JPS60195162A - Dye composition for polyester/cellulose blend fiber - Google Patents

Abstract

PURPOSE:To provide a dye composition containing a dispersant, an antidrying agent, a defoaming agent and a water-insoluble halomethylphthalocyanine, and capable of dyeing the titled fiber in uniform and clear turquoise blue color having excellent light fastness. CONSTITUTION:The objective composition can be produced by compounding (A) a dispersant (preferably a combination of a nonionic dispersant and an anionic dispersant), (B) an antidrying agent (e.g. ethylene glycol), (C) a defoaming agent (e.g. silicone defoaming agent) and (D) a water-insoluble or hardly soluble halomethylphthalocyanine compound of formula I [Me is Cu, Ni, Co or Fe; Pc is phthalocyanine residue; X is Cl or Br; n is 0 or 1; m is 1-4 (the average number of halomethyl groups)] (e.g. the compound of formula II). The amounts of the components A, B, C and D are preferably 4-8(wt)%, 5-10%, 0.01-0.1% and 8-12%, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a dye composition for dyeing blue.

Specifically, the present invention relates to a specific 7-talocyanine dye composition that has a halogenated methyl group as a reactive group and dyes cellulose fibers in a covalent bond state.

Conventionally, a 7-talocyanine dye shown by the following structural formula [11] has been known as a dye capable of dyeing polyester/cellulose mixed fibers in turquoise blue (%
Kaiaki &j-JF4'#? Publication No.).

However, when polyester/cellulose is printed using the above-mentioned dyes, the dyeability is not sufficient, and as a result, in the cleaning process to remove undyed dyes, the areas that should be left as hot water are contaminated. Unable to obtain quality printed products. In addition, since the above dye (Ell) is attached to cellulose fibers in an adsorbed or clathrated state, there is a problem that the dye dissolves into solvents such as tetrachlorethylene and contaminates hot water during dry cleaning. ing.

The present invention is directed to a dye composition containing 7 talocyanines that are sparingly soluble or insoluble in water, have a specific reactive group, can obtain high-quality printed products, have excellent fastness properties, and are free from hot water stains during dry cleaning. The purpose is to provide something.

That is, the present invention provides a dispersant, an anti-drying agent, an antifoaming agent, and 7 types or 2s or more of the general formula [■] (in the formula, M13
#-1 represents Cu, Ni, Co or Fe, Pc
represents a phthalocyanine residue, X represents a chlorine atom or a bromine atom, n represents 0 or /, and m represents /
-4 (representing the average value of halomethyl groups)) The gist thereof is a polyester/cellulose mixed fine dye composition containing a halomethyl 7-talocyanine that is sparingly soluble or insoluble in water.

The dispersant toshite, which is a layering component of the dye composition of the present invention, is
Conventional nonionic and anionic dye dispersants can be used.

As a nonionic dispersant, especially JP-A-36-1.2g
Adducts obtained by reacting phenol, metacresol or paracresol with styrene and ethylene oxide or propylene oxide as described in Japanese Patent No. 370 can be preferably used.

Examples of anionic dispersants include ligninsulfonic acid groups,
Sulfonic acid salts of phenol-formaldehyde low condensates, sulfonic acids of naphthalene-aldehyde low condensates” 1
etc. can be suitably used.

In particular, a combination of the above-mentioned nonionic dispersant and anionic dispersant is suitable from the viewpoint of cleaning effect.

Also, as anti-drying agents, ethylene glycol, propylene glycol, /,! - Bentanediol, diethylene glycol A variety of known polyethylene glycols can be used, such as polyethylene glycol with a low molecular value of about xaoo to 1 Ioo molecules.

In addition, as an antifoaming agent, a silicone antifoaming agent such as X'FS Antiform tp+" (trademark) manufactured by Dow Corning,
Various known antifoaming agents can be used, such as Pluronic antifoaming agents such as Adekanol LG-2t' (trade name) manufactured by Asahi Denka.

