A method for enzymatic anti-felting finishing of low-strength-loss colored wool fabrics

Abstract

The present invention discloses a method for enzymatic anti-felting finishing of low-strength-loss colored wool fabrics. First, keratinase is used for the pretreatment of colored wool fabrics to hydrolyze the outer layer of wool scales and destroy the structural integrity of the scale layer. Then, protease and sodium hexyl sulfate are used to promote the enzymatic hydrolysis of the scale layer on the wool surface. After washing and drying, a colored anti-felting wool fabric with low strength loss and low felting shrinkage rate is obtained. The specific steps include: (1) pretreatment with wool keratinase; (2) treatment with an anti-felting treatment solution; (3) post-treatment of fabric washing and drying. The present invention combines the application of keratinase, protease and sodium hexyl sulfate for anti-felting finishing of colored wool fabrics. The colored wool fabric after finishing has a relatively low strength loss. The finishing method does not damage the dye structure and has little impact on the appearance of the wool fabric. The wool fabric finished by the method of the present invention has excellent anti-felting effect and soft handfeel.

Description

Technical Field

[0001] The invention relates to a method for enzyme-based anti-felting finishing of low-strength-loss colored wool fabric, belonging to the technical field of textile dyeing and finishing. Background Art

[0002] Wool fiber is composed of scale layer, cortex layer and medulla layer. It is a high-grade textile fiber with excellent warmth retention and soft touch. On the other hand, when wool fabric is subjected to mechanical force in a wet state, the jagged scale layer on the fiber surface will cross-entangle and interlock with each other, causing the wool fabric to shrink in size, become hard and have unclear texture during washing, affecting the wearing performance of the wool fabric.

[0003] At present, wool fiber products are mostly treated with chlorination for anti-felting finishing, among which the most widely used is the chlorination-Hercosett process. However, this treatment method will produce a large amount of adsorbable organic halide AOX (Adsorbable Organic Halide) during production, and its inherent toxicity, non-microbial degradability and carcinogenicity are extremely harmful to the human body and the environment. At the same time, chlorination treatment will also destroy the dye structure, causing serious impact on the color appearance of colored wool fabrics, resulting in defects such as light color and color spots on the appearance of colored wool fabrics. In addition, there are also studies on the use of reducing agents such as thiourea dioxide to perform anti-felting finishing on wool fabrics. For example, patent CN 113062113 A discloses a method for surface treatment of wool fabrics using thiourea dioxide. Although the reduction method finishing can also obtain a lower felting rate, it also has the problems of serious pollution and easy destruction of the color appearance of colored wool fabrics.

[0004] Compared with the above-mentioned chemical wool anti-felting method, the use of biological enzyme method for wool anti-felting has many advantages, including mild treatment conditions, soft fabric feel after finishing, and less impact on the color appearance of colored wool fabrics. Protease is the most widely used protease in wool bioenzyme anti-shrinkage finishing, that is, the use of protease to destroy the scale layer structure of wool fibers to achieve the purpose of subtractive anti-felting finishing. Although there are many research reports on the use of protease for wool anti-felting, the anti-shrinkage finishing effect of a single protease method in actual production is not ideal, mainly because the protease is easy to diffuse into the fiber scale layer to hydrolyze the intercellular matrix and cortex layer, thereby causing greater damage to the wool fibers. Therefore, how to construct a colored wool fabric anti-felting method with low strength loss, so that the colored wool fabric after finishing not only has low felting rate and low strength loss, but also has less impact on the color appearance of wool fibers, is a technical problem that needs to be solved urgently. Summary of the invention

[0005] Aiming at the problems that chemical anti-felting affects the color appearance of colored wool fabrics and a single protease method for anti-felting is prone to cause fiber damage, the purpose of the present invention is to provide a method for enzymatic anti-felting finishing of low-strength-loss colored wool fabrics. Keratinase can hydrolyze the highly cross-linked disulfide bonds in the wool scale layer and destroy the integrity of the scale layer structure. On this basis, by combining sodium hexyl sulfate with protease, the hydrolysis effect of protease on the wool surface scale layer is improved, and a method for enzymatic anti-felting finishing of colored wool fabrics with low felting shrinkage rate, low strength loss, and less influence on color appearance is constructed.

