JPS6228228B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, metal atoms in the dye structure dyed on the fibers, heavy metals such as copper, chromium, cobalt, and nickel react abnormally with the oxygen bleach during washing of metal-containing dye-dyed textile products using an oxygen bleach. The present invention relates to 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 washing. Metal-containing dye-dyed textile products are generally products that increase the dye fastness of dyes (to sunlight, washing, friction fastness, etc.), increase the number of dye colors, make dyes with vividness, or allow easy dyeing processing. Refers to textile products dyed with metal-containing reactive dyes, metal-containing direct dyes, metal salt post-treated direct dyes, etc., in which the above-mentioned metal ions are mixed as metal complexes into reactive dyes or direct dyes. Recently, there have been many complaints in Japan that when cleaning colored striped shirts with oxygen-based bleaches (sodium perborate, soda percarbonate, etc.), the fibers become crumbly and brittle, and the color changes and fades. It became a big problem and was covered in newspapers and on TV. At first, it was thought that fiber embrittlement, color change and fading were caused by heavy metal contamination, natural embrittlement, etc., but as the problem became more serious, the Ministry of International Trade and Industry and other organizations began investigating and considering that fiber embrittlement, color change, and fading were caused by heavy metal contamination, natural embrittlement, etc. It was revealed that heavy metals in the dye structure were the main cause. In other words, fiber embrittlement and color change and fading occur when cellulose fibers, etc. dyed with dyes containing metals in the dye chemical structure (metallic dyes) are washed using oxygen bleaching agents. was found, and fiber embrittlement,
The cause of color change and fading is that due to an abnormal reaction between the heavy metals in the dye structure and the oxygen bleach, violent decomposition of the oxygen bleach occurs in the area dyed with the metal-containing dye, resulting in polymerization of the polymeric substance. It has been found that loss of strength occurs, leading to embrittlement of the fibrous material, and destruction of the dye structure occurs, leading to discoloration and fading of the color. Therefore, the Ministry of International Trade and Industry conducted various washing experiments using oxygen bleach for textile products dyed with metal-containing dyes.
In June 1952, the following administrative guidance was given to each industry. For the dyeing industry, avoid dyeing thin textile fabrics containing metals, and be sure to check in advance and be careful when using dyes that may cause problems when treated with oxygen bleach. For the cleaning industry, treatment with oxygen bleach should be carried out under conditions that minimize embrittlement, color change, and fading (usually below standard washing conditions);
It was advised to avoid using oxygen bleach when washing thin fabrics dyed with metal-containing dyes, which have poor fabric strength. In view of the above, the inventors of the present invention have found that when washing metal-containing dye-dyed textile products using an oxygen bleach, it is possible to wash them not only under standard washing conditions but also under harsh conditions (above standard washing conditions). We also conducted intensive research to see if it would be possible to wash thin dyed textile products with poor fabric strength while minimizing fiber embrittlement and color change and fading. As a result, 0.05 to 2% of the aminocarboxylate organic chelating agent and water-soluble salts were added to the washing bath using oxygen bleach.
g/, and (1) sugar alcohols or (2) water-soluble salts of aldonic acids or lactones thereof, 0.2 to 2 g/
The present inventors have discovered that fiber embrittlement and color change and fading caused by heavy metals in the dye structure can be significantly improved by the presence of . In the present invention, the metal-containing dye is a dye containing a heavy metal, and the heavy metal in the dye structure is a component of the dye for improving the dyeing quality of textile products.
If the heavy metals in the dye are simply sequestered or removed to prevent fiber embrittlement, the dye structure will be destroyed, causing color change and fading, and the heavy metals will deteriorate the dyeing quality of the product. Examples of the water-soluble salts of the aminocarboxylate organic chelating agent used in the present invention include nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and cyclohexanediaminetetraacetic acid (CyDTA). Examples of water-soluble salts include Na salt and K salt. These are 0.05-2g/in the washing bath.
, preferably 0.2 to 1 g/
Used within the range of If the amount is less than 0.05 g, favorable results will not be obtained, and if it is more than 2 g, the bath stability of the oxygen bleach will be significantly destabilized, resulting in significant discoloration and fading. In the present invention, an aminocarboxylate organic chelating agent and a sugar alcohol or aldonic acid are used in combination. Even when aminocarboxylate organic chelating agents are used alone, fiber embrittlement, color change and fading,
Although the stability of peroxide in the bath is significantly improved, it is not sufficient in terms of color change and fading. However, when used in combination with sugar alcohols or aldonic acids, the color discoloration and fading are further improved, particularly for those with low washing fastness such as copper salt post-treated direct dyes and copper complex direct dyes. Fiber embrittlement and peroxide stability in the bath are also slightly improved. Examples of sugar alcohols used in the present invention include D-glucinate, D-mannite, D-xylet, and erythromannoctite. These are used in the washing bath in a range of 0.2 to 2g/, and below 0.2g/the bath stability decreases.
There is a tendency for color change and fading to occur, and on the other hand, at 2 g/or more, this tendency becomes remarkable. Examples of the aldonic acid used in the present invention include aldonic acids obtained from aldoses such as D-mannose, D-xylose, and D-glucose. Furthermore, these water-soluble salts such as Na
Salts, K salts, etc. or lactones of these acids can be used. These are 0.2-2g/in the washing bath.
If the amount is less than 0.2 g, the bath stability will decrease and the color will tend to change or fade, while if it is more than 2 g, this tendency will become noticeable. Oxygen bleaches that can be applied to the present invention include hydrogen peroxide, hydrogen peroxide adducts (sodium perborate, sodium percarbonate, urea peroxide, etc.), sodium peroxide, organic peracids (peracetic acid, etc.), etc. Here are the commonly used ones. The fibrous material applied to the present invention is a natural, synthetic or semi-synthetic fiber, or a blended, woven, knitted or other textile product of these fibers. The textile products dyed with metal-containing dyes applied to the present invention are textile products dyed with metal-containing reactive dyes, metal-containing direct dyes, metal salt post-treated direct dyes, or textile products dyed in combination with these various dyes. can be given. As for the washing method, the conditions normally used in the cleaning industry are applied, but the standard washing conditions can also be applied to conditions that are harsher than the standard washing conditions. (as soda percarbonate), powdered soap type 0.5g/
, sodium metasilicate 3g/, bath ratio 1:20, washing temperature 60℃, washing time 30 minutes, but severe conditions are defined as oxygen bleach 2.5g/or more, washing temperature 60℃ or more, washing time 30 minutes or more. etc. According to the present invention, not only normal standard washing conditions but also
Even under harsh washing conditions or when washing textile products with poor fabric strength, there is almost no problem. Discoloration and fading can be significantly improved. The present invention will be explained in more detail with reference to Examples below. The metal-containing dye-dyed textile products used in the following examples were dyed with metal-containing dyes on bleached test fabrics measuring 31 cm long and 28 cm wide to facilitate measurement of strength reduction and color change/fading. was created. Plain dyeing and printed striped printing are dyed using metal-containing dyes according to conventional methods. Printed striped printing is made by dyeing 40 printed striped lines (20 cm long) with a width of 3 mm at intervals of 2 mm. Created by 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 sample fabrics before and after washing were measured as follows. (b) Strength measurement Plain dyed fabric is a sample with a width of 4 cm and length of 21 cm in the warp direction. Printed striped dyed fabric is a sample of a width of 4 cm and length of 21 cm in the warp direction.
cm, samples containing 40 printed stripes, heavy metal-contaminated cloth, and samples with the contaminated area in the center of the sample are measured using a Schottspur type tensile strength tester. (b) Measurement of color change and fading Using Nippon Denshoku Industries Co., Ltd.'s Color Studio,
The wavelength of maximum absorbance of each dyed raw fabric was measured, and the absorbance of each dyed fabric after washing treatment was measured at those wavelengths of maximum absorbance. The lower the absorbance, the greater the degree of color change and fading, and the closer the absorbance is to that of the original dyed fabric, the smaller the color change and fading. Example 1 Each of the inhibitors shown in Table 1 was added to a washing bath, and a 100% cotton broadcloth that was contaminated with heavy metals and dyed with metal-containing dyes was subjected to JIS standard (JIS L 1072) commercial laundry 102.
Washed under normal standard conditions and harsh conditions in accordance with the law. For washing, use sodium perborate (available oxygen 10.3% product)
2.5g/ or 10g/, powdered soap 0.5g/
Using an aqueous solution containing 3 g of sodium metasilicate to which the inhibitor shown in Table 1 was added, washing was carried out at a bath ratio of 1:20 at 60°C or 80°C for 30 minutes according to JIS standards.
Washing was repeated five times based on the specifications. Table 1 shows the tensile strength, absorbance, and decomposition rate of sodium perborate after the first washing of the test cloth obtained. For comparison, raw dyed fabrics and test fabrics washed without using the inhibitor are also shown in Table 1. According to the present invention, fiber embrittlement, color change and fading, and peroxide stability are improved more than the aminocarboxylate organic chelating agent alone, and in particular, color change and fading are significantly improved.

【table】

[Table] Example 2 100% cotton fabric with poor strength, dyed with metal-containing dyes by adding each of the inhibitors shown in Table 2 to the washing bath.
Kanakin and 100% cotton foil meet JIS standards (JIS L
1072) Laundered in accordance with the Commercial Laundry Act. For washing, use soda percarbonate (available oxygen 13.6% product) 5
Using an aqueous solution containing 0.5 g of powdered soap, 3 g of sodium metasilicate, and the inhibitor shown in Table 2, the bath ratio was 1:20 at 80°C.
Washing was repeated 5 times for 30 minutes based on JIS standards. The tensile strength of the obtained sample fabric,
Table 2 shows the absorbance and the decomposition rate of sodium percarbonate after the first washing. For comparison, Table 2 also shows dyed original fabrics, sample fabrics washed without using inhibitors, etc. According to the present invention, it is possible to suitably wash clothes not only under standard washing conditions but also under severe conditions. Even for textile products with poor fabric strength, we can increase the stability of the bleaching agent and perform effective bleaching, minimizing fiber embrittlement and color change and fading while washing textile products dyed with metal-containing dyes. can do. Furthermore, according to the present invention, fiber embrittlement, color change and fading, and peroxide stability are improved compared to when an aminocarboxylate organic chelating agent is used alone, and in particular, color change and fading are significantly improved.

【table】

[Table] Example 3 Each of the inhibitors shown in Table 3 was added to a washing bath, and various dyed fabrics dyed with metal-containing dyes were stained according to JIS standards (JIS standards).
L 1072) Laundered in accordance with Commercial Laundry Law 102. For washing, an aqueous solution containing 5 g of 35% hydrogen peroxide, 0.5 g of powdered soap, and 3 g of sodium metasilicate was added with the inhibitor shown in Table 3, at a bath ratio of 1:20 and at 70°C. Washing process for 45 minutes with
Washing was repeated 5 times based on JIS standards.
Table 3 shows the tensile strength, absorbance, and hydrogen peroxide decomposition rate of the dyed fabric obtained after the first washing. For comparison, the tensile strength, absorbance, and hydrogen peroxide decomposition rate of the undyed fabric and the dyed fabric washed without using an inhibitor are shown in Table 3. According to the present invention, the prevention of fiber embrittlement is significantly improved. Further, according to the present invention, for copper salt post-treated direct dyes and copper complex salt direct dyes with low washing fastness, the color change and fading is significantly improved compared to when an aminocarboxylate organic chelating agent is used alone.

【table】

Claims (1)

[Claims] 1. When washing and bleaching metal-containing dye-dyed textile products using an oxygen bleach, water-soluble salts of aminocarboxylate organic chelating agents are added to the washing bath.
0.05~2g/(1) General formula CH ₂ OH (CHOH)
0.2 to 2 g of sugar alcohols represented by nCH ₂ OH (in the formula, n is an integer of 2 to 6)/or (2) General formula CH ₂ OH (CHOH) nCOOH (in the formula, n is 3 to 6)
A washing method characterized by the presence of 0.2 to 2 g of aldonic acid, its water-soluble salts, or its lactones, represented by the following integer: