JPS61130318A - Diallylamine polymer, its production and dye fixing agent containing the same - Google Patents

Abstract

PURPOSE:To obtain the titled polymer which is useful as a dye fixing agent and can give a dyed product excellent in fastness to chlorine, washing and light and resistant to discoloration, by polymerizing a diallylamine sulfate and/or diallylmethylamine sulfate. CONSTITUTION:A diallylamine polymer having a structural unit of the formula (wherein R is H or CH3) is obtained by polymerizing diallylamine sulfate and/or diallylmethylamine sulfate and, optionally, other copolymerizable monomers (e.g., a salt of allylamine with an acid) at 30-100 deg.C for 3-48hr in the presence of 0.1-7wt% radical polymerization initiator (e.g., ammonium persulfate). A dyeing solution containing 0.1-2wt% (in terms of solid) this polymer is formed, and an object to be dyed is submerged in this solution and treated at a liquor ratio of 1/10-20 and a temperature of normal -80 deg.C for 5-20min to obtain a dyed product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diallylamine polymer, a method for producing the same, and uses thereof. More specifically, the present invention relates to a diallylamine polymer useful for improving the fastness of dyed products obtained using reactive dyes, a method for producing the same, and a dye fastness improver containing the same.

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 treatment with an aqueous polyamine solution can prevent the dye from falling off to a certain extent, there are disadvantages such as discoloration of the dyed product, a decrease in chlorine fastness, and a decrease in light fastness.

It has been proposed to use diallylamine/acid polymers obtained by polymerizing organic acids or inorganic acid salts of tulamines as chlorine resistance improvers for dyed cellulose fibers with reactive dyes.

However, the publications described in the same publication, for example, diallylmethylamine hydrochloride polymer and diallylethylamine
Some dyes, such as sulfate polymers, do not show sufficient improvement in chlorine resistance depending on the dyes used for dyeing cellulose fibers, or are insufficient in other properties such as washing fastness, light fastness, or color change during processing. Improvements are still desired.

The present inventors 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 present inventors discovered a compound obtained by polymerizing sulfates of specific diallylamines. The inventors discovered that a polymer or copolymer was suitable for the purpose and completed the present invention.

That is, the present invention relates to a polymer having a structural unit represented by the following general formula (1) (wherein R represents a hydrogen atom or a methyl group), a method for producing the same, and a color fastness obtained by containing the same. Provides an enhancer.

The polymer of the present invention includes a polymer obtained by polymerizing diallylamine sulfate and/or diallylmethylamine sulfate, and a copolymer obtained by polymerizing other monomers that can be copolymerized with them. .

Copolymerizable monomers include allylamine and acid salts, triallylamine and acid salts, diallyldimethylammonium chloride, vinylpyrrolidone, dimylaminoethyl methacrylate, β-methacryloyloxyethyltrimethylammonium chloride, acrylamide, acrylonitrile, Examples include hydroxyethyl acrylate, methyl methacrylate, vinyl acetate, and styrene.

The polymer of the present invention is obtained by neutralizing diallylamine and/or diallylmethylamine with sulfuric acid, optionally adding the copolymerizable monomer (h), and then polymerizing the mixture in the presence of a radical polymerization initiator. 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. Examples include persulfate salts such as ammonium persulfate and potassium persulfate, azo compounds such as azobisisobutyronitrile, peroxides such as di-t-butyl peroxide, cumene hydroperoxide, and hydrogen peroxide. . The initiator is usually used in an amount of 0.1 to 7% by weight based on the weight of the monomer. Polymerization is usually carried out at 80-100°C1
It is preferably carried out at 40-80°C for 3-48 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 polymer thus obtained is particularly useful as a dye fastness improver, and the method for treating the dyed product is not particularly limited, and conventionally known methods can be applied. When processing using the immersion method, the concentration of the processing solution is usually 0 per solid content.
．． It is 1 to 2% by weight. 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 dyed products treated with the polymer 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. be.

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

Example 1 500 m equipped with thermometer, condenser and stirring device
1 flask (charged with 48.611 y of diallylamine and 63.1 y of ion-exchanged water, and 84.5 y of 71% sulfuric acid under cooling)
1 was added dropwise. Thereafter, under a nitrogen stream, the internal temperature was raised to 50°C, and ammonium persulfate was added to 1. After adding Of, polymerization was carried out for 4 hours with stirring, and then stationary polymerization was further carried out at 50'C for 24 hours, and ion-exchanged water 1461 was added to obtain a polymer aqueous solution (A) with a solid content of 25%.

Example 2 Diallylmethylamine 55.6 was added to the same apparatus as in Example 1.
f, 70.1 f of ion-exchanged water, and cooled to 1
% sulfuric acid was added dropwise.

After that, ammonium persulfate was added at 50″C under a nitrogen stream.
．． After adding Of, polymerization was carried out for 5 hours with stirring, and then stationary polymerization was further carried out for 24 hours. Ion exchange water 160.2
F was added to obtain an aqueous polymer solution CB) with a solid content of 25%.

Example 3 A 50% diallylamine sulfate aqueous solution 181.6F 150% acrylamide aqueous solution 7.1 was placed in the same apparatus as in Example 1.
ammonium persulfate at 50°C under a nitrogen stream. Of was added and polymerization was carried out for 4 hours while stirring. That night, 188.7 f of soaked water, which had been subjected to stationary polymerization for 24 hours, was added to dilute the solution to obtain a polymer aqueous solution (C) with a solid content of 25%.

Example 4 Into the same apparatus as in Example 1, 144.21 F of 50% diallylmethylamine sulfate aqueous solution and 2.7 t of acrylonitrile were added.
, 2.7y of ion-exchanged water was added, and heated at 50°C under a nitrogen stream.
ammonium persulfate at 1. , Oy were added and polymerization was carried out for 5 hours while stirring. That night, the stationary polymerization was carried out for another 24 hours, resulting in 149.6 yen! was added to obtain a polymer aqueous solution [D] with a solid content of 25%.

Comparative Example 1 A 50% diallylamine hydrochloride aqueous solution (138.6 F) was charged into the same apparatus as in Example, and 1.0 y of ammonium persulfate was added at 50° C. under a nitrogen stream, followed by polymerization for 7 hours with stirring. After further static polymerization for 24 hours that night,
It was diluted with 138.6 y of water to obtain a polymer aqueous solution (E) with a solid content of 25%.

Comparative Example 2 105.59 g of a 70% diallylmethylamine hydrochloride aqueous solution was charged into the same apparatus as in Example, and 1.1 g of ammonium persulfate was added at 50'C under a nitrogen stream. Polymerization was carried out under stirring for 5 hours, and in the evening, stationary polymerization was further carried out for 24 hours.

It was diluted by adding 189.8 F of water to obtain an aqueous polymer solution CF) with a solid content of 25%.

Comparative Example 3 70% diallylethylamine sulfate was charged into the same apparatus as in Example, and 1.0 y of ammonium persulfate was added at 50'C under a nitrogen stream. After polymerization was carried out for 10 hours under stirring, stationary polymerization was carried out for 48 hours. Wednesday 224.01
was added to dilute the solution to obtain an aqueous polymer solution CG) with a solid content of 25%.

25 of the polymers obtained in Example 12 and Comparative Examples 1 to 3 above
% aqueous solution viscosity, weight average molecular weight and cation equivalent were measured, and the results shown in the table below were obtained.

Hiromi and the catfish side” Hiro! Measurement is performed at 25°C using a Brookfield viscometer.

*2 Weight average molecular weight Measured by gel permeation chromatography using polyethylene glycerol as a standard substance. (Toyo Soda Kogyo's TSK Gel PW was used as the column) *8 Cation equivalent toluidine blue was used as the indicator, and T? It is measured by tachoroid titration method using rrf-N folihynyl potassium sulfate solution. (Measurement pH is 8.0.) Example 5 Using the aqueous polymer solutions obtained in the above examples and comparative examples, a cotton stockinette knit dyed with a reactive dye according to the conventional method No. ζ was subjected to the dipping method. Processing was performed.

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

■Method for making dyed cloth Name of test dye〉 Sumifix Br1lliant BlueR (C
I, Reactive Blue19)//
S@avlet H-2G (a Red48) Sumifix Tuvquolse BlueGl
50% (u B1ue21) Sumifix Sup vine Navy Blue 2
GF (// B1ue1g4) Unmercerized knitted fabric was dyed with the above dye at 3%-owf in a conventional manner.

■Dye fastness improver treatment conditions The dye fastness improver treatment was carried out using the exhaustion method. The concentration of the improver used was 0.5971 (solid content). or,
The other conditions were general usage conditions.

■Dyeing fastness test method (1) Discoloration and fading of the dyed product subjected to processing discoloration treatment was determined using a play scale. (Grade) (11) Washing fastness Tested according to JIS-L-0844A-4 method. Judgments were made on gray scale for discoloration and fading of dyed fabrics, cotton stains, and wool stains.

(Class) (According to IIO chlorine-treated water fastness l5O-R-105. (Available chlorine 20
(2/l, 25°C, 14 hours) Clear tap water chlorine fastness The treated fabric was placed in running tap water at 61/min for 5 hours, and discoloration and fading were judged on a gray scale. (available chlorine 1.3 scraps 9/
11 Temperature 15-20'C)) Lightfastness Tested according to JIS-L-0842.

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

Claims (3)

[Claims] (1) General formula below ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom or a methyl group. Was. ) A diallylamine polymer having a structural unit represented by: (2) The following general formula is characterized by polymerizing diallylamine sulfate or/and diallylmethylamine sulfate in the presence of a radical polymerization initiator ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is hydrogen A method for producing a diallylamine polymer having a structural unit represented by (representing an atom or a methyl group). (3) Improved color fastness by containing a diallylamine polymer having a structural unit represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a hydrogen atom or a methyl group.) agent.