JPH0410509B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-soluble copper phthalocyanine compound and a method for dyeing textile materials using the same. More specifically, in the free acid form, formula (1) [In formula (1), Pc represents a copper phthalocyanine group,
m, 1 is a number from 1 to 3, n is a number from 0 to 2, R ₁ ,
R ₂ and R ₃ each independently represent a hydrogen atom or a C ₁ -C ₂ alkyl group, R ₄ represents a phenyl group optionally substituted with a methyl group, a sulfonic acid group, a carboxyl group, or a chlorine atom, and A represents _C2 - _C3 alkylene group; represents a phenylene group optionally substituted with a sulfonic acid group or a carboxyl group. (However, the carboxyl group of the pyridine nucleus is bonded to the 3 or 4 position of the pyridine nucleus, and the positive charge of the nitrogen atom of the pyridine nucleus is electrically neutralized by OH ^- , Cl ^- , SO ₃ ^- or COO ^- . )] This invention relates to a water-soluble copper phthalocyanine compound represented by the following and a method for dyeing cellulose fibers or cellulose fiber-containing fiber materials using the same. Reactive dyes for cellulose fibers are used in large quantities because they have superior fastness and brightness compared to other dyes for cellulose fibers. For example, reactive dyes with reactive groups such as dichlorotriazinyl, monochlorotriazinyl, fluorochloropyrimidinyl, dichloroquinoxazinyl, methylsulfonylchloropyrimidinyl, vinylsulfonyl, sulfatoethylsulfonyl, etc. are used as acid binders. or substances that release acid binders by the action of heat (e.g., sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, triphosphate)
Adjust the pH of the dye bath to 10 or higher by using potassium, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, sodium trichloroacetate, alone or in combination, and add sodium chloride, sulfuric acid. Cellulose fibers are dyed at temperatures below 100°C in the presence of neutral electrolytes such as sodium. On the other hand, mixed fiber materials (blends) containing cellulose fibers are increasingly used as fiber materials for clothing, and blends of polyester fibers and cellulose fibers, particularly cotton (hereinafter referred to as T/C blends), are suitable for clothing. It has come to be widely used for reasons such as excellent durability and economical efficiency. And T/C
The following methods have generally been used to dye blends using reactive dyes and disperse dyes. (i) One-bath two-step method First, the polyester fiber side is dyed with a disperse dye by a carrier dyeing method, a high temperature dyeing method, etc., and then the cellulose fiber side is dyed with a reactive dye in the same bath. Or use the opposite method. (ii) Two-bath method First, the polyester fiber side is dyed by the method described above, and then the cellulose fiber side is dyed in a separate bath. Or use the opposite method. However, recently, from the viewpoint of shortening the dyeing time, rationalizing the dyeing process, and saving energy, efforts have been made to use the T/C mixture in the same bath and finish dyeing in one dyeing process (one-bath, one-step method). Ta. By the way, there are several obstacles to dyeing a T/C blend with a reactive dye and a disperse dye using a high temperature method or the like in one step in one bath. For example, acid binders required for dyeing reactive dyes or substances releasing acid binders can agglomerate or decompose the disperse dyes in the dyebath. or,
For example, 130 for dyeing the polyester fiber side
In an aqueous medium at a high temperature such as 0.degree. C., reactive dyes are hydrolyzed by acid binders and the like, and are no longer dyed onto cellulose fibers. Therefore, there has been a strong demand for the development of reactive dyes that can dye T/C mixtures in one step in one bath. As a result of extensive research to meet these demands, the present inventors discovered that the compound represented by formula (1) has extremely high suitability for one-bath, one-step dyeing of T/C mixtures, and thus achieved the present invention. It is ivy. The compound of the present invention not only shows excellent suitability for T/C mixed one-bath one-stage dyeing method, but also has sufficient suitability for dyeing cellulose fibers by ordinary methods. , the novel compounds of the present invention can be used in the absence of an acid binder or a substance releasing an acid binder, or when the dye bath has a pH of 4 to 10, especially 5.
The point is that a T/C mixture can be dyed in one bath and in one step at a dyeing temperature of 100 to 150°C in the presence of a disperse dye, simply by coexisting with a chemical having a buffering action necessary to maintain the temperature at a temperature of -9. T/C with disperse dye using the compound of the present invention
When the mixture is dyed in one bath in one step, the T/C mixture can be uniformly dyed without causing aggregation of the disperse dye or decomposition of the disperse dye and the reactive dye. The compound of the present invention dyes cellulose fibers in a turquoise hue, and the dyed product has excellent wet fastness, chlorine fastness, light fastness, and sweat/sunlight fastness. The compound of the present invention can be applied to cotton, recycled viscose fiber,
The most remarkable effect is obtained when used for dyeing cellulose fibers such as hemp, T/C blends, but other dyes include cellulose fibers, triacetate fibers, polyacrylonitrile fibers, modified polyacrylic fibers,
It is applied to the dyeing of mixed fiber materials with polyamide fibers, wool, silk, etc., and excellent effects can be obtained even when dyeing the cellulose fiber side. In these cases, by using disperse dyes, basic dyes, cationic dyes, acid dyes, acidic metal-containing dyes, etc., it is possible to obtain a dyed blend in which each fiber forming the blend is uniformly dyed. The novel water-soluble phthalocyanine compound represented by formula (1) has the formula (2) in its free acid form. (In the formula, Pc, R ₁ , R ₂ , R ₃ , R ₄ , A, m, n,
l has the same meaning as above. ) can be obtained by reacting the compound represented by nicotinic acid or isonicotinic acid in water at 50-100°C and PH3-8. Conventional salting out methods and acid precipitation methods are used to extract the target product from the reaction solution.
It can also be obtained by spray drying. Next, to produce the water-soluble phthalocyanine compound represented by formula (2), for example, the following method is used. First, the formula (3) in the free acid form (p represents 1-3, q represents 1-4, Pc
represents the above meaning. ), a compound of the formula NH ₂ A-NH ₂ (A represents the same meaning as above) and a compound of the formula NHR ₃ R ₄ (R ₃ R ₄ represents the same meaning as above) Formula (4) obtained by condensing the compound of ) and cyanuric chloride in any order (A, R ₃ R ₄ represent the same meanings as above) or amines represented by the following formula NHR ₁ R ₂ (R ₁ R ₂ represent the same meanings as above) in any order. It can be obtained by reacting with Compound (2) can also be obtained by the following method. i.e. in the free acid form formula (5) (In the formula, Pc, R ₁ , R ₂ , A, m, n, l represent the same meanings as above.) Compounds represented by the formula NHR ₃ R ₄ (R ₃ , R ₄
has the same meaning as above. ) and the compound 1,3,
5-Trichlortriazine is condensed in any order. Used in producing the compound of formula (2)
Specific examples _of compounds represented by _H2NA - _NH2 , _HNR3R4 , and _HNR1R2 are shown _below . An example shown as _H2NA - _NH2 ;