[0006] For the above purpose, the present invention provides a method for enzymatic anti-felting finishing of low-strength-loss colored wool fabrics. First, pretreat the colored wool fabrics with keratinase, then treat the pretreated colored wool fabrics with an anti-felting treatment solution, and fully wash and dry the fabrics. The anti-felting treatment solution includes protease and sodium hexyl sulfate.

[0007] In an embodiment of the present invention, the method specifically includes the following steps:

[0008] (1) Wool keratinase pretreatment: Immerse the colored wool fabrics in a keratinase solution for pretreatment for 30 - 60 min to obtain the wool fabrics treated with keratinase.

[0009] (2) Anti-felting treatment solution treatment: Immerse the wool fabrics treated with keratinase obtained in step (1) in the anti-felting treatment solution for treatment for 30 - 60 min. The anti-felting treatment solution includes protease and sodium hexyl sulfate.

[0010] (3) Fabric washing and drying post-treatment: Inactivate the enzyme of the fabric treated in step (2) for 15 - 30 min under the environmental condition of 80 °C, wash it after treatment, and dry it at 40 - 60 °C.

[0011] First, pretreat the colored wool fabrics with keratinase. Through enzymatic hydrolysis reaction, the outer layer of the scale rich in disulfide bonds on the wool fiber surface is hydrolyzed, destroying the integrity of the scale layer structure and reducing the structural tightness of the wool surface scale layer. Then, combine and apply protease and sodium hexyl sulfate to promote the enzymatic hydrolysis of protease on the wool surface scale layer, while improving the anti-felting effect and reducing the internal damage of wool fibers. Finally, fully wash and dry the fabrics to obtain a method for enzymatic anti-felting finishing of low-strength-loss colored wool fabrics.

[0012] In an embodiment of the present invention, the colored wool fabrics include any one of wool woven fabrics, knitted fabrics, and non-woven fabrics. The dyeing methods of the colored wool fabrics include one or a combination of direct dyeing, acid dyeing, acid mordant dyeing, neutral dyeing, and wool reactive dyeing.

[0013] In one embodiment of the present invention, the keratinase solution contains keratinase and a penetrant. The enzyme activity of the keratinase is 5000 - 10000 U / mL, the concentration of keratinase is 1 - 5 g / L, and the concentration of the penetrant is 0.1 - 1 g / L.

[0014] In one embodiment of the present invention, the penetrant includes non-ionic and / or anionic surfactants. The non-ionic surfactants include polyoxyethylene ethers of alkylphenols, fatty alcohol polyoxyethylene ethers, fatty acid methyl ester polyoxyethylene ethers, fatty acid polyoxyethylene ethers, etc. The anionic surfactants include sodium alkyl sulfonate, alkyl aryl sulfonate, sodium alkyl sulfate, secondary alkyl sulfate, etc.

[0015] In one embodiment of the present invention, when using the keratinase solution to pretreat the colored wool fabric, the temperature is 50 - 60 °C, and the pH of the keratinase solution is 8 - 9.

[0016] In one embodiment of the present invention, the concentration of sodium hexyl sulfate in the anti-felting treatment liquid is 10 - 15 g / L, the enzyme activity of the protease is 5000 - 10000 U / mL, and the concentration of the protease is 1 - 5 g / L.

[0017] In one embodiment of the present invention, the sodium hexyl sulfate salt includes at least one of sodium N-cyclohexylsulfamate, 2-cyclohexylaminoethanesulfonic acid sodium salt, and 3-(cyclohexylamino)-1-propanesulfonic acid sodium salt.

[0018] In one embodiment of the present invention, when using the anti-felting treatment liquid to treat the colored wool fabric, the temperature is 50 - 60 °C, and the pH of the anti-felting treatment liquid is 8 - 9.

[0019] In one embodiment of the present invention, the keratinase and protease include enzyme varieties from different sources such as animals, plants, and microorganisms.

[0020] The present invention also provides a colored wool fabric obtained by finishing according to the above method.

[0021] Advantages of the present invention

[0022] (1) The present invention combines the application of keratinase, protease, and sodium hexyl sulfate salt to conduct anti-felting finishing on the colored wool fabric. The strength loss of the finished colored wool fabric is relatively low. The finishing method does not damage the dye structure and has little impact on the appearance of the wool fabric. The wool fabric obtained by finishing with the method of the present invention has excellent anti-felting effect and soft handfeel.

[0023] (2) Bioenzymes belong to biological agents and are themselves macromolecules of the protein class, with good ecological properties; during the finishing process, no chlorine-containing oxidants or chemical reducing agents are used, achieving zero AOX emissions during the anti-felting finishing process of wool fabrics, and the entire finishing process is environmentally friendly and ecological.

[0024] (3) Treating wool with keratinase can damage the integrity of the outer structure of the scales. After the addition of sodium hexyl sulfate and the protease are combined, the scope of action of the protease macromolecule is restricted, promoting efficient enzymatic hydrolysis based on the scale layer structure on the surface of wool, reducing the strong damage easily caused by the hydrolysis of the protease to the intercellular substance and cortical layer of wool scale cells. After finishing, the wool fabric not only has a low felting shrinkage rate (felting shrinkage rate less than 6%) and a small strength loss (strength loss rate less than or equal to 10%), but also has a soft handfeel and excellent drapability.

[0025] (4) Enzyme molecules have high specificity and only hydrolyze wool scale proteins without damaging the dye structure; therefore, it has significant advantages over traditional chlorination methods or reduction anti-shrinkage methods, and can effectively avoid defects such as light color, color mottling, and hue angle changes during anti-felting finishing. Specific Embodiments

[0026] The following describes the preferred embodiments of the present invention. It should be understood that the embodiments are for better explaining the present invention and are not used to limit the present invention.

[0027] In the following embodiments, keratinase was purchased from Jinan Best Biotechnology Co., Ltd.; the protease was Savinase 16L purchased from Novozymes.

[0028] Example 1

[0029] A method for enzymatic anti-felting finishing of low-strength-loss colored wool fabrics. The colored wool fabric used is a all-wool gabardine (woven fabric) dyed with 3% o.w.f neutral dye Lanaset Red, and specifically includes the following steps:

[0030] (1) Wool keratinase pretreatment: Immerse the colored wool fabric in a keratinase solution for pretreatment for 30 min to obtain the wool fabric after keratinase pretreatment. The enzyme activity of keratinase in the keratinase solution is 5000 U / mL, the concentration of keratinase is 1 g / L, the penetrant is a non-ionic surfactant JFC, its concentration is 0.1 g / L, the pretreatment temperature is 50 °C, and the pH of the keratinase solution is 8;

[0031] (2) Treatment with the anti-felting treatment solution: Immerse the wool fabric treated in step (1) in an anti-felting treatment solution containing sodium N-cyclohexylsulfamate and protease for treatment for 30 min. The treatment temperature is 50 °C. The concentration of sodium N-cyclohexylsulfamate in the anti-felting treatment solution is 10 g / L, the concentration of protease is 1 g / L, and the pH of the anti-felting treatment solution is 8;

[0032] (3) Post-treatment of fabric washing and drying: The fabric treated in step (2) is inactivated with enzymes at 80 °C for 15 min, then washed and dried at 40 °C.

[0033] Example 2

[0034] A method for enzymatic anti-felting finishing of low-strength-loss colored wool fabric, using a woolen knitted fabric dyed with 3% o.w.f wool reactive dye Lanasol Bule as the colored wool fabric, which specifically includes the following steps:

[0035] (1) Wool keratinase treatment: The colored wool fabric is impregnated in a keratinase solution for 60 min to obtain the wool fabric pretreated with keratinase. The enzyme activity of keratinase in the keratinase solution is 8000 U / mL, the concentration of keratinase is 2 g / L, the concentration of penetrant T is 0.2 g / L, the pretreatment temperature is 55 °C, and the pH of the keratinase solution is 9;

[0036] (2) Anti-felting treatment liquid treatment: The wool fabric treated in step (1) is impregnated in an anti-felting treatment liquid containing 2-cyclohexylaminoethanesulfonic acid sodium and protease for 45 min. The treatment temperature is 55 °C. The concentration of 2-cyclohexylaminoethanesulfonic acid sodium in the anti-felting treatment liquid is 10 g / L, the enzyme activity of protease is 8000 U / mL, the concentration of protease is 1.5 g / L, and the pH of the anti-felting treatment liquid is 9;

[0037] (3) Post-treatment of fabric washing and drying: The fabric treated in step (2) is inactivated with enzymes at 80 °C for 30 min, then washed and dried at 60 °C.

[0038] Example 3

[0039] A method for enzymatic anti-felting finishing of low-strength-loss colored wool fabric, using a worsted (woven fabric) dyed with 3% o.w.f wool reactive dye Lanasol Red as the colored wool fabric, which specifically includes the following steps:

[0040] (1) Wool keratinase treatment: The colored wool fabric is impregnated in a keratinase solution for 60 min to obtain the wool fabric pretreated with keratinase. The enzyme activity of keratinase in the keratinase solution is 1000 U / mL and the concentration is 5 g / L. The penetrant is non-ionic surfactant JFC-2 with a concentration of 1 g / L. The pretreatment temperature is 60 °C, and the pH of the keratinase solution is 9;

[0041] (2) Treatment with anti-felting treatment liquid: Immerse the wool fabric treated in step (1) in an anti-felting treatment liquid containing sodium 3-(cyclohexylamino)-1-propanesulfonate and protease for 60 min at a treatment temperature of 60 °C. The concentration of sodium 3-(cyclohexylamino)-1-propanesulfonate in the anti-felting treatment liquid is 15 g / L, the enzyme activity of the protease is 10,000 U / mL, and its concentration is 5 g / L. The pH of the anti-felting treatment liquid is 9;

[0042] (3) Post-treatment of fabric washing and drying: Inactivate the enzyme of the fabric treated in step (2) at 80 °C for 30 min, wash it after treatment, and dry it at 60 °C.

[0043] Comparative Example 1

[0044] The difference between Comparative Example 1 and Example 1 is that the all-wool gabardine is not treated with anything.

[0045] Comparative Example 2

[0046] The difference between Comparative Example 2 and Example 1 is that the all-wool gabardine is only treated with steps (2) and (3), and in step (2), the anti-felting treatment liquid does not contain N-cyclohexylsulfamic acid sodium.

[0047] Comparative Example 3

[0048] The difference between Comparative Example 3 and Example 1 is that the all-wool gabardine is only treated with steps (2) and (3).

[0049] Comparative Example 4

[0050] The difference between Comparative Example 4 and Example 1 is that the all-wool gabardine after pretreatment with keratinase is subjected to anti-felting finishing by the pad-dry-cure method. The specific process is as follows: Immerse and pad the wool fabric treated in step (1) in the anti-felting treatment liquid, control the liquor pickup rate at 70%, pad twice and dry at 100 °C, and then cure at 160 °C for 4 min.

[0051] Comparative Example 5

[0052] The difference between Comparative Example 5 and Example 2 is that the all-wool knitted fabric is not treated with anything.

[0053] Comparative Example 6

[0054] The difference between Comparative Example 6 and Example 2 is that the all-wool knitted fabric is only treated with steps (2) and (3), and in step (2), the anti-felting treatment liquid does not contain 2-cyclohexylaminoethanesulfonic acid sodium.

[0055] Comparative Example 7

[0056] The difference between Comparative Example 7 and Example 2 is that the all-wool knitted fabric is only treated with steps (2) and (3).