The poorly soluble or insoluble halomethyl phthalocyanine used in the present invention is represented by the general formula (1) above, where Me is preferably Cu, and m is λ~3. Nolotatilphthalocyanines are preferred.

In the formula, %m represents the average value of halomethyl groups.

The halomethylphthalocyanine of the present invention can be prepared by a known method,
For example, British Patent No. Ag 9,133, French Patent No. 1,1103. ．． It can be easily synthesized according to the method described in No. 133.

For example, ffIJ can be easily synthesized by reacting phthalocyanines and bisno-romethyl ether in sulfuric acid at a temperature of θ0 to 90C.

The dye composition of the present invention is produced as follows. That is, the above-mentioned sparingly soluble or insoluble halomethyl phthalocyanine and the necessary amount of dispersant, anti-drying agent, antifoaming agent, etc. are added to water, and the mixture is mixed with water using a grain crusher such as a sand grinder or paint conditioner. 10 Methyl phthalocyanine 0.07~10μ Preferably 0.0/~O
, Sμ, and then dispersed to obtain an aqueous dye composition.

The aqueous dye composition of the present invention, in the composition, the amount of rotatilphthalocyanine i% ff~/kojumonchi, dispersant is 7~
3% by weight, anti-drying agent! It is preferable to adjust the amount of antifoaming agent to 10% by weight, 1% by weight and 0.07 to 0.7% by weight.

/Nionic content When using a Q agent and an anionic dispersant together, it is preferable that the nonionic dispersant + - j weight and the anionic dispersant J 71j weight or less.

Examples of polyester fibers such as polyester/cellulose mixed fibers suitably dyed with the dye composition of the present invention include polyethylene terephthalate, polybutylene terephthalate, and modified polyesters obtained by modifying these with isophthalic acid or the like.

On the other hand, examples of cellulose fibers include cotton, hemp, viscose rayon, polynosic rayon, copper ammonia rayon, and the like. Of these, cotton is particularly suitable. The forms of polyester/cellulose mixed fibers are blended,
Examples include woven and knitted fabrics such as mixed fibers, mixed weaves, and mixed knits.

Next, the dyeing method for dyeing polyester/cellulose mixed fiber using the aqueous dye composition of the present invention will be explained.
A padding dyeing method and a textile dyeing method can be suitably used.

In preparing the padding bath and printing dyeing paste, a wide range of alkaline compounds or alkali precursor compounds which generate alkali when heated in the presence of water can be added as acid binders.

The amount of these acid binders to be used is usually such that the pH of the dyeing bath, pub-bubble bath or printing paste becomes 7.5 to 9.0.

Furthermore, when dyeing linear mixed fibers, it is preferable to include a cellulose fiber leavening agent in the dye bath or color paste.

As a cover for using cellulose fiber swelling agent, use 3 to 50% for dye bath or color paste! in the range i% by weight, preferably g to 13
% ranges may be mentioned.

In order to dye the mixed fibers etc. with the dye represented by the above general formula [I] of the present invention, the mixed fibers etc. are impregnated or imprinted in a dye bath or colored paste prepared and produced by the above method in accordance with a conventional method. It is best to perform printing, drying, heat treatment, and then washing with hot water containing a surfactant.

By dyeing the above-mentioned various fibers using the dye composition of the present invention, bright and uniform dyeing with various fastnesses,
In particular, it is possible to obtain turquoise blue fibers with good light fastness.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Examples / Copper phthalocyanine dye represented by the formula [1[1,1% formula% () lθ part, 3 parts of lignin sulfonates, polyoxyethylene glycol nonylphenyl ether (HLB/3.3) lI part, ethylene Krikol (1 part, silicone antifoaming water 0.1 parts and water 7 parts)
the law of nature,? A water-based dye composition was prepared by finely dispersing the mixture using a paint shaker as a fine dispersion machine. Using this dye composition, make the following composition Dye composition t, left 2% sodium alginate aqueous solution 3S v Pyongyeon OO
Polynige 94 Liglycol Dimebso lzm-Til 9
A printing dyeing paste (pH !) with v water residue total of 100 f was prepared, and a polyester/cotton (mixing ratio A!r/, 3!r) blended fabric was printed using a screen printing machine, and the color was θC. After drying for 3 minutes with /
It was fixed by high temperature steaming at 90C for 3 minutes and 11JJ. After washing this with water, use a nonionic surfactant (Score Roll #de θO (
Trademark), manufactured by Kao Soap Co., Ltd.), using a cleaning solution containing 2t/l at a bath ratio of /:30 for 20 minutes on troC, resulting in a Turkish soap with a light fastness of grade 1 and a washing fastness of grade 3. A blue dyeing was obtained.

