JPS5936711B2 - Washing method for metal-containing dye-dyed textile products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for washing metal-containing dye-dyed textile products using an oxygen bleach to remove metal atoms, heavy metals such as copper, chromium, cobalt, and nickel in the dye structure dyed onto the fibers. A method for washing textile products dyed with metal-containing dyes while preventing adverse effects on the physical properties of textile materials (fiber embrittlement) and discoloration and fading of dyes caused by an abnormal reaction between the dye and oxygen bleach. Regarding.

Metal-containing dye processing generally refers to the color fastness of the dye (sunlight,
The above metal ions are added to reactive dyes or direct dyes in order to increase the washing, friction fastness, etc.), increase the number of dye colors, make dyes with vividness, or enable easy dyeing processing. A metal-containing reactive dye mixed as a metal complex,
It refers to a dyeing process using a metal-containing direct dye, or a dyeing process in which a metal complex is formed in the fiber by performing a metal salt post-treatment after dyeing with a direct dye.

These treatments also include dyeing methods using two or more different metal-containing dyes in combination depending on the desired hue. As heavy metal ions, copper, chromium, cobalt, nickel, etc. are used depending on the hue and the like. recently,
Clean colored striped shirts with oxygen bleach (sodium perborate,
There have been many complaints in Japan that cleaning with soda (soda percarbonate, etc.) causes the fibers to become crumbly and brittle, and the color changes and fades.This has become a major problem, and has been reported on in newspapers and on TV.

Therefore, the Ministry of International Trade and Industry and other organizations conducted an investigation and determined that the above-mentioned fiber embrittlement and color change and fading could be caused by the treatment of cellulose fibers dyed with dyes containing metals in the chemical structure of the dyes (metallic dyes) using oxygen bleaching agents. The cause of fiber embrittlement and color change and fading is that heavy metals in the dye structure and oxygen bleach react abnormally, causing heavy metals to adhere to the parts of the dye. It has been found that the oxygen bleach undergoes severe decomposition, resulting in a decrease in the degree of polymerization of the polymeric substance, resulting in fiber embrittlement, and destruction of the dye, resulting in color change and fading. Subsequently, the Ministry of International Trade and Industry and other organizations continued to conduct various washing experiments using oxygen bleach for textile products dyed with metal-containing dyes, and in June 1972, the Ministry of International Trade and Industry issued the following administrative guidance to various industries. It has reached this point. For the dyeing industry: 1. Avoid dyeing thin textile fabrics with metal-containing dyes.

When using dyes that may cause problems with dioxygen bleach treatment, be sure to check in advance and be careful.
For the cleaning industry, 1. Processing with oxygen bleach should be carried out under conditions that minimize embrittlement, discoloration and fading (normally below standard washing conditions), and 2. It was advised to avoid using oxygen bleach when washing clothes.

Therefore, in view of the above, the present inventors have proposed that when washing metal-containing dye-dyed textile products using an oxygen bleach, it is possible to wash the fabric under not only normal standard washing conditions but also under harsh conditions (above standard washing conditions). We conducted extensive research to find out whether it is possible to wash thin dyed textile products with poor strength while minimizing fiber embrittlement and color change and fading.

As a result, the present inventors have discovered that fiber embrittlement and color change and fading can be significantly improved by allowing a specific organic nitrogen compound to exist in the washing bath. According to the present invention, it is also possible to prevent wasteful decomposition of oxygen bleach in the laundry bath,
More effective washing and bleaching can be performed. Heavy metals in the structure of metal-containing dyes significantly decompose oxygen-based bleach during washing, resulting in unnecessary consumption of oxygen-based bleach; however, when the above nitrogen compounds are present in the washing bath, they degrade the structure of metal-containing dyes. The wasteful decomposition of oxygen bleach caused by heavy metals is significantly suppressed. That is, the present invention provides that when textile products dyed with metal-containing dyes are washed and bleached using an oxygen bleach, the washing bath contains (1) at least two or more nitrogen atoms in the molecule, and (2) One of the nitrogen atoms is present as a primary or secondary amino group, the other as a primary, secondary or tertiary amino group or a sulfonamide; (3) the nitrogen atoms are carbon atoms; This is a washing method characterized by the presence of an organic nitrogen compound or a salt thereof in which not more than 6 atoms are bonded via a saturated hydrocarbon or a partially cyclic saturated or aromatic hydrocarbon.

Typical examples of organic nitrogen compounds used in the present invention include the following.

Ethylenediamine, hexamethylenediamine, triethylenetetramine, N-carboxyethylenediamine, piperazine, N,N'-dimethyl-P-phenylenediamine, P-phenylenediamine, P-aminobenzenesulfonamide, 2-methylbenzimidazole, 0-tolylbiguanide , 1-phenyl biguanide, biguanide,
Examples include 1-alkylbiguanide, 1,5-dialkylbiguanide, 1,1'-ethylene dibiguanide, 1-phenyl-5,5-diethylbiguanide, and salts thereof. Examples of the salt include sodium salt. For deep color dyeing, biguanides or their salts are preferred. The concentration of these organic nitrogen compounds cannot be determined depending on the degree of dyeing and the type of metal-containing dye, but the concentration in the washing bath is in the range of 0.01 to 10 y/l, preferably 0.05 to 10 y/l. Used at 1y/l.

If it is less than 0.017/l, a desirable effect cannot be obtained, and 10
Above y/l, the effect no longer increases and is meaningless.

Oxygen bleaches applicable to the present invention include hydrogen peroxide,
Examples of commonly used hydrogen peroxide adducts include sodium perborate, percarbonate sorter (urea peroxide, etc.), and peroxide sorter (organic peracid (peracetic acid, etc.)).

The fiber materials applicable to the present invention are natural, synthetic or semi-synthetic fibers, blends, blends, knits, and other fiber products of these fibers. The metal-containing dye dyeing process applied to the present invention includes a dyeing process using a metal-containing reactive dye, a metal-containing direct dye, a metal salt post-treatment process after direct dye dyeing, or a combined dyeing process using these various dyes.

As the washing method, the conditions normally used in the cleaning industry are applied, but conditions more severe than the normal standard washing conditions can also be applied.

Standard washing conditions are oxygen bleach 2.57/l (as sodium perborate or soda percarbonate), powdered soap 0.5/l
7/11 sodium metasilicate 3y/11 bath ratio 1:20, washing temperature 60°C, washing time 30 minutes, but harsh conditions include, for example, oxygen bleach 257//l or more, washing temperature 60°C.
℃ or more, washing time is 30 minutes or more, etc. According to the present invention, not only normal standard washing conditions but also severe washing conditions can be used.
In addition, it significantly improves the fiber embrittlement and color change and fading that occur when washing textile products dyed with metal-containing dyes using oxygen bleach without causing any problems even when textile products with poor fabric strength are washed. I can do it.

The metal-containing dye-dyed textile products used in the following examples are:
In order to easily measure the degree of decrease in strength and the degree of color change and fading, a metal-containing dye was used on a bleached test cloth measuring 31 cm by 28 cm.
It is made by dyeing plain dyeing and striped printing using conventional methods.

Printed striped printing is a printed striped line with a width of 3mm (length 20mm).
Cr1L) was stained in such a manner that 40 lines were stained at intervals of 2 m1L in width. The dyed fabric thus obtained has exactly the same quality as actual textile products.

The degree of decrease in strength and degree of color change and fading of the original dyed fabric and after washing were measured as follows.

(b) Strength measurement The tensile strength in the warp direction was measured for a plain dyed cloth sample with a width of 4C7rL1 and a length of 21c7n in the warp direction, and for a printed striped cloth sample with a width of 4 and a length of 21 in the warp direction and 40 printed striped lines. Measurements were made using a shovel type tensile strength tester, and comparisons were made between the dyed original fabric and the washed fabric.

(b) Measurement of color change and fading The wavelength of maximum absorbance of each raw dyed fabric was measured using a color studio manufactured by Nippon Denshoku Kogyo Co., Ltd., and the wavelength of maximum absorbance of each dyed fabric after washing was measured at those wavelengths of maximum absorbance. Absorbance was measured.

The lower the absorbance, the greater the color change and fading, and the closer the absorbance is to the dyed original fabric, the smaller the color change and fading. Example 1 A required amount of the organic nitrogen compound shown in Table 1 was added as an inhibitor to the washing bath, and cotton 1 was dyed with the metal-containing dye shown in Table 1.
The 00% Prode cloth was washed under normal standard conditions and harsh conditions based on the JIS Standard (JISLIO72) Commercial Laundry 102 Method.

For washing, use sodium perborate (available oxygen 10.3% product) 2.5
y/l or 107/11 powder stone type 0.5t/11
Using an aqueous solution containing 37/l of sodium metasilicate and adding the organic nitrogen compounds shown in Table 1, the bath ratio was 1:20.
, 60° C. or 80° C. for 30 minutes, and was washed 5 times in accordance with JIS standards. Table 1 shows the tensile strength, absorbance, and decomposition rate of sodium perborate at the first washing of the dyed fabric obtained. For comparison, the tensile strength, light absorption, and decomposition rate of sodium perborate at the first washing of the original dyed fabric and the dyed fabric washed without using an organic nitrogen compound are also shown in Table 1. By adding organic nitrogen compounds, the bath stability of sodium perborate is increased not only under standard conditions but also under harsh conditions, and effective bleaching is performed to minimize fiber embrittlement and color change and fading. can be used to wash textile products dyed with metal-containing dyes.

Example 2 The required amount of the organic nitrogen compound shown in Table 2 was added as an inhibitor to the washing bath, and the dyed fabric, which had been dyed with a metal-containing dye and had a relatively weak fabric strength, was dyed according to the JIS Standard (JISLIO72) Commercial Laundry 102 method. I washed it.

For washing, use soda percarbonate (13.6% effective oxygen product) 5f/'
, Powder Stone Ken-type 0.5f/11 Sodium Metasilicate 3f
J
Washing was repeated five times based on IS standards.

Table 2 shows the tensile strength, absorbance, and decomposition rate of sodium percarbonate at the first washing of the dyed fabric obtained. For comparison, the tensile strength, absorbance, and decomposition rate of sodium percarbonate at the first washing of the original dyed fabric and the dyed fabric washed without using an organic nitrogen compound are also shown in Table 2. According to the present invention, even fiber products with poor fabric strength, such as foils and lawns, can be washed while minimizing fiber embrittlement and color change and fading.

Example 3 The required amount of the organic nitrogen compound shown in Table 3 was added as an inhibitor to the washing bath, and various dyed fabrics dyed with metal-containing dyes shown in Table 3 were subjected to the JIS Standard (JISLIO72) Commercial Laundry 102 method. I actually washed it.

Washing with 35% hydrogen peroxide 5f/11 powdered stone type 0.
Using an aqueous solution containing 37/l of 5r/11 sodium metasilicate and adding an organic nitrogen compound, the bath ratio was 1:20.
Washing was repeated 5 times at 700C for 45 minutes based on JIS standards.

Claims (1)

[Claims] 1. When washing textile products dyed with metal-containing dyes using an oxygen bleach, the following (1) to (5) are added to the washing bath.
) Washing method for metal-containing dye-dyed textile products characterized by the presence of at least one organic nitrogen compound or its salt (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Polyalkylene polyamines ( In the formula, R is a hydrogen atom or -COOH, m = 0 or 1 to 3, and when m = 0, n = 1 to 3, m = 1 to
3, n=1, when R is COOH, m=0, n=1
It is. )(2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Aromatic amine or aromatic diamine [where R
_1 is a hydrogen atom or a methyl group, R_2 is NHR' (R
' is the same as R_1) or SO_2NH_2](
3) Biguanides represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a hydrogen atom, methyl group, phenyl group, tolyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_2, R_3, R_4 is a hydrogen atom, a methyl group or an ethyl group. (However, R_2, R_3 and R_4 are all methyl groups,
Excluding the ethyl group, and when R_1 is ▲Numerical formula, chemical formula, table, etc.▼, R_2, R_3 and R_4 are hydrogen atoms. )] (4) Piperazine (5) Methylbenzimidazole