JPS6090263A - Copper phthalocyanine compound and dyeing of fibrous material using it - Google Patents

Abstract

NEW MATERIAL:A compound in the form of a free acid shown by the formula I [Pc is copper phthalocyanine; m and l are 1-3; n is 0-2; R1-R3 are H, or 1-2C alkyl; R4 is phenyl which may be replaced with methyl, sulfonic group, carboxyl, or chlorine; A is 2-3C alkylene or phenylene which may be replaced with methyl, sulfonic group, or carboxyl), with the proviso that COOH at pyridine nucleus is linked at 3- or 4-position, and positive charge of pyridine nucleus is electrically neutralized with OH<->, Cl<->, SO3<->, or COO<->]. EXAMPLE:A compound shown by the formula II. USE:Dye for dyeing cellulose fiber, especially mixed fabric of polyester fiber and cotton in Turkish color. PREPARATION:For example, a compound shown by the formula III is reacted with (iso)nicotinic acid in water at 50-100 deg.C at 3-8pH.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble steel phthalosyanyl compound and a method for dyeing textile materials using the same. More specifically, in the form of a free acid, the formula (1) [In formula (1), Pc represents a copper phthalocyanine group, and In
.

1 is a number from 1 to 3, n is a number from O to 2, R, , R2゜゜, each independently represents a hydrogen atom or an alkyl group from 01 to C2, it4 is a methyl group, a sulfonic acid group, A phenyl group which may be substituted with a carboxyl group or a chlorine atom,
represents a C2-C8 alkylene group; a phenylene group which may be substituted with a methyl group, 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 with OH-, CI, so3' or coo-. This invention relates to a water-soluble steel phthalocyanine compound represented by the following formula 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 groups such as dichlorotriazinyl, monochlorotriazinyl, fluorochloropyrimidinyl, dichloroquinoxacinyl, methylsulfonylchlorohirimicinyl, vinylsulfonyl, sulfatoethylsulfonyl, etc.
Acid binders using reactive dyes or substances that release acid binders by the action of heat (e.g., sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, tristrium phosphate) , tripotassium phosphate, birJ sodium phosphate, potassium birophosphate,
Sodium bicarbonate, sodium trichloroacetate)
By adjusting the I)H of the dye bath to 10 or more by using L or a mixture of two or more, the Ir of neutral electrolytes such as I, lithium and sodium sulfate can be adjusted so that the I)H of the dye bath is 10 or more. Currently, cellulose fibers are dyed at temperatures below 100°C.

On the other hand, mixed fiber materials (blends) containing cellulose fibers are increasingly being used as textile materials for clothing, especially blends of polyester fibers and cellulose fibers, especially cotton (hereinafter referred to as T/C blends). (abbreviated)) has come to be widely used because it is suitable for clothing and is economical. The following method has generally been used to dye T/C blends using reactive dyes and disperse dyes.

(1) - Two-bath 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.

(it) Two-part 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, streamlining the dyeing process, and saving energy, it has become possible to mix T/C in the same bath and only once.
Efforts have been made to finish the dyeing process during the dyeing process (-bath one-stage method).

However, there are several obstacles to dyeing a T/C blend using a reactive dye and a disperse dye in one bath and one step using a high temperature method or the like. For example, acid binders required for dyeing reactive dyes or substances releasing acid binders can agglomerate or decompose the disperse dyes in the dyebath. Furthermore, in a high temperature aqueous medium of, for example, 130° C. for dyeing the polyester fiber 4111, the reactive dye is hydrolyzed by the acid binder and the like, so that it does not dye the cellulose fiber.

Therefore, there has been a strong demand for the development of a reactive dye that enables dyeing of T/C mixtures in one step in one bath.

The present inventors have conducted intensive research to develop 114 without such a request, and as a result, the compound represented by formula (1) has been found to be T/
It was discovered that the suitability of the C mixture for one-bath one-step dyeing was extremely high, leading to the present invention.

The compound of the present invention not only shows excellent suitability for the T/C mixed one-bath one-stage dyeing method, but also has sufficient suitability for dyeing cellulose fibers by the usual method. , the novel compounds of the invention can be used in the absence of an acid binder or a substance that releases an acid binder, or when the dyebath is
I-14 to 10, especially in the presence of a disperse dye, can be reduced to 100 by simply coexisting with a drug that has the necessary buffering effect to maintain the range from 5 to 9.
The advantage is that T/C blend can be dyed in one step in one bath at a dyeing temperature of ~150°C.

When the compound of the present invention is used in one-bath one-step dyeing of a γ mixture together with a disperse dye, the T/C mixture can be dyed uniformly without causing aggregation of the disperse dye or decomposition of the disperse dye or reactive dye. I can do it.

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 has the most remarkable effect when used for dyeing cotton, recycled viscose fiber, cellulose fiber such as hemp, and T/C blend, but it can also be used to dye cellulose fiber, triacetate M fiber, and polyester fiber. It is applied to the dyeing of mixed fiber materials with acrylonitrile fibers, modified polyacrylic fibers, polyamide fibers, wool, silk, etc., and even when dyeing the cellulose fiber side, excellent Nakosu can be obtained.

In these cases, disperse dyes, basic dyes, cationic dyes,
By using acid dyes, acidic metal-containing dyes, etc. in combination, 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) (wherein Pc, &, J(12,11131几4.A
, Ill, II, I have the same meaning as above.

) can be obtained by reacting the compound represented by nicotinic acid or isonicotinic acid in water at 50-400''C; The water-soluble phthalocyanine compound represented by formula (2) can be produced by, for example, the following method. Phthalocyanine sulfonic acid chloride represented by the formula (3) (p represents 1-3, q represents 1-4, and PC represents the above meaning) in the form of a free acid, and phthalocyanine sulfonic acid chloride of the formula NH2A NH2 (A is Formula (4) (A, 几) obtained by condensing a compound of the formula NHR3R4 (R3 has the same meaning as above) and cyanuric chloride in any order. a & represents the same meaning as above), or a compound of the following formula NHRI R2 (RX 几2 represents the same meaning as above).

) in any order.

Compound (2) can also be obtained by the following method.

That is, in the form of a free acid, the formula (5) (where pc, 几1. R2, A,, 111. +1
．． I represents the same meaning as above. ) and the compound represented by the general formula NtIRal (R3,R
4 represents the same meaning as above. ) σ) Condensate the compound with 1.3°5-trichlorotriazine in any order.

H2 used in producing the compound of formula (2)
N A NH2, HNI% 4. and IiN! Specific examples of compounds in which t and 1 are also represented by 2 are shown below.

1-Iz N A N1 (example indicated by z; NH, ()
COOI(, NH2Cl-I2'CH2NH2゜NH2 NH□CH2CH20142NH2 Example of a compound represented by formula HNRa R4; Formula HN R
1 of the compound represented by I R2; NH3, N1-1
2 Cl-1:l, N-1(CH3)2, N1
-I□C2H5, NH (C21-IS)2 Next, a method for dyeing cellulose fibers and cellulose fiber-containing fiber materials (blends) using the compound of the present invention will be described.

When dyeing cellulose fibers using the compound of the present invention by the Nototsuchi Tatami method, 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 for 50 to 50 min. Under heating to 90°C lO ~ 60
After staining for minutes, add an acid binder, e.g. bicarbonate l-I.
Jum, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, metasilicate, trisodium phosphate, tripotassium phosphate, sodium birophosphate, potassium birophosphate, trichloroacetic acid) IJ
Add umum alone or in combination of two or more kinds, and further dyeing is carried out at the same temperature for 20 to 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.

