阅读说明：本技术 一种基于atp活化的羊毛低温漂白/防缩整理同浴处理方法 (ATP activation-based wool low-temperature bleaching/shrink-proof finishing one-bath treatment method ) 是由 何雪梅 吴超 梁慧星 蔡露 冒海燕 周天池 郑成辉 于 2021-09-16 设计创作，主要内容包括：本发明公开了一种基于ATP活化的羊毛低温漂白/防缩整理同浴处理方法,将羊毛织物加入到由三磷酸腺苷、过氧化氢酶、H-(2)O-(2)、甲壳素微晶、三聚氰胺、焦磷酸钠、三乙醇胺、pH调节剂组成的功能整理液中,浴比1：10-50,50～60℃震荡,取出,水洗,烘干,制得漂白、防缩功能化处理的羊毛织物。本发明使用的整理液含有能量活化剂,漂白剂双氧水,催化剂过氧化氢酶,偶联剂甲壳素微晶,防缩整理剂三聚氰胺、金属离子吸附剂焦磷酸钠、强力保护剂三乙醇胺,pH调节剂,纤维整理后,低温条件下去除了色素、同时增强了羊毛纤维之间的交联作用,将漂白和防缩同浴进行,同时提高染漂白和防缩效果。(The invention discloses a wool low-temperature bleaching/shrink-proof finishing one-bath treatment method based on ATP activation, which adds wool fabricIs added to the mixture of adenosine triphosphate, catalase and H 2 O 2 The functional finishing liquid consists of chitin microcrystal, melamine, sodium pyrophosphate, triethanolamine and a pH regulator, wherein the bath ratio is 1: 10-50, shaking at 50-60 ℃, taking out, washing with water, and drying to obtain the bleached and shrink-proof functional treated wool fabric. The finishing liquid used by the invention contains an energy activating agent, a bleaching agent, hydrogen peroxide, a catalyst, catalase, a coupling agent, chitin microcrystal, a shrink-proof finishing agent, melamine, a metal ion adsorbent, sodium pyrophosphate, a strong protective agent, triethanolamine and a pH regulator, after the fibers are finished, pigments are removed under the low-temperature condition, the cross-linking effect between wool fibers is enhanced, the bleaching and shrink-proof are carried out in the same bath, and the dyeing bleaching and shrink-proof effects are improved.)

1. A wool low-temperature bleaching/shrink-proof finishing one-bath treatment method based on ATP activation is characterized in that: adding wool fabric to the mixture of adenosine triphosphate, catalase and H₂O₂The functional finishing liquid consists of chitin microcrystal, melamine, sodium pyrophosphate, triethanolamine and a pH regulator, wherein the bath ratio is 1: vibrating at the temperature of 50-60 ℃ and at the temperature of 10-50 ℃, taking out, washing with water, and drying to obtain a bleached and shrink-proof functionalized wool fabric; wherein the concentration of the adenosine triphosphate is 2-10 g/L; said H₂O₂The volume concentration is 5-20 mL/L; the concentration of the catalase is 2-10 g/L; the mass concentration of the chitin microcrystal is 1-10 g/L; the mass concentration of the melamine is 2-20 g/L; the mass concentration of the sodium pyrophosphate is 2-5 g/L; the mass concentration of the triethanolamine is 1-5 g/L.

2. The ATP-activation based wool low-temperature bleaching/shrink-proof finishing one-bath treatment method according to claim 1, wherein: the grain size of the chitin microcrystal is 100-600 nm.

3. The ATP-activated based low temperature bleaching/shrink-proof finishing one-bath treatment method for wool according to claim 1 or 2, characterized in that: the pH regulator consists of 0.04mol/L phosphoric acid, 0.04mol/L boric acid, 0.04mol/L acetic acid and 0.2mol/L NaOH, and the pH value is adjusted to 3-8.

4. The ATP-activated based low temperature bleaching/shrink-proof finishing one-bath treatment method for wool according to claim 1 or 2, characterized in that: and the oscillation is carried out for 30-120 min.

5. The ATP-activated based low temperature bleaching/shrink-proof finishing one-bath treatment method for wool according to claim 1 or 2, characterized in that: the drying is carried out at 40-50 ℃.

6. The ATP-activated based low temperature bleaching/shrink-proof finishing one-bath treatment method for wool according to claim 1 or 2, characterized in that: the concentration of the adenosine triphosphate is 6-8 g/L; the mass concentration of the chitin microcrystal is 2-4 g/L; the mass concentration of the melamine is 10-12 g/L.

7. The ATP-activated based low temperature bleaching/shrink-proof finishing one-bath treatment method for wool according to claim 1 or 2, characterized in that: the pH regulator is used for regulating the pH to 5.

8. The ATP-activated based low temperature bleaching/shrink-proof finishing one-bath treatment method for wool according to claim 1 or 2, characterized in that: the triethanolamine has the mass concentration of 2-4 g/L.

Technical Field

The invention belongs to the technical field of textile fiber material bleaching shrink-proof finishing, and particularly relates to a wool low-temperature bleaching/shrink-proof finishing one-bath treatment method based on ATP activation.

Background

The wool fiber is a natural protein fiber, and compared with other fibers, the wool fiber has better hand feeling, good moisture permeability, heat retention, comfort and ready-to-wear effect. However, natural wool is yellow or light yellow due to the influence of growth environment, and some products have higher requirements on the whiteness of fabrics, so that the wool needs to be subjected to bleaching treatment. At present, the common wool bleaching methods at home and abroad comprise oxidation bleaching, reduction bleaching, oxidation-reduction bleaching, activator bleaching and the like, but the bleaching methods are carried out at higher temperature or higher pH value, so that the damage to wool is large easily, and the whiteness of the treated wool is not durable. In addition, wool is easy to felt due to the existence of scale layers, the phenomenon of wool shrinkage is serious, and the traditional wool shrink-proof method uses a chlorine-containing oxidant-reducing agent or resin finishing method. The traditional method needs to carry out bleaching and shrink-proof finishing in steps due to different required systems, and adsorbable organic halide (AOX) is generated in the chlorination processing process of wool, and has toxicological property, carcinogenic property and non-biodegradability, so that serious ecological environment pollution is caused. The most prominent problems in the processing of wool textile printing and dyeing industry are the problems caused by chlorination descaling mercerization shrink-proof process and the problems of formaldehyde pollution and strength damage caused by resin finishing. Therefore, the development of wool shrink proofing technology which is environmentally friendly has become one of the goals of textile workers. The fundamental solution for solving the pollution in the wool shrink-proof finishing is to adopt an ecological and environment-friendly chlorine-free processing technology and a chlorine-free polymer as substitutes for chlorine and derivatives thereof or formaldehyde-free finishing.

Disclosure of Invention

This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.

The invention provides a wool low-temperature bleaching/shrink-proof finishing one-bath treatment method based on ATP activation, which adds wool fabrics into a solution prepared from adenosine triphosphate, catalase and H₂O₂The functional finishing liquid consists of chitin microcrystal, melamine, sodium pyrophosphate, triethanolamine and a pH regulator, wherein the bath ratio is 1: vibrating at the temperature of 50-60 ℃ and at the temperature of 10-50 ℃, taking out, washing with water, and drying to obtain a bleached and shrink-proof functionalized wool fabric; wherein the concentration of the adenosine triphosphate is 2-10 g/L; said H₂O₂The volume concentration is 5-20 mL/L; the concentration of the catalase is 2-10 g/L; the mass concentration of the chitin microcrystal is 1-10 g/L; the mass concentration of the melamine is 2-20 g/L; the mass concentration of the sodium pyrophosphate is 2-5 g/L; the mass concentration of the triethanolamine is 1-5 g/L.

As a prior scheme of the ATP-activated-based low-temperature bleaching/shrink-proof finishing one-bath treatment method for the wool, the method comprises the following steps: the grain size of the chitin microcrystal is 100-600 nm.

As a prior scheme of the ATP-activated-based low-temperature bleaching/shrink-proof finishing one-bath treatment method for the wool, the method comprises the following steps: the pH regulator consists of 0.04mol/L phosphoric acid, 0.04mol/L boric acid, 0.04mol/L acetic acid and 0.2mol/L NaOH, and the pH value is adjusted to 3-8.

As a prior scheme of the ATP-activated-based low-temperature bleaching/shrink-proof finishing one-bath treatment method for the wool, the method comprises the following steps: and the oscillation is carried out for 30-120 min.

As a prior scheme of the ATP-activated-based low-temperature bleaching/shrink-proof finishing one-bath treatment method for the wool, the method comprises the following steps: the drying is carried out at 40-50 ℃.

As a prior scheme of the ATP-activated-based low-temperature bleaching/shrink-proof finishing one-bath treatment method for the wool, the method comprises the following steps: the concentration of the adenosine triphosphate is 6-8 g/L; the mass concentration of the chitin microcrystal is 2-4 g/L; the mass concentration of the melamine is 10-12 g/L.

As a prior scheme of the ATP-activated-based low-temperature bleaching/shrink-proof finishing one-bath treatment method for the wool, the method comprises the following steps: the pH regulator is used for regulating the pH to 5.

As a prior scheme of the ATP-activated-based low-temperature bleaching/shrink-proof finishing one-bath treatment method for the wool, the method comprises the following steps: the triethanolamine has the mass concentration of 2-4 g/L.

The invention has the beneficial effects that:

(1) the finishing liquid used by the invention contains an energy activating agent, a bleaching agent, hydrogen peroxide, a catalyst, catalase, a coupling agent, chitin microcrystal, a shrink-proof finishing agent, melamine, a metal ion adsorbent, sodium pyrophosphate, a strong protective agent, triethanolamine and a pH regulator, after the fibers are finished, pigments are removed under the low-temperature condition, the cross-linking effect between wool fibers is enhanced, the bleaching and shrink-proof are carried out in the same bath, and the dyeing bleaching and shrink-proof effects are improved.

(2) The invention overcomes the defects of strong damage, poor hand feeling and the like caused by long-time high-temperature boiling dyeing and bleaching of the traditional wool under the alkaline condition, and meets the processing requirements of ecological green sustainable dyeing and finishing technology.

(3) The bleaching and finishing process is carried out under the weak acid condition, all the used auxiliaries are ecological and environment-friendly, have little influence on the environment, can be implemented at a lower temperature, and reduces the consumption of energy.

(4) The low-temperature wool bleaching and shrink-proofing method disclosed by the invention is ecological and environment-friendly in process, energy-saving, simple in process, convenient to operate and wide in application prospect.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:

FIG. 1 shows the effect of treatment temperature change on whiteness and shrink resistance of wool fabric.

Figure 2 is a graph of the effect of different pH on wool whiteness and shrink resistance.

FIG. 3 is a schematic structural diagram of modified wool after finishing according to the present invention.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.

Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.

Example 1:

adding 1g wool fabric to a mixture of 4g/L Adenosine Triphosphate (ATP),5g/L catalase, 30% H₂O₂The final volume concentration is 8mL/L, the mass concentration of the chitin microcrystal is 2g/L, the grain size of the chitin microcrystal is 500nm, the melamine is 5g/L, the mass concentration of the sodium pyrophosphate is 2g/L, the triethanolamine is 1g/L, the pH value is 5, the bath ratio is 1: 30, oscillating the functional finishing liquid in a constant-temperature oscillation dyeing machine for 60min at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and shrink-proof wool fabric.

Example 2:

adding 1g wool fabric to 6g/L adenosine triphosphate, 5g/L catalase, 30% H₂O₂The volume concentration is 10mL/L, the mass concentration of the chitin microcrystal is 2g/L, the grain size of the chitin microcrystal is 500nm, the melamine is 8g/L, the mass concentration of the sodium pyrophosphate is 2g/L, the triethanolamine is 1g/L, the pH value is 5, the bath ratio is 1: 30, oscillating the functional finishing liquid in a constant-temperature oscillation dyeing machine for 60min at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and anti-shrink functionally treated wool fabric.

Example 3:

1g wool textile was added to a mixture of 6g/L Adenosine Triphosphate (ATP),5g/L catalase, 30% H₂O₂The volume concentration is 12mL/L, the mass concentration of the chitin microcrystal is 2g/L, the grain size of the chitin microcrystal is 500nm, the melamine is 10g/L, the mass concentration of the sodium pyrophosphate is 2g/L, the triethanolamine is 1g/L, the pH value is 5, the bath ratio is 1: 30, oscillating the functional finishing liquid in a constant-temperature oscillation dyeing machine for 60min at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and anti-shrink functionally treated wool fabric.

Example 4:

adding 1g of wool fabric into a mixture of 8g/L of adenosine triphosphate, 5g/L of catalase, 12mL/L of 30% H2O2 volume concentration, 4g/L of chitin microcrystal mass concentration, 500nm of chitin microcrystal particle size, 10g/L of melamine, 2g/L of sodium pyrophosphate mass concentration, 1g/L of triethanolamine, pH5, bath ratio of 1: 30, oscillating the functional finishing liquid in a constant-temperature oscillation dyeing machine for 60min at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and anti-shrink functionally treated wool fabric.

Example 5:

adding 1g of wool fabric into a mixture of 8g/L of adenosine triphosphate, 8g/L of catalase, 30% H2O2, 15mL/L of volume concentration, 4g/L of mass concentration of chitin microcrystal, 500nm of particle size of the chitin microcrystal, 12g/L of melamine, 2g/L of mass concentration of sodium pyrophosphate, 1g/L of triethanolamine, pH5, bath ratio of 1: 30, oscillating the functional finishing liquid in a constant-temperature oscillation dyeing machine for 60min at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and anti-shrink functionally treated wool fabric.

Example 6:

adding 1g of wool fabric into a mixture of 6g/L of adenosine triphosphate, 8g/L of catalase, 12mL/L of 30% H2O2 volume concentration, 4g/L of chitin microcrystal mass concentration, 500nm of chitin microcrystal particle size, 15g/L of melamine, 2g/L of sodium pyrophosphate mass concentration, 1g/L of triethanolamine, pH5, bath ratio of 1: 30, oscillating the functional finishing liquid in a constant-temperature oscillation dyeing machine for 60min at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and anti-shrink functionally treated wool fabric.

FIG. 1 shows the addition of 1g wool fabric to 6g/L adenosine triphosphate, 5g/L catalase, 30% H₂O₂The volume concentration is 12mL/L, the mass concentration of sodium pyrophosphate is 2g/L, the mass concentration of chitin microcrystal is 2g/L, melamine is 10g/L, triethanolamine is 1g/L, the pH value is 5, the bath ratio is 1: 30, in the bleaching finishing liquid, shaking for 60min at room temperature, 30 ℃, 45 ℃, 50 ℃, 60 ℃, 80 ℃ and 90 ℃ respectively in a constant-temperature oscillation dyeing machine, taking out, washing with water, and drying to obtain the bleached and anti-shrink treated wool fabric. It can be seen that the whiteness of the wool fabric increases with increasing temperature. The wool fabric is treated at 60 ℃ to obtain better whiteness and shrink-proof effect. The technical scheme of the invention obviously improves the whiteness value of the surface of the wool fabric.

FIG. 2 shows the effect of different pH values on whiteness and shrink resistance of wool fabrics, and the treatment conditions are as follows: adding 1g wool fabric to 6g/L adenosine triphosphate, 5g/L catalase, 30% H₂O₂The volume concentration is 12mL/L, the mass concentration of sodium pyrophosphate is 2g/L, the mass concentration of chitin microcrystal is 2g/L, the mass concentration of melamine is 5g/L, and the triethanolamine isAmine 1g/L, pH 1.8, 2, 3, 4, 5, 6, 7, 8, bath ratio 1: 30, in the bleaching finishing liquid, in a constant-temperature oscillation dyeing machine, oscillating for 60min at a constant temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and shrink-proof treated wool fabric. It can be seen that the whiteness of the wool fabric is enhanced and the shrink-proof performance becomes better with the increase of the treatment pH. When the pH value of the treatment is about 5, a better bleaching and shrink-proof effect can be obtained. The technical scheme of the invention obviously improves the whiteness value of the surface of the wool fabric.

And (3) performance testing:

and (3) whiteness testing: WS-SD color whiteness Meter (Winzhou instruments, Inc.).

And (3) testing the breaking strength: the width of the test specimen is 50mm, the distance between the jaws of the tester is 100mm (to the nearest 1mm), the test specimen is stretched to break within (30 ± 5) s at a specified rate, each test specimen is tested 3 times, and the results are the average of 3 tests.

And (3) testing the bending rigidity: the fabric bending stiffness was tested on a FAST tester.

Felt shrinkage test A17 cm x 17cm sample was marked with Dacron fabric in the longitudinal and transverse directions, washed in a drum washer with water amount of 10L and detergent 1g/L, and then padded to give 0.125kg of fabric, washed at room temperature for 3h, and the area felt shrinkage was calculated according to the formula.

Area felting ratio (area of pre-wash mark-area of post-wash mark)/area of pre-wash mark × 100%

Table 1 comparison of whiteness values and shrink resistance, strength, drape properties of wool fabrics treated with different formulations (examples 1-6) with untreated wool fabrics. As can be seen from table 1, the whiteness, shrinkage, strength, drape performance of the wool were improved and enhanced after the different treatments compared to the untreated wool fabric. The preferable conditions are 6g/L of adenosine triphosphate, 5mL/L of catalase, 12mL/L of 30% H2O2 volume concentration, 2g/L of chitin microcrystal mass concentration and 10g/L of melamine, the obtained fabric has good whiteness, small area shrinkage, no damage to strength, larger bending rigidity and good draping performance.

TABLE 1 Properties after different workup

The invention provides a finishing method which can bleach wool fabrics at low temperature and prevent shrinkage under acidic conditions, and the modification method is ecological, environment-friendly, simple and effective, can reduce energy consumption, saves printing and dyeing auxiliaries, protects the strength of fibers and endows the fabrics with soft hand feeling.

The invention adopts adenosine triphosphate as an energy activator, hydrogen peroxide as a bleaching agent, catalase as a catalyst, chitin microcrystal as a cross-linking agent, melamine as a shrink-proof finishing agent and triethanolamine as a strong protective agent, and performs activated bleaching shrink-proof one-bath treatment on wool under the conditions of low temperature and acidity. The adenosine triphosphate and the melamine are crosslinked on the wool fabric under the action of the chitin microcrystal, simultaneously, the whiteness and the shrink-proof effect of the fabric are improved, and the fiber has good flame retardant effect and ultraviolet resistance effect. The invention adopts a one-bath impregnation method to carry out bleaching/shrink-proof finishing on the wool fibers, can replace the traditional method of high-temperature treatment of an oxidant, a reducing agent and a shrink-proof finishing agent, reduces the bleaching finishing temperature, reduces the damage of the wool, does not need bleaching under the alkaline condition, and achieves the purposes of energy conservation, emission reduction and environmental protection. The process is simple and convenient to operate, bleaching and shrink-proof are carried out in one step, and the process has a wide application prospect.

Comparative example 1:

1g of wool fabric was added to a solution of catalase 5ml/L, 30% H₂O₂The volume concentration is 12mL/L, the mass concentration of the chitin microcrystal is 2g/L, the grain size of the chitin microcrystal is 500nm, the melamine is 10g/L, the mass concentration of the sodium pyrophosphate is 2g/L, the triethanolamine is 1g/L, the pH value is 5, the bath ratio is 1: 30 in a constant-temperature oscillation dyeing machine for 60min at 60 ℃, taking out, washing with water, and drying to obtain the bleached and shrink-proof functionally treated wool fabric. As a result, it was found that the whiteness of the treated wool was not substantially changed. Because the conventional hydrogen peroxide bleaching needs to be performed under the alkaline condition, the hydrogen peroxide is formedThe oxygen-hydrogen ions play a role in bleaching, and hydrogen peroxide is relatively stable and cannot be effectively bleached under the weak-acid condition of pH 5.

Comparative example 2:

1g of wool fabric was added to a mixture of 6g/L, Tetraacetylethylenediamine (TAED), catalase 5ml/L, 30% H₂O₂The volume concentration is 12mL/L, the mass concentration of the chitin microcrystal is 2g/L, the grain size of the chitin microcrystal is 500nm, the melamine is 10g/L, the mass concentration of the sodium pyrophosphate is 2g/L, the triethanolamine is 1g/L, the pH value is 5, the bath ratio is 1: 30, oscillating the functional finishing liquid in a constant-temperature oscillation dyeing machine for 60min at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and anti-shrink functionally treated wool fabric. As a result, it was found that Tetraacetylethylenediamine (TAED), which is a common bleach activator, is an organic acyl compound, and H₂O₂The hydrolysis reaction of (2) can make perhydroxyl ion acyl to generate peroxyacetic acid, but the oxidation resistance of protein is poor, and the peroxyacid is a strong oxidant, so that when the peroxyacid exceeds a certain concentration, the protein structure of wool fiber can be oxidized and developed, and the bleaching effect is poor.

Comparative example 3:

adding 1g wool fabric to 6g/L Adenosine Triphosphate (ATP), catalase 5ml/L, 30% H₂O₂The volume concentration is 12mL/L, the mass concentration of glutaraldehyde is 2g/L, the mass concentration of melamine is 10g/L, the mass concentration of sodium pyrophosphate is 2g/L, the mass concentration of triethanolamine is 1g/L, the pH value is 5, the bath ratio is 1: 30, oscillating the functional finishing liquid in a constant-temperature oscillation dyeing machine for 60min at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the bleached and anti-shrink functionally treated wool fabric. The result shows that the addition of glutaraldehyde easily causes serious yellowing of wool fabrics, and the wool fabrics are not ecological and environment-friendly enough and are not environment-friendly.

It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.