[0057] Comparative Example 8

[0058] The difference between Comparative Example 8 and Example 2 is that the full wool knitted fabric after pretreatment with keratinase is subjected to anti-felting finishing by padding and curing. The specific process is as follows: the wool fabric treated in step (1) is padded in the anti-felting treatment liquid, the liquor pickup is controlled at 70%, padded twice and dried at 100°C and then cured at 160°C for 4 min.

[0059] Comparative Example 9

[0060] The difference between Comparative Example 9 and Example 3 is that the full wool serge is not subjected to any treatment.

[0061] Comparative Example 10

[0062] The difference between Comparative Example 10 and Example 3 is that the full wool serge is only treated in step (2) and step (3), and in step (2), the anti-felting treatment liquid does not contain 3-(cyclohexylamino)-1-propanesulfonic acid sodium.

[0063] Comparative Example 11

[0064] The difference between Comparative Example 11 and Example 3 is that the full wool serge is only treated in step (2) and step (3).

[0065] Comparative Example 12

[0066] The difference between Comparative Example 12 and Example 3 is that the full wool serge after pretreatment with keratinase is subjected to anti-felting finishing by padding and curing. The specific process is as follows: the wool fabric treated in step (1) is padded in the anti-felting treatment liquid, the liquor pickup is controlled at 70%, padded twice and dried at 100°C and then cured at 160°C for 4 min.

[0067] The colored wool fabrics obtained in Examples 1 to 3 and Comparative Examples 1 to 12 were respectively subjected to performance measurement. The area felting shrinkage rate (%) of the colored wool fabrics after finishing was measured with reference to GB / T8628-2013; the warp breaking strength of the colored wool woven fabrics before and after finishing was measured with reference to GB / T 3923.1-1997, the bursting strength of the colored wool knitted fabrics before and after finishing was measured with reference to GB / T19976-2005, and the relative strength change rate was calculated and recorded as the sample strength loss rate (%); the drape coefficient (%) of the colored wool fabrics was measured with reference to GB / T 23329-2009; the chromaticity values of the samples were measured with a colorimeter, and the dyeing depth K / S value and hue angle (°) were respectively recorded (the color measurement conditions were D65 light source and 10° field of view), and the results are shown in Table 1.

[0068] Table 1

[0069]

[0070] As can be seen from Table 1:

[0071] a. The area felting shrinkage rates of the colored wool fabrics (Examples 1, 2, and 3) prepared by the method of the present invention are all less than 6%, meeting the requirements of shrink-resistant wool fabrics; at the same time, the strength loss rates of the specimens are all less than or equal to 10%, indicating that the decrease in the strength of the specimens after enzyme treatment is relatively low; the drape coefficients of the above-mentioned colored fabrics after finishing are relatively low, indicating that the feel of the specimens is good; compared with the untreated specimens (Comparative Examples 1, 5, and 9), the hue angles of the colored wool fabrics finished by the method described in the present invention do not change significantly, and the color depth K / S values are at the same level as those of the untreated specimens respectively, indicating that finishing by the method described in the present invention has little effect on the color appearance of the specimens.

[0072] b. The fabric surface felting shrinkage rates of the specimens without any treatment (Comparative Examples 1, 5, and 9) are relatively high (all higher than 20%), indicating poor anti-felting effect; the drape coefficients of the specimens are relatively high, indicating that the feel of the fabric is relatively average.

[0073] c. The area felting shrinkage rates of the specimens (Comparative Examples 2, 6, and 10) treated only by steps (2) and (3) (without adding sodium hexyl sulfate) decrease to a certain extent compared with the untreated specimens, but are still higher than 10%, not meeting the shrink-resistant wool standard; at the same time, the strength loss rates of the specimens after only protease treatment are all greater than 12.5%, indicating that in the single protease treatment, the intercellular matrix components and cortical layers of wool scale cells are hydrolyzed, resulting in relatively serious fiber damage. This result shows that using only protease for wool anti-felting finishing not only makes it difficult to meet the requirements of the felting shrinkage rate, but also easily causes relatively large strength loss.

[0074] d. The area felting shrinkage rates of the specimens (Comparative Examples 3, 7, and 11) treated by steps (2) and (3) are still higher than 9.5%, but due to the interaction between sodium hexyl sulfate and enzyme protein during the treatment, the strength loss of the specimens decreases significantly, and the strength loss rates are all less than 8.5%, indicating that sodium hexyl sulfate can reduce fiber damage in wool protease anti-felting finishing; on the other hand, due to the lack of keratinase pretreatment, the felting shrinkage rate of the specimens does not meet the requirement of <6%, verifying the important role of keratinase in loosening the dense structure of the fiber scale layer, promoting the removal of the scale layer by protease, and enhancing the anti-felting effect.

[0075] e. The samples treated by the pad-steam-bake method (Comparative Example 4, Comparative Example 8, Comparative Example 12) have poor felting resistance, and the area felting shrinkage rates are all higher than 13.5%. It shows that when protease is used as a shrink-proof finishing agent in combination with sodium hexyl sulfate, the pad-steam-bake method cannot improve the felting resistance of wool fabrics. The reason is that protease is extremely prone to thermal inactivation under the pad-steam-bake method, and the combination of sodium hexyl sulfate and protease cannot endow wool fabrics with good felting resistance. The fabric drape coefficient is also relatively high, indicating that the handle of the wool fabric after pad-steam-bake becomes worse than that of the untreated sample.

[0076] It can be seen from this that the samples of Example 1, Example 2 and Example 3 treated by the method of the present invention not only have a low felting shrinkage rate, obtain good felting resistance, but also have a low strength loss of the samples; the fabric drape has been significantly improved compared with the untreated sample; compared with the original colored wool fabric without treatment, the color appearance of the sample finished by the method described in the present invention has not changed significantly.

[0077] Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with this technology can make various modifications and decorations without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the claims.

Claims

1. A method for enzymatic anti-felting finishing of low-strength-loss colored wool fabrics, characterized in that, the method includes the steps of first pretreating the colored wool fabric with keratinase, then treating the pretreated colored wool fabric with an anti-felting treatment solution, and fully washing and drying the fabric, specifically including the following steps: (1) Wool keratinase pretreatment: Immerse the colored wool fabric in a keratinase solution for pretreatment for 30 - 60 min to obtain the wool fabric treated with keratinase; (2) Treatment with anti-felting treatment solution: Immerse the wool fabric obtained in step (1) in the anti-felting treatment solution for treatment for 30 - 60 min, and the anti-felting treatment solution includes protease and sodium hexyl sulfate; (3) Fabric washing and post-drying treatment: Inactivate the enzyme of the fabric treated in step (2) at 80 °C for 15 - 30 min, wash it after treatment, and dry it at 40 °C - 60 °C.

2. The method according to claim 1, characterized in that, the keratinase solution includes keratinase and a penetrant, the enzyme activity of keratinase in the keratinase solution is 5000 - 10000 U / mL, the concentration of keratinase is 1 - 5 g / L, and the concentration of the penetrant is 0.1 - 1 g / L.

3. The method according to claim 2, characterized in that, the penetrant includes non-ionic and / or anionic surfactants.

4. The method according to claim 1, characterized in that, when using keratinase to pretreat the colored wool fabric, the temperature is 50 - 60 °C, and the pH of the keratinase solution is 8 - 9.

5. The method according to claim 1, characterized in that, the concentration of sodium hexyl sulfate in the anti-felting treatment solution is 10 - 15 g / L, the enzyme activity of protease is 5000 - 10000 U / mL, and the concentration of protease is 1 - 5 g / L.

6. The method according to claim 1, characterized in that, the sodium hexyl sulfate includes at least one of sodium N-cyclohexylsulfamate, 2-cyclohexylaminoethanesulfonic acid sodium salt, and 3-(cyclohexylamino)-1-propanesulfonic acid sodium salt.

7. The method according to claim 1, characterized in that, when using the anti-felting treatment solution to treat the colored wool fabric, the temperature is 50 - 60 °C, and the pH of the anti-felting treatment solution is 8