The dye used in Example 1 was synthesized by the following method.

That is, 9 parts of paraformaldehyde were added to 2 parts of s #sulfuric acid, and 70 parts of chlorosulfonic acid was added without cooling.

Copper phthalocyanine 1 was added to this, and the temperature was raised to gOC. 70 parts of common salt was gradually added and the mixture was stirred at goC for 10 hours. After the reaction was completed, it was discharged into ice water, and the precipitate deposited was filtered out, washed with water, and dried at so0~AOC.

Example Copper phthalocanine dye IO part represented by formula (IV), naphthalene sulfonic acid-formaldehyde condensate part a, following formula [■
] Part S of nonionic dispersant, Part S glycerin, 0.7 part silicone antifoaming agent, CH.

and 77.9 parts of water were finely dispersed using a sand grinder to prepare an aqueous dye composition.

Using this dye composition, create the following composition dye composition 6? A padding bath (pHg, !r) of CHaO + C, H, O dirt CH, / 0 / water was prepared and impregnated into a polyester/cotton (mixing ratio AA; /3!;) blended fabric.
After squeezing to 1%, dry at 100C for 2 minutes,
Dry heat attachment was carried out at 20θC/min. By washing this product in a hot ethanol bath, a dyed product of turquoise blue color having a light fastness of class J and a washing fastness of class 4t-3 was obtained.

The dye used in this example was synthesized by the following method.

That is, 3.7 parts of copper phthalocyanine to 1OO% sulfuric acid! 7
After adding Part A to Part A and stirring the mixture for 7 hours, bis-bromomethyl ether/0. g m, 230~3
Added at 0C. After that, the temperature was raised to 901C and this temperature tW
The reaction was carried out for −g hours. Next, the mixture was cooled to 20-30C, poured into ice water tqQs, and stirred at 0-tC for 7 hours. The final precipitate was filtered off and dried under reduced pressure.

Example 3 Phthalocyanine dyes listed in Table 7 were synthesized according to the method described in Example 1 or Example 2, and then an aqueous dye composition was prepared according to the method described in Example 1. Using this composition, polyester/cotton (
ts73r) The blended fabric was printed.

The obtained dyed product had no staining in the white part and had particularly excellent light fastness and wet fastness.

Table 1 Examples The 7 talocyanine dyes listed in Table 1 were synthesized according to the method described in Example 1 or Example 1, and then an aqueous dye composition was prepared according to the method described in Example 1. was prepared. Using this composition, a polyester/cotton (63/1) blend fabric was padded and dyed by the method described in Example C.

The light fastness and wet fastness of the dyed product obtained were particularly excellent.

Table 12

Claims (3)

[Claims] (1) Dispersant, anti-drying agent 1. Antifoaming agent and 7 types or 2 or more types of general formula (1) (wherein MeldCu, N soil, CO or Fe is represented, Pc represents a phthalocyanine residue, X represents a chlorine atom or a bromine atom, A dye composition for a polyester/cellulose mixed fiber containing a halomethylphthalocyanine which is sparingly soluble or insoluble in water and is represented by the following formula: n represents 0 or 1, and m represents 1-hiro (average value of halomethyl groups). (2)! #Polyester M according to claim 1
A composition in which e is Cu. (3) The dye composition for polyester/cellulose mixed fibers according to claim 1, wherein m is 1 to J.