[Formula] (o-, m-, p-)

【formula】

【formula】

【formula】

[Formula] NH ₂ CH ₂ CH ₂ NH ₂ , NH ₂ CH ₂ CH ₂ CH ₂ NH ₂ Examples of compounds represented by the formula HNR ₃ R ₄ ;

【formula】

[Formula] (SO ₃ H is o, m or p)

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Examples of compounds represented by the formula HNR ₁ R ₂ ; NH ₃ , NH ₂ CH ₃ , NH(CH ₃ ) ₂ , NH ₂ C ₂ H ₅ ,
NH(C ₂ H ₅ ) ₂ Next, a method for dyeing cellulose fibers and cellulose fiber-containing fiber materials (blended fibers) using the compound of the present invention will be described. When dyeing cellulose fibers using the compound of the present invention by batch dyeing, the dye bath is prepared with an inorganic salt, such as sodium sulfate or sodium chloride, and the compound of the present invention, and the fiber is immersed at 50 to 90°C.
After staining for 10-60 minutes under heating, add an acid binder, such as sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide,
Sodium metasilicate, trisodium phosphate, tripotassium phosphate, sodium pyrophosphate, potassium pyrophosphate, and sodium trichloroacetate were added singly or in a mixture of two or more, and further heated at the same temperature for 20-
Perform staining for 60 minutes. In this case, the acid binder may be added to the dye bath from the beginning, or it is possible to treat the dye with a separate bath containing the acid binder and an inorganic salt after dyeing. Also, T/C can be dyed using the compound of the present invention by a dyeing method.
When dyeing a mixture, use the compound of the present invention, a disperse dye, an inorganic salt, and, if necessary, a buffer to maintain the pH value of the dye bath at 5 to 9 (for example, a mixture of acetic acid and sodium acetate, monopotassium phosphate and phosphorus). A dye bath is prepared from a mixture of disodium acid, a mixture of monosodium phosphate and disodium phosphate), a surfactant, a reduction inhibitor, etc., and the T/C mixture is immersed in this dye bath.
Heat to 150℃ and stain for 20 to 90 minutes. The compound of the present invention makes it possible to dye T/C mixtures in one step in one bath in the coexistence of disperse dyes, and has extremely large economic effects in terms of shortening dyeing time, streamlining the dyeing process, and saving energy. . Next, the present invention will be specifically explained with reference to Examples.
In the examples, parts are by weight, and sulfonic acid groups and carboxyl groups are expressed in free form. In addition, the positive charge of the nitrogen atom in the pyridine nucleus causes OH ^- from the reaction solution,
Assume that it is electrically neutralized by Cl ^- or COO ^- or SO ₃ ^- in the compound. Moreover, Pc is a copper phthalocyanine nucleus. Example 1 Formula Dissolve 19.4 parts of the compound represented by in 200 parts of water,
3.4 parts of nicotinic acid was added to adjust the pH to 6. This mixture was heated to 85° C. and continued to be stirred for 10 hours while maintaining the pH at 6. Next, salting out with common salt and over-drying the precipitated crystals yields compound 36 represented by formula (7).
part was obtained. The maximum absorption wavelength of this substance was 626 nm (in water). Compound (6) was obtained as follows. Disperse 3.8 parts of cyanuric chloride in cold water;
3.5 parts of an aqueous solution of 3-aminobenzenesulfonic acid was poured into this, and condensation was carried out at 5° C. while maintaining the pH at 4-6. 6 parts of ethylenediamine hydrochloride was added thereto, and the mixture was allowed to react at 25°C and PH4 for 2 hours, the temperature was gradually raised to 50°C, and the reaction was further carried out at PH6 for 3 hours. The obtained product

[Formula] 17.5 parts were added, the pH was kept at 5-6, the temperature was kept at 20°C, and the mixture was stirred for 5 hours. Furthermore, when 3.4 parts of isonicotinic acid is used in place of the nicotinic acid used to obtain the compound of formula (7), formula (8) is obtained.
The compound of formula (6) was also replaced with 3-aminobenzenesulfosic acid used in producing the compound of formula (6).
-Amino-6-chlorobenzenesulfonic acid is used to react with nicotinic acid to obtain the compound of formula (9), and the maximum absorption wavelength of each is 626 nm (in water).
It was hot. Example 2 Formula (10) 21 parts of the compound was dissolved in water, 3.4 parts of nicotinic acid was added, the pH was adjusted to 7.5, and the mixture was stirred at 80°C for 6 hours.
Salting out with 10% of the liquid volume of common salt, separating the precipitated crystals and drying at 70°C, yielded 40 parts of turquoise powder. This means that the maximum absorption wavelength expressed by equation (11) is
It was 629nm (water). Compound (10) was obtained as follows. The following formula was reacted with twice the molar amount of 2,4-diaminobenzenesulfonic acid at 10°C, PH4-6, then twice the molar amount of cyanuric chloride was reacted at 10°C, PH7-8, and then aniline was reacted at 40°C, PH4-6. 7 to react,
Finally, aqueous ammonia was reacted at 20°C. In the above, the same amount of 2,5-diaminobenzenesulfonic acid was used instead of 2,4-diaminobenzenesulfonic acid, and nicotinic acid was further reacted to obtain a compound having a maximum absorption wavelength of 629 nm. Furthermore, even when orthotoluidine or paratoluidine was used in place of aniline in the above, a compound with a maximum absorption wavelength of 629 nm was obtained. Furthermore, cyanuric chloride was condensed with 1,4-diaminobenzenesulfonic acid and then aniline under acidic conditions, and then condensed with the following: Finally, when ammonia is reacted, equation (12) is obtained. The compound represented by (13) was obtained by quaternizing this compound with nicotinic acid. (628nm (water)) Example 3 2 parts of the compound of formula (11) obtained in Example 2, 60 mg of Glauber's salt
1 part, 2 parts of disodium phosphate, 1 part of potassium phosphate
A dye bath was prepared consisting of 0.5 parts of sodium metanitrobenzene sulfonate, 1 part of sodium metanitrobenzene sulfonate, and 934.5 parts of water. The pH value of the dye bath at this time was 7. Unsilced cotton stockinette that has been scoured and bleached in this dye bath at room temperature.
50 parts were added, the temperature was raised to 130°C over 30 minutes while stirring, and dyeing was carried out at that temperature for 60 minutes. The PH value after staining was 7, unchanged from before the start of staining. After dyeing, wash with water and apply a 1000ml aqueous solution containing 2 parts of anionic surfactant.
The dyed material was washed with water and dried for 10 minutes at 100° C. to obtain a turquoise dyed product. This product had excellent wet fastness, chlorine fastness, light fastness, and sweat/sunlight fastness. Example 4 1 part of the compound of formula (7) obtained in Example 1, 0.5 part of Color Index Disperse Blue 60, Glauber's salt
80 parts, 1 part of sodium metanitrobenzenesulfonate, 2 parts of formalin condensate of naphthalene sulfonic acid (dispersant), and adjusted to pH 7.0 with a buffer consisting of disodium phosphate and monopotassium phosphate, total volume 1000. Add 50 parts of polyester fiber/cotton (50/50) blended fabric to the same dye bath and dye 130% in 20 minutes.
The temperature was raised to ℃ and dyeing was carried out at this temperature for 60 minutes. After washing with water, it was soaped in 1000 parts of water containing 2 parts of anionic surfactant and 2 parts of sodium carbonate at 100°C for 20 minutes, then washed with water and dried. A dyed product was obtained in which both the polyester fiber side and the cotton side were dyed in turquoise color. Example 5 2 parts of the compound of formula (7) obtained in Example 1, 80 mg of Glauber's salt
Prepare a dye bath using 1,000 parts of water and 1,000 parts of water.
After 50 parts of cotton stockinette was soaked and dyed at 80° C. for 30 minutes, 20 parts of sodium carbonate was added and dyed subsequently at the same temperature for 60 minutes. It was then soaped as in Example 3 and then dried, giving a turquoise dyeing. This product had excellent wet fastness, light fastness, and chlorine fastness. Example 6 Formula (12) 20.0 parts of the compound and 3.4 parts of isonicotinic acid were dissolved in water, the pH was adjusted to 7, and the mixture was stirred at a temperature of 90°C for 5 hours. Next, salting out and filtering and drying the precipitated crystals,
33 parts of the compound of formula (13) was obtained. (628nm (water)) Furthermore, the compound (12) is

[Formula] was condensed with paraacetylaminoaniline and deacetylated, and then a condensate of cyanuric chloride and 2,5-disulfoaniline was reacted. Examples 7 to 21 Compounds of formula (1) were produced according to Examples 1, 2, and 6, and cotton was dyed.

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Claims (1)

[Claims] 1 Formula (1) in the form of free acid [In formula (1), Pc represents a copper phthalocyanine group,
m is a number from 1 to 3, n is a number from 0 to 2, R ₁ ,
R ₂ and R ₃ each independently represent a hydrogen atom or a C ₁ -C ₂ alkyl group, R ₄ represents a phenyl group optionally substituted with a methyl group, a sulfonic acid group, a carboxyl group, or a chlorine atom, and A represents _C2 - _C3 alkylene group; represents a phenylene group optionally substituted with a sulfonic acid group or a carboxyl group. (However, the carboxyl group of the pyridine nucleus is bonded to the 3 or 4 position of the pyridine nucleus, and the positive charge of the nitrogen atom of the pyridine nucleus is electrically neutralized by OH ^- , Cl ^- , SO ₃ ^- or COO ^- . water-soluble copper phthalocyanine compound 2 represented by the formula (1) in the free acid form [In formula (1), Pc represents a copper phthalocyanine group,
m, 1 is a number from 1 to 3, n is a number from 0 to 2, R ₁ ,
R ₂ and R ₃ each independently represent a hydrogen atom or a C ₁ -C ₂ alkyl group, R ₄ represents a phenyl group optionally substituted with a methyl group, a sulfonic acid group, a carboxyl group, or a chlorine atom, and A represents _C2 - _C3 alkyler group; represents a phenylene group optionally substituted with a sulfonic acid group or a carboxyl group. (However, the carboxyl group of the pyridine nucleus is assumed to be bonded to the 3rd or 4th position of the pyridine nucleus, and the positive charge of the nitrogen atom of the pyridine nucleus is electrically neutralized with OH ^- , Cl ^- , SO ₃ ^- , or COO ^- . A method for dyeing cellulose fibers or cellulose fiber-containing fiber materials, characterized by using a water-soluble copper phthalocyanine compound represented by: