JPH07292584A - Colored product dyed with direct dye - Google Patents

Abstract

PURPOSE:To provide a dye-fixing agent composed of a polymer of a monoallylamine derivative or its salt or a copolymer of the derivative, etc., and a monomer having unsaturated double bond and copolymerizable with the derivative, etc., and effective for improving the wet color fastness of fabric dyed with a direct dye. CONSTITUTION:The wet color fastness and the chlorine fastness of fabric dyed with a direct dye are improved without lowering the light fastness by treating the dyed fabric with a polymer of a monoallylamine derivative of formula (R is H, a 1-18C alkyl, a substituted alkyl, an aralkyl or a cycloalkyl) or its salt or a copolymer of the derivative or its salt and a monomer having unsaturated double bond and copolymerizable with the derivative, etc., e.g. a polymer of monoallylamine hydrochloride, a polymer of monoallylamine, a polymer of N-isopropylallylamine hydrochloride, a copolymer of monoallylamine hydrochloride and N-isopropylallylamine hydrochloride and a copolymer of allylamine hydrochloride and dimethyldiallylammonium chloride.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dye fixing agent for a direct dye. More specifically, it relates to an improved dye fixing agent which improves the fastness of the dyed article dyed with a direct dye, and a dyed article obtained by treating with the fixing agent.

[0002]

2. Description of the Related Art Direct dyes are widely used for dyeing cellulose fibers such as cotton and hemp, mixed-spun woven products of cellulose fibers and synthetic fibers, paper, wood, leather and the like. This is (1) the dyeing operation with a direct dye is simple and easy to use, and (2) the cost is relatively low and economical. It is thought to be due to the following characteristics: (3) No pollution to polyester, acrylic fiber, etc., (4) Extremely large number of colors, (5) Many things that are relatively easy to decolorize and can be re-dyed. .

On the other hand, there has been a problem with the fastness of direct dyes. In particular, the fastness to wetness (fastness to washing, fastness to water, etc.) is not good because the dye has almost no exception and has a sulfonic acid group and is easily soluble in water. As a countermeasure against this, generally, after dyeing, the dyed product is treated with a polyamine-based dye fixing agent, that is, a condensate of dicyandiamide and polyethylene polyamine, and some effects are exhibited. However, treatment with this type of dye fixing agent causes a problem that other fastnesses, such as chlorine fastness and light fastness, are rather lowered as compared with the case of untreated.

On the other hand, efforts are being made to improve the fastness by directly improving the dye itself, and recently, products having considerably improved wet fastness have been put on the market. However, the wet fastness is still insufficient, and it is essential to improve the fastness by using a dye fixing agent at present.

Therefore, there has been a demand for the development of a dye fixing agent which improves the wet fastness of the dyed product dyed with a direct dye, while not lowering the light fastness and the chlorine fastness as desired.

[0006]

In view of the above situation, the present invention improves chlorine fastness while improving wet fastness of a dyed product dyed with a direct dye, and does not cause deterioration of light fastness. The purpose is to develop a dye fixing agent.

[0007]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to achieve the above-mentioned object, the general formula

[Chemical 3] (In the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, a substituted alkyl, an aralkyl group, or a cycloalkyl group)
Dyeing with a direct dye with a polymer of a monoallylamine derivative or a salt thereof represented by, or a copolymer of the monoallylamine derivative or a salt thereof and a monomer having an unsaturated double bond copolymerizable therewith The present invention has been completed based on the finding that treating a product improves wet fastness and chlorine fastness and does not reduce light fastness. That is, the present invention relates to a dye fixing agent for improving the dyeing fastness of a dyed product dyed with a direct dye, wherein the fixing agent is the above-mentioned polymer or copolymer. Is.

General formula used in the present invention

[Chemical 4] (Wherein R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, a substituted alkyl group, an aralkyl group, or a cycloalkyl group), a polymer of a monoallylamine derivative or a salt thereof is exemplified by an allylamine polymer. , Allylamine hydrochloride polymer, allylamine sulfate polymer, allylamine phosphate polymer, N-methylallylamine polymer (the corresponding salt polymer is omitted hereinafter), N-ethylallylamine polymer, Nn-propyl Allylamine polymer, N-
iso-propylallylamine polymer, N-n-butylallylamine polymer, N-sec-butylallylamine polymer, N-tert-butylallylamine polymer, N
-Iso-butylallylamine polymer, N-octylallylamine polymer, N-cetylallylamine polymer, N
-Stearylallylamine polymer, N-hydroxyoxyethylallylamine polymer, N-benzylallylamine polymer, N-cyclopentylallylamine polymer, N-
A cyclohexyl allylamine polymer etc. can be mentioned.

Further, examples of the copolymer of the monoallylamine derivative represented by the general formula (I) or a salt thereof used in the present invention and a monomer having an unsaturated double bond copolymerizable therewith include: 1) Allylamine / N-methylallylamine copolymer,
Hydrochloride, phosphate, sulfate of the copolymer (the corresponding salt type is omitted below), allylamine /
N-ethylallylamine copolymer, allylamine / N-
n-Propylallylamine Copolymer, Allylamine / N
-Iso-propylallylamine copolymer, allylamine / N-n-butylallylamine copolymer, allylamine / N-sec-butylallylamine copolymer, allylamine / N-tert-butylallylamine copolymer,
Allylamine / N-iso-butylallylamine copolymer, allylamine / N-cyclohexylallylamine copolymer, allylamine / diallylamine copolymer, allylamine / N-methyldiallylamine copolymer, allylamine / N-ethyldiallylamine copolymer, allylamine / N-propyldiallylamine copolymer, allylamine / N-butyldiallylamine copolymer, allylamine / N-benzyldiallylamine copolymer, allylamine / dimethyldiallylammonium chloride copolymer, allylamine / diethyldiallylammonium chloride copolymer, allylamine / Methylbenzylammonium chloride copolymer 2) Using N-methylallylamine instead of allylamine in 1) above (provided that allylamine is used) / N-
(Except the case of methylallylamine) 3) Similarly, instead of allylamine in 1), N-ethylallylamine, N-n-propylallylamine, N-iso-propylallylamine, N-n-butylallylamine, N-sec-butyl respectively. Allylamine, N
-Tert-butylallylamine, N-iso-butylallylamine, N-octylallylamine, N-cetylallylamine, N-stearylallylamine, N-hydroxyoxyethylallylamine, N-benzylallylamine, N-cyclopentylallylamine, N-cyclohexylallylamine The used one can be mentioned. The polymer or copolymer used in the present invention may be a salt type, or a part or all of the salt type may be a free amine type. The salt-type polymer or copolymer is
The corresponding mineral acid salt of one or more monomers is treated with ammonium persulfate, benzoyl peroxide, in water or a polar solvent.
tert-butyl hydroperoxide, azobisisobutyronitrile, azobis (2-acidinopropane)
It can be obtained by polymerizing with a radical polymerization initiator such as hydrochloride. Moreover, caustic soda is added to the produced polymer,
When an alkali such as caustic alkali is added, the mineral acid corresponding to the added alkali is neutralized and released, so that a part or all of the free amine type polymer or copolymer can be obtained.

The method for treating a dyed product with the above-mentioned polymer or copolymer according to the present invention is not particularly limited, and a conventionally known method can be appropriately used. For example, in an aqueous solution of the polymer or copolymer having a concentration of 0.1 g / l to 5 g / l,
The dyed product to be treated may be dipped for a predetermined time, washed with water and dried. The bath ratio is usually 1:10 to 20, the treatment temperature is usually room temperature to 80 ° C., and the treatment time is usually 5
~ 20 minutes.

In order to further clarify the present invention, a production example of a polymer or a copolymer which is the dye fixing agent of the present invention is shown as a reference example, and then, a dyed product is treated with the fixing agent of the present invention, and An example of the result will be shown. The examples are representative examples, and the present invention is not limited to the examples.

[0012]

【Example】

Reference Example 1 1 mol of 35% hydrochloric acid was added to 1 mol of monoallylamine,
Monoallylamine hydrochloride having a concentration of 59.1% was obtained. This was concentrated to a concentration of 66.7% with a rotary evaporator.

After heating 50 g of this monomer aqueous solution to 60 ° C., 2.5% by weight of azobis (2-amidinopropane) hydrochloride was added to the monomer and polymerized for 48 hours. After the completion of the polymerization, the polymerization solution was precipitated in methanol, filtered, and dried under reduced pressure to obtain a white monoallylamine hydrochloride polymer. The polymerization rate was 97%.

Reference Example 2 10 g of monoallylamine hydrochloride polymer obtained in Reference Example 1
Then, 20 g of water was added and dissolved therein, and 22 g of a 20% aqueous solution of sodium hydroxide was added thereto. This solution was dialyzed against water using hollow fibers for 24 hours to remove the salt produced as a by-product, and then freeze-dried to obtain a monoallylamine polymer.

Reference Example 3 1 mol of 35% hydrochloric acid was added to 1 mol of N-iso-propylallylamine to obtain a 66.7% aqueous solution of N-iso-propylallylamine. After heating 20 g of this solution to 60 ° C., 2.5% by weight of azobis (2-amidinopropane) hydrochloride was added to the monomer, and the mixture was polymerized for 48 hours. After completion of the polymerization, the solution was precipitated in acetone,
A polymer of N-iso-propylallylamine hydrochloride was obtained by filtration and drying under reduced pressure. The polymerization rate was 94%.

Reference Example 4 14 g of a 66.7% aqueous solution of allylamine hydrochloride and N-
A solution obtained by mixing 20 g of a 66.7% aqueous solution of iso-propylallylamine hydrochloride was heated to 60 ° C.,
Azobis (2-amidinopropane) hydrochloride was added as a catalyst in an amount of 2.5% with respect to both monomers, and the mixture was polymerized for 48 hours.
After completion of the polymerization, this solution was treated in the same manner as in Reference Example 3 to obtain a white monoallylamine hydrochloride / N-iso-propylallylamine hydrochloride copolymer. Polymer is 94
%Met.

Reference Example 5 1 mol of 35% hydrochloric acid was added to 1 mol of diallylamine to obtain an aqueous solution of diallylamine hydrochloride having a concentration of 66.4%.
20 g of this solution was mixed with 14 g of a 66.7% aqueous solution of allylamine hydrochloride, heated to 60 ° C., and 2.5 wt% of azobis (2-amidinopropane) hydrochloride was added to both monomers, and the mixture was added for 48 hours. Polymerized. After completion of the reaction, this solution was treated in the same manner as in Reference Example 3 to obtain an allylamine hydrochloride / diallylamine hydrochloride copolymer. Yield is 100
%Met.

Reference Example 6 16 g of an aqueous solution of allylamine hydrochloride having a concentration of 59.1%, 16 g of dimethyldiallylammonium chloride and 5 g of water
Was added and dissolved to obtain an aqueous solution, which was heated to 60 ° C., and 2.5% by weight of azobis (2-amidinopropane) hydrochloride was added to both monomers for polymerization. After completion of the polymerization, this solution was treated in the same manner as in Reference Example 3 to obtain an allylamine hydrochloride / dimethyldiallylammonium chloride copolymer. The polymerization rate was 92%.

Reference Example 7 66.7% of N-iso-propylallylamine hydrochloride
To a solution obtained by adding 15 g of a 66.7% aqueous solution of diallylamine hydrochloride to 15 g of an aqueous solution, azobis (2-amidinopropane) hydrochloride was added as a catalyst to both monomers in an amount of 2.5.
%, And polymerized for 48 hours. After completion of the polymerization, this solution was treated in the same manner as in Reference Example 3 to obtain an N-iso-propylallylamine hydrochloride / diallylamine hydrochloride copolymer. The polymerization rate was 97%.

Example 1 Evaluation of Washing Fastness A 0.1% aqueous solution of each of the polymers and copolymers obtained in Reference Examples 1 to 7 was prepared. Then, the cotton cloth dyed with the following direct dye at a concentration of 2% (based on the weight of the fiber) is immersed in an aqueous solution of the polymer or copolymer at a bath ratio of 1:20 and a temperature of 50 ° C. for 20 minutes.
After soaking for 1 minute, it was washed with water and air dried. The dyes used are Serious Supra Yellow GD and Serious Supra Red 4B.
L, Serious Supra Blue B (manufactured by Bayer).

Similarly, a 0.1% aqueous solution of a condensate of dicyandiamide and diethylenetriamine was prepared and treated in the same manner as above. This is shown as a comparative example. Next, the wash fastness of this treated dyed cloth was evaluated by the A-2 method of JIS-L-0844. The results are summarized in Table 1.

[Table 1]

Example 2 Evaluation of Fastness to Chlorine Each of the polymers, copolymers obtained in Reference Examples 1 to 7 above,
And a 0.1% aqueous solution of a dicyandiamide-diethylenetriamine condensate used as a comparative example was prepared. Then, a cotton cloth dyed with the following direct dye at a concentration of 2% (based on the weight of the fiber) was treated in the same manner as in Example 1. The dye used is Solophenyl Blue 3RL (manufactured by Ciba Geigy),
They are Sumilite Supra Brown G (manufactured by Sumitomo Chemical Co., Ltd.) and Kayaras Supra Blue FFRL (manufactured by Nippon Kayaku).

Next, the chlorine fastness of this treated dyed cloth is determined by JIS.
-L-0884 strong chlorine test method (effective chlorine 2
It was examined by a method of 0 mg / l, pH 7, temperature of 27 ° C., Raku ratio of 200: 1, and time of 30 minutes. The results are summarized in Table 2.

[Table 2]

Example 3 Evaluation of light fastness A 0.1% aqueous solution of each of the polymers and copolymers obtained in Reference Examples 1 to 7 and the dicyandiamide-diethylenetriamine condensate used as a comparative example was prepared. Then, a cotton cloth dyed with the following direct dye at a concentration of 2% (based on the weight of the fiber) was treated in the same manner as in Example 1. The dyes used are Sumiride Spra Yellow BC, Sumilite Spra Red 4BL, and Sumilite Spra Blue FGL (manufactured by Sumitomo Chemical Co., Ltd.).

Next, the light fastness of this treated dyed cloth is determined by JI.
Using the fade meter in the method of SL-0842, 2
It was irradiated for 0 hours and examined. The results are shown in Table 3.

[Table 3]

[0026]

According to the dye fixing agent of the present invention, the following effects can be obtained with respect to the dyeing fastness of the dyed product dyed with the direct dye. 1) With respect to the fastness to washing, it is possible to obtain the same improvement effect as that of the conventional direct dye fixing agent. 2) Chlorine fastness is lowered in the conventional adhesive, whereas it is increased in the adhesive of the present invention. 3) Further, while the conventional fixing agent lowers the light fastness, the fixing agent of the present invention does not lower it.

Claims (3)

[Claims] 1. A dyed product dyed with a direct dye; (Wherein R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, a substituted alkyl group, an aralkyl group or a cycloalkyl group), a polymer of a monoallylamine derivative or a salt thereof, or the above monoallylamine derivative or a salt thereof. When,
A dye fixing agent for a direct dye, which is a copolymer with a monomer having an unsaturated double bond capable of being copolymerized therewith; 2. A dyed product dyed with a direct dye; monoallylamine hydrochloride polymer, monoallylamine polymer, N-
iso-propylallylamine hydrochloride polymer, monoallylamine hydrochloride / N-iso-propylallylamine hydrochloride copolymer, allylamine hydrochloride / diallylamine hydrochloride copolymer, allylamine hydrochloride / dimethyldiallylammonium chloride copolymer or N -A dyed product obtained by treating with a dye fixing agent for a direct dye, which is an iso-propylallylamine hydrochloride / diallylamine hydrochloride copolymer. 3. A dyed product dyed with a direct dye; (Wherein R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, a substituted alkyl group, an aralkyl group or a cycloalkyl group), a polymer of a monoallylamine derivative or a salt thereof, or the above monoallylamine derivative or a salt thereof. When,
A process for producing a dyed product, which comprises treating with a dye fixing agent for a direct dye, which comprises a copolymer with a monomer having an unsaturated double bond which is copolymerizable therewith.