH, COOH, CH_
3SO_2, CH_3CONH, NH_2, C_1_~
_3 alkyl group, C_1_-_3 alkoxy group, C
_1_-_4 represents an alkylamino group or halogen, l represents 0, 1, or 2) or ▲ Numerical formula, chemical formula, table, etc. ▼ (p is 0 to 3
), and Z is CH_3, C_2H_
5, represents COOH or NH_2); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R_5 represents CONH_2, CH_2SO
_3H or CN, R_6 is CH_3, C_2H_5,
C_3H_7, -(CH_2)-_qCOOH (q is 1
represents an integer from 5 to 5), -(CH_2)-_qSO_
3H (q represents the same meaning as above), C_1_-_5
represents a hydroxyalkyl group. ); ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (l represents the same meaning as above) or ▲ Mathematical formulas, chemical formulas,
There are tables, etc. Represents ▼ (p has the same meaning as above). 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, and α+β+γ≦4. However, each of SO_3H, SO_2A and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is assumed to be bonded to the different benzene rings of the phthalocyanine at the 3 or 4 position, and Pc
contains a metal, the metal 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 the following.