JPS61203155A - Dye fixing agent - Google Patents

Abstract

PURPOSE:To provide a dye fixing, agent which gives dyed materials having improved fastness to chlorine, washing and light when dyed with reactive dyes, containing an allylamine polymer and a diallylamine polymer. CONSTITUTION:95-5mol% of an allyamine polymer contg. a structural unit of formula I (wherein X is a counter ion on an acid) is mixed with 5-95mol% of a diallylamine polymer contg. a structural unit of formula II (wherein R1-R4 are each H, methyl) to obtain a dye fixing agent. A dyed material obtd. by dyeing a material with a reactive dye is immersed in a treating solution obtd. by dissolving 0.1-2wt% said fixing agent in water, and treated at a bath ratio of 1:10-20 and at room temp. to 80 deg.C for 5-20min.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dye fastness improver containing an allylamine polymer and a diallylamine polymer. More particularly, the present invention relates to color fastness improvers useful for improving the fastness of dyed products obtained using reactive dyes.

Dyeings dyed using reactive dyes have vivid colors and excellent wet fastness, so in recent years they have been increasingly used in place of direct dyes. .

Reactive dyes form covalent bonds with the hydroxyl and amino groups of the fibers and become fixed, but 20-50% of the dyes used remain unreacted on the fibers, so they easily fall off and affect washing fastness. lower. Moreover, the dye that has formed a covalent bond also undergoes hydrolysis over time, and a phenomenon in which the dye falls off is observed.

In order to improve these problems, it is known to treat dyed products with an aqueous solution of polyamine. However, although the treatment with an aqueous polyamine solution can prevent the dye from falling off to some extent, it also causes permanent discoloration of the dyed product, decrease in chlorine fastness, decrease in light fastness, etc.

Japanese Patent Publication No. 45-1457 describes that a polymer obtained by polymerizing acid salts of diallylamines can be used as a washing fastness improver for dyed cellulose fibers. Diallylamine polymers have shown some improvement in discoloration of dyed products, reduction in chlorine fastness, and reduction in light fastness, but the effects are insufficient and improvements are still needed.

Furthermore, JP-A-58-81185 describes that polymers obtained by polymerizing allylamine acid salts are useful as dye fastness improvers for dyed products dyed with reactive dyes. . Some allylamine polymers have excellent chlorine fastness and light fastness, but
Washing fastness is insufficient and improvement is desired.

The inventors of the present invention have conducted intensive studies to find a compound that does not cause discoloration of dyed products and can improve the fastness to chlorine, light fastness, washing fastness, etc. As a result, the aim was to find a mixture of an allylamine polymer and a diallylamine polymer. The present invention was completed based on the discovery that the present invention is suitable for the following purposes.

That is, the present invention provides a polymer having a structural unit represented by the following general formula (r) (wherein, X represents an acid counteranion), and a polymer having the following general formula (U) (wherein, R1, R2, The present invention relates to a color fastness improver containing a polymer having a structural unit represented by the following formula: Ra and Ra each represent a hydrogen atom or a methyl group, and X represents an acid counteranion.

In general formulas (I) and (It), X is Ct
.

Halogen atoms such as Br, I, 804, NOs,
O■8Cω.

Examples include counter anions of acids such as PO4, and preferred are Ct, Br, Boa, and PO4.

In general formula (I[), R1, R2, Ra, and R4 are preferably hydrogen atoms.

In the present invention, the ratio of the polymer having a structural unit represented by the general formula (T) and the polymer having a structural unit represented by the general formula (I[) is arbitrary, but preferably the mole of the structural unit is The ratio is (1)/(II)=95-575-95
The ratio is more preferably 80-20/20-80, still more preferably 80-50/20-50.

The polymer of the present invention may consist only of structural units of general formula (1) and general formula (II), respectively, and may also contain structural units derived from other copolymerizable monomers. It may also be a copolymer.

Other copolymerizable monomers include vinylpyrrolidone,
Examples include dimethylaminoethyl methacrylate, β-methacryloyloxyethyltrimethylammonium chloride, acrylamide, acrylonitrile, hydroxyethyl acrylate, methyl methacrylate, vinyl acetate, and styrene.

The polymers used in the present invention are generally obtained by radical polymerization of corresponding monomers.

The polymerization is generally carried out in an aqueous solution at a monomer concentration of 20 to 90% by weight, preferably 40 to 70% by weight, but the polymerization may also be carried out in a solvent such as methanol, dimethyl sulfoxide or dimethylformamide.

As the radical polymerization initiator, commonly used initiators can be used. For example, persulfates such as ammonium persulfate and potassium persulfate, azo compounds such as 2,2'-diamidinyl-2,21-azopropane dihydrochloride, azobisisobutyronitrile, di-t-butyl peroxide, and cumene hydroperoxide. , peroxides such as hydrogen peroxide, and the like. The amount of initiator is usually 0.1 based on the monomer weight.
An amount of ˜20% by weight is used.

Polymerization is usually carried out at 80 to 100°C, preferably 40 to 80°C, for 8 to 48 hours. Although polymerization can be carried out in the presence of oxygen, it is preferable to carry out the polymerization while blowing nitrogen gas.

The mixture of polymers thus obtained is useful as a color fastness enhancer.

The method for treating the dyed material is not particularly limited, and conventionally known methods can be applied. When the treatment is carried out by the immersion method, the concentration of the treatment liquid is usually 0.1 to 2% by electric amount based on the solid content. The bath ratio is usually 1:10-20. The treatment temperature is usually room temperature to 80°C, and the treatment time is usually 5 to 20 minutes.

The respective polymers may be mixed in advance and added to the processing solution, or may be added separately at the time of preparing the processing solution.

The dyed products treated with the polymer mixture of the present invention are excellent in terms of chlorine fastness, washing fastness, light fastness, and process discoloration, regardless of the type of dye used for dyeing. It is.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, % represents weight %.

Synthesis Example 1 A 70% aqueous solution of allylamine hydrochloride (188.6F) was charged into a 500 flask equipped with a thermometer, a condenser, and a stirring device, and 2.2-diamidinyl-2.2'-azopropane hydrochloride 2 was heated at 50°C under a nitrogen stream. ．． Added Of. After polymerization was carried out for 8 hours with stirring, polymerization was further carried out for 488 hours. It was diluted by adding 240.5 f of water to obtain an aqueous polymer solution [A] with a solid content of 25%.

Synthesis Example 2 240.8 f of a 50% diallylamine hydrochloride aqueous solution was charged into the same apparatus as in Synthesis Example 1, and 2.0 g of ammonium persulfate was added at 70° C. under a nitrogen stream. 0 every hour thereafter.
Polymerization was carried out for 5 hours while adding 51 ammonium persulfate. It was diluted by adding 240.8 II of water to obtain an aqueous polymer solution CB) with a solid content of 25%.

Synthesis Example 8 Into the same apparatus as in Synthesis Example 1, 168.6 f of a 70% diallylmethylamine hydrochloride aqueous solution was charged, and 8, Of ammonium persulfate was added at 55° C. under a nitrogen stream. 24 hours under stirring
After polymerization for a period of time, 808.4j' of water was added to dilute the mixture to obtain an aqueous polymer solution (C) with a solid content of 25%.

Synthesis Example 4 Into the same apparatus as in Synthesis Example 1, 161.5 liters of a 70% diallyldimethylammonium chloride aqueous solution was charged, and 2.01 liters of ammonium persulfate was added at 50'C under nitrogen gas. Thereafter, polymerization was carried out for 8 hours while adding 1.0 g of ammonium persulfate every 2 hours. It was diluted by adding 290.7 f of water to obtain an aqueous polymer solution V with a solid content of 25%.

Example 1 The aqueous polymer solution (A) obtained in the synthesis example and [''B] were mixed at a ratio of [mu]/(B) = 55/45 (weight ratio) to obtain a polymer mixture. A cotton stockinette knit dyed with a reactive dye by a conventional method was treated by a dipping method.

The color fastness test results are shown in Tables 1 to 4. The test method for color fastness is as follows.

■ How to make dyed cloth Test dye name 2 Sumifiz Br1lliant Blue R (
C, 1, Reactive Blue19) 8carl
et H-2G (Red48) 8umifiz Turquoise Blue G
150% (Blue21) 8umifiz 5upra Navy Blue
e2GF (B1ue194) Unsilced knitted knitted fabric was dyed with the above dye at 8% owf in a conventional manner. (2) Conditions for treatment with dye fastness improver Treatment with the dye fastness improver was carried out by an exhaustion method. The concentration of the improver used was o, 5y, and t (solid content).The other conditions were general conditions.

(Dye fastness test method) Discoloration and fading of dyed products that had been processed and discolored was judged on a gray scale. (Class) (i) Washing fastness Tested according to method JI8-L-0844A-4. Judgments were made on gray scale for discoloration and fading of dyed fabrics, cotton stains, and wool stains. (Grade) (ip Fastness to chlorinated water Tested according to 18O-R-105.

(20q/l available chlorine, 25℃, 4 hours) (iV)
Tap water chlorine fastness The treated fabric was placed in running tap water at 6 L/min for 5 hours, and discoloration and fading were evaluated on a gray scale.

(Available chlorine 1.8q/A, temperature 15-20℃) q) Light fastness It was conducted according to JI8-L-0842.

Example 2 Polymer aqueous solution ['A)/CC')
The test was conducted in the same manner as in Example 1 except that the weight ratio was 80/70.

Example 8 Polymer aqueous solution CA), CD] (A)/(:'D)
The test was conducted in the same manner as in Example 1 except that the weight ratio was 80/20.

Comparative Examples 1 to 4 Polymer aqueous solutions (A), [B), (C), [
The test was conducted in the same manner as in the example except that D) was used alone.

The results of each fastness test show that the color fastness improver of the present invention is superior to known fastness improvers and improves each fastness.

Claims (1)

[Claims] A polymer having a structural unit represented by the following general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, X represents an acid counteranion.) Shown by the following general formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1, R_2, R_3, and R_4 each represent a hydrogen atom or a methyl group, and X represents an acid counteranion.) A dye fastness improver comprising a polymer having a structural unit.