JPH0434595B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a stabilizer for hydrogen peroxide used when bleaching textile materials with hydrogen peroxide. [Description of prior art] Generally, bleaching with hydrogen peroxide is carried out in an alkaline environment, but if the bleaching bath is simply made alkaline, the reaction formula: 2H ₂ O ₂ → Decomposition of hydrogen peroxide occurs according to 2H ₂ O + O ₂ and thus
Other reaction formula: H ₂ O ₂ → H ⁺ + OOH ^- According to this, the production amount of perhydroxyl ion (OOH ^- ), which is considered to be the active ingredient of hydrogen peroxide bleaching, decreases and the bleaching effect cannot be improved. It has been known. In this case, a method is generally adopted in which a stabilizer is added to the hydrogen peroxide bleaching system to suppress the decomposition of hydrogen peroxide into molecular oxygen. Conventionally, as a hydrogen peroxide stabilizer as mentioned above,
Sodium silicate is used, and it is known that it can improve the stabilizing effect of the bleaching system and improve the whiteness of the resulting bleached product. However, sodium silicate needs to be used in a relatively large amount, which has the disadvantage that silicic acid scale adheres to the object to be bleached, which deteriorates the texture of the resulting fiber material. Further, in this case, there is also a drawback that silicic acid scale is deposited on the device. In addition to sodium silicate, stabilizers include organic chelating agents such as EDTA and DTPA, inorganic chelating agents such as condensed phosphates (MOL April 1960 issue, page 42), and water-soluble proteins such as soy protein and casein. (Tokuko Showa 50
-34675) can be used. However, these stabilizers other than sodium silicate have a certain degree of stabilizing effect in batch bleaching processes with large bath ratios, and have achieved industrial success, but they cannot be used in continuous bleaching processes with small bath ratios. In the process, compared to sodium silicate, it is inferior in stabilizing effect, product whiteness, and embrittlement prevention effect, and the work stability is also insufficient, so it has not yet achieved sufficient results industrially. (Yuho Matoba, Consideration of dynamic causation and future dyeing, No. 132,
Senkeizai Shimbun). Also, JP-A-51-111812 and JP-A-52-
No. 103386 discloses that a bleach stabilizer made of sodium poly-α-hydroxyl acrylate (hereinafter abbreviated as PHAS) exhibits unprecedented levels of stabilization and whiteness improvement as a non-silicic acid compound. It has been disclosed that it has excellent hydrogen peroxide stability and anti-catalytic properties comparable to silicates, and also has an action as a protective agent. However, PHAS has an excessively strong stabilizing power of hydrogen peroxide, and therefore sometimes shows unsatisfactory results in terms of bleaching effect, especially in its ability to remove cotton seeds. Also, PHAS is very expensive and therefore
When PHAS is used in amounts sufficient to achieve a sufficient bleaching effect, bleaching costs become extremely high, making industrial use impossible. To solve this problem, JP-A-55-76161 discloses a method of using PHAS and condensed phosphate in combination. However, with this method, the texture of the bleached material obtained tends to deteriorate, and therefore, its practical use is considered undesirable. Furthermore, JP-A-48-54278 discloses that a hydrogen peroxide bleaching solution is mixed with alkylidene diphosphonic acid or its salts, and if necessary, urea, a urea derivative, an amide, or an imide. It has been disclosed that the bleaching power can be activated to exhibit extremely excellent bleaching power near neutrality. However, even when such a bleaching aid is used, the bleaching power and cotton seed removal power of the bleaching solution are still unsatisfactory. [Problems to be Solved by the Invention] The purpose of the present invention is to eliminate silicate damage and to achieve a bleaching effect higher than that achieved when sodium silicate, PHAS, and organic phosphonic acid compounds are used alone, even in continuous bleaching methods. To provide a hydrogen peroxide bleaching stabilizer which is particularly effective in removing cotton seeds, provides a bleached material with good texture, and is economically useful industrially. There is a particular thing. The present inventor has focused on the excellent properties of PHAS, and has conducted research to improve it so that bleaching operations can be carried out industrially advantageously using PHAS. When PHAS is used alone, it can be used in combination with an organic phosphonic acid compound of
Or, it shows a bleaching effect that is superior to that when using sodium silicate, and is also excellent in anti-catalytic properties and as a protective agent for seed removal ability, and also has a good texture on the bleached material. The hydrogen peroxide bleach stabilizer of the present invention has been completed. Although the mechanism by which the hydrogen peroxide bleach stabilizer of the present invention exhibits excellent effects has not been fully clarified, the present inventors have discovered that PHAS and a specific organic phosphonic acid have different chelating powers. The main causes are that they complement each other, and that the strong stabilizing effect of PHAS on hydrogen peroxide and the mild activation effect of hydrogen peroxide of specific organic phosphonic acids exhibit a synergistic effect. I think I'm getting used to it. [Means and effects for solving the problems] The hydrogen peroxide bleach stabilizer of the present invention contains the following components: (A) poly-α-hydroxyacrylic acid, a salt thereof;
and at least one hydroxyacrylic acid polymer selected from polylactone thereof, and (B) an organic phosphonic acid of the following formulas (), (), and (): [However, in the above formula, X ¹ represents a hydrogen atom or an alkyl group, X ² represents hydrogen, a hydroxyl group, or an alkyl group, and Y ¹ and Y ² each independently,

[Formula] represents a group or a hydrogen atom, and Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently,

〔Example〕

The present invention will be explained below with reference to Examples. Example 1 and Comparative Example 1 In each of Example 1 (Experiments 1 to 4) and Comparative Example 1 (Comparative Experiments 1 to 5), cotton knitted fabric (40 count) was subjected to steam bleaching under the following conditions. . The bleaching effect is shown in Table 1. The composition and bleaching conditions of the bleaching bath were as follows. H ₂ O ₂ (35%) 40ml/Stabilizer (Table 1) Specified amount shown in Table 1 Sunmol S-50 1g/ (Anionic, nonionic surfactant manufactured by NICCA Chemical Co., Ltd.) NaOH (flake) ) 3g/ Squeezing rate...100% Temperature and processing time...100℃, 40 minutes Whiteness: Macbeth MS-2020 colorimeter Reflectance measurement...Wavelength 440mμ Texture: 10cm× using Tensilon manufactured by Toyo Baldwin Co., Ltd. 10cm cloth with a diameter of 3cm and a thickness of 0.5mm
It is expressed as the resistance value when passing through a stainless steel ring. Example 2 and Comparative Example 2 In each of Example 2 (Experiments 1 to 4) and Comparative Example 2 (Comparative Experiments 1 to 10), broadcloth (40 count) was subjected to steam bleaching under the following conditions. . The bleaching results are shown in Table 2. The composition of the bleaching bath and bleaching conditions are as follows. H ₂ O ₂ (35%) 20ml/Stabilizer (Table 2) Specified amount shown in Table 2 Sunmol S-50 1g/ (Anionic, nonionic surfactant manufactured by NICCA Chemical Co., Ltd.) NaOH (flake) ) 2g/ Squeezing rate...90% Temperature and processing time...95℃, 30 minutes Cotton seed removal property: By visual judgment ○ means no seeds at all △ means a few seeds remain × means a lot of seeds remain Table 2 (Comparative Example 2, As is clear from experiment numbers 8 to 10), 1-hydroxyethylidene-1,1-
When diphosphonic acid, aminotri(methylenephosphonic acid), and ethylenediaminetetra(methylenephosphonic acid) are used alone,
The bleaching power and cotton seed removal power of the resulting bleach bath are:
All of them were defective, but each of these
When used in combination with PHAS, superior bleaching was achieved compared to when PHAS was used alone (Comparative Example 2 - Experiment No. 3-4) and when PHAS was used in combination with EDTA (Comparative Example 2 - Experiment No. 5) power and
Particularly unexpectedly, it has been confirmed that it exhibits an extremely excellent ability to remove cotton seeds. Example 3 and Comparative Example 3 In each of Example 3 (Experiments 1 to 3) and Comparative Example 3 (Comparative Experiments 1 to 3), an aqueous solution of FeSO ₄ , 7H ₂ O was applied to a cotton poplin (40 count) desizing cloth. , or
A certain amount of a 1% aqueous solution of CUSO ₄ , 5H ₂ O was spotted, and after drying, bleaching was carried out under the same conditions as in Experimental Example 2. However, as the stabilizer, one having the composition shown in Table 3 was used. The tensile strength of the obtained bleached cloth was measured. Strength: Tensile strength autograph JIS-L-1068 (constant speed tension type) Measured 5 times at a tension distance of 5 cm and a tensile speed of 200 mm/min, and the average value was calculated. The results are shown in Table 3.

【table】

【table】

[Table] *4...Ethylenediaminetetraacetic acid soda

〔Effect of the invention〕

According to the present invention, due to the synergistic effect of the hydroxyacrylic acid polymer component and the specific organic phosphonic acid compound component, the hydrogen peroxide bleaching effect is significantly superior to the bleaching effect obtained using sodium silicate as a stabilizer. is obtained. Therefore, it is free from the problem of silicate disorder that occurs when sodium silicate is used as a stabilizer, and it is also more effective than when the hydroxyacrylic acid polymer and the above-mentioned specific organic phosphonic acid compound are used alone. It has a high degree of whiteness, and is surprisingly effective in removing cotton seeds. It also shows little loss in fiber strength after bleaching, has excellent metal removal ability and metal ion sequestration ability, and is highly effective against wind. A product to be bleached with good compatibility can be obtained. Thus, by using the stabilizer of the present invention, it is possible to obtain an excellent bleaching effect that cannot be obtained with known hydrogen peroxide bleaches.

Claims (1)

[Claims] 1. The following components: (A) poly-α-hydroxyacrylic acid, a salt thereof,
and at least one hydroxyacrylic acid polymer selected from polylactone thereof, and (B) an organic phosphonic acid of the following formulas (), (), and (): [However, in the above formula, X ¹ represents a hydrogen atom or an alkyl group, X ² represents hydrogen, a hydroxyl group, or an alkyl group, and Y ¹ and Y ² each independently represent a [Formula] group, or a hydrogen atom, Z ₁ , Z ₂ , Z ₃ and Z ₄ each independently represent a [Formula] group or a hydrogen atom, n represents an integer from 0 to 4] and a salt thereof A hydrogen peroxide bleach stabilizer comprising: at least one selected organic phosphonic acid compound.