In addition, when dyeing an i''/C mixture using the compound of the present invention by the dip dyeing method, the compound of the present invention, a disperse dye, and an inorganic salt, and if necessary, the pl-1 value of the dye bath is adjusted to 5 to 9. Keep buffer (
For example, a dye bath is prepared from a mixture of acetic acid and sodium acetate, a mixture of monopotassium phosphate and disodium phosphate, a mixture of monosodium phosphate and disodium phosphate), a surfactant, a reduction inhibitor, etc. The 'I'/C mix is immersed in the bath, heated to 100-150°C, and dyed for 20-90 minutes.

The compound of the present invention makes it possible to dye T/C mixtures in one bath in the coexistence of disperse dyes, and its economic effects are extremely significant in terms of shortening dyeing time, streamlining the dyeing process, and saving energy. Hey.

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. It is also assumed that the positive charge of the nitrogen atom of the pyridine nucleus is electrically neutralized by OH"-, CI- from the reaction solution, or C00-, SO in the compound. Also, Pc is a copper phthalocyanine nucleus. .

Example 1: 194 parts of the compound represented by ``Brown'' was dissolved in 200 parts of water, and 34 parts of nicotinic acid was added to adjust pa+ to 6.

This mixed solution was heated to 85° C., and stirring was continued for 10 hours under the following conditions: 1) Keeping 11 to 6; Next, salting out with common salt was carried out, and the precipitated crystals were filtered and dried to obtain 36 parts of a compound represented by the formula (force).

The maximum absorption wavelength of this one was 62 G+on (
underwater). Compound (6) was obtained as follows.

3.8 parts of cyanuric chloride is dispersed in cold water, and 3.8 parts of cyanuric chloride is dispersed in cold water. An aqueous solution of 3-aminobenzenesulfonic acid in part S was poured into the mixture, and condensation was carried out at 5° C. while maintaining pi-I at 4-6.

Add 4 parts of ethylene def and 6 parts of hydrochloride to this and heat at 25°C.
, react for 2 hours with pi-I 4 and gradually increase the temperature to 50°C.
and react for an additional 3 hours at pl-I 6, p
l-15-,6, the temperature was maintained at 20°C and 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), the compound of formula (8) is converted to the 3-amino acid used in the production of the compound of Bunmu (6). 3-amino-6- instead of benzenesulfosic acid
When nicotinic acid was reacted with the chlorobenzenesulfonic acid moiety, compounds of the formula (9+) were obtained, each having a maximum absorption wavelength of 626111n (in water).

001-I Example 2 21 parts of the compound of formula (10) 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 salt, the precipitated crystals were separated from house to house, and
After drying at 0° C., 40 parts of turquoise powder was obtained.

This is expressed by equation (11), and the maximum absorption wavelength is 629 n
m (Wed).

Compound (10) was obtained as follows.

to react with twice the molar amount of 2,4-deaminobenzenesulfonic acid at 10°C pi-I 4-6, and then react with twice the molar amount of cyanuric chloride at 10°C with I) I-17-s, Further, aniline was reacted at 40°C and pH 4-7, and finally aqueous ammonia was reacted at 20°C.

In addition, in the above, the same amount of 2,5-deaminobenzenesulfonic acid was used instead of 2,4-deaminobenzenesulfonic acid, and nicotinic acid was further reacted to obtain a maximum absorption wavelength of 629.
n+n compounds were obtained.

Furthermore, even if orthotoluidine or paratoluidine is used in place of aniline in the above, the maximum absorption wavelength is 629 nm.
m compound was obtained. When cyanuric acid is condensed with 1,4-deaminobenzenesulfonic acid and then aniline under acidic conditions, and then finally reacted with ammonia, a compound of formula (12) is obtained, and this compound When this was quaternized with nicotinic acid, the compound represented by (13) was obtained.

(628n+n (water)) Example 3 2 parts of the compound of formula (11) obtained in Example 2, 60 parts of Glauber's salt
1 part, 2 parts of disodium phosphate, 0.5 parts of monopotassium phosphate, sodium metanitrobenzenesulfonate.

A dye bath was prepared consisting of 1 part of aluminum and 9345 parts of water. At this time, the dye bath 1) H value was 7. Fifty parts of mercerized cotton stockinette that had been scoured and bleached was placed in this dye bath at room temperature, heated to 130° C. over 30 minutes while stirring, and dyed at that temperature for 60 minutes. The pH value after staining was 7, the same as before the start of staining. After dyeing, it was washed with water, soaped at 100° C. for 10 minutes using parts i and ooo of an aqueous solution containing 2 parts of an anionic surfactant, and then washed with water and dried 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, 600.5 parts of Color Index Disperse Blue, 80 parts of Glauber's Salt, 1 part of sodium metanitrobenzenesulfonate, formalin condensate of naphthalene sulfonic acid ( 50 parts of a polyester fiber/cotton (50150) blended fabric was introduced into a dye bath of 1000 parts in total, containing 2 parts of dispersant) and adjusted to pH 7.0 with a buffer consisting of disodium phosphate and monopotassium phosphate. h Increase the temperature to 130℃ in 20 minutes, and at this temperature
Stained for 0 minutes. After washing with water, 2 parts of anionic surfactant at 100°C in 1000 parts of water containing 2 parts of sodium carbonate.
It was soaped for 0 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 Kukisu color.

Example 5 A dye bath was prepared using 2 parts of the compound of formula (7) obtained in Example 1, 80 parts of Glauber's salt, and 1,000 parts of water.
After dyeing 0 parts of cotton knitted fabric at 80° C. for 30 minutes, 20 parts of IJ carbonate was added thereto, followed by dyeing at the same temperature for 60 minutes. It was then soaped in the same manner as in Example 3 and dried with lukewarm water to obtain a turquoise dyed product.

This product had excellent wet fastness, light fastness, and chlorine fastness.

Example 6 20.0 parts of the compound of formula (12) and 3.4 parts of isonicotinic acid were dissolved in water, the pl-I was adjusted to 7, and the mixture was stirred at a temperature of 90°C for 5 hours. Next, the crystals precipitated by salting out were filtered and dried, and the formula (
33 parts of compound 13) were obtained. (628 nm (water)) After condensing and deacetylating minoaniline, it was obtained by reacting a condensate of cyanuric chloride and 2.5-disulfoaniline.

Examples 7 to 21゜Producing the compound of formula (1) according to Example 1, 2.6,
I dyed cotton.

Claims (1)

[Claims] (1) Formula (1) in the form of a free acid [In formula (1), PC represents a copper phthalocyanine group, 1]
]・1 is the number from 1 to 3, 1] is the number from () to 2, It
,I. INJ2. It3 is each independently a hydrogen ring or C1 to C
2 is an alkyl group, 4 is a methyl group; A is a phenyl group which may be substituted with a sulfonic acid group, a carboxyl group or a chlorine atom; A is a C2-C3 alkylene group; a methyl group, a sulfonic acid group Or represents a phenylene group which may be substituted with 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 OH, CI,
Water-soluble steel phthalosyanine compound (2) represented by the formula (1) in the form of a free acid [In formula (1), Pc is a copper phthalosyanine group. ,+
11. I C is the number from 1 to 3, I] is the number from o to 2, R
1゜lLz, R3 are each independently a hydrogen atom or C1~
c2 alkyl group, (14 is a methyl group, a sulfonic acid group, a carboxyl group, or a phenyl group which may be substituted with a chlorine atom, A is a C2-C3 alkylene group; a methyl group, a sulfonic acid group, or a carboxyl group) Represents a phenylene group which may be substituted with a group. (However, the carboxyl group of the pyridine nucleus is bonded to the 3- and 71st position of the pyridine nucleus, and the positive charge of the nitrogen atom of the pyridine nucleus is OH. Cellulose fiber or cellulose fiber-containing fiber 4A characterized by using a water-soluble steel phthalate compound represented by -, CI, SO; 'PI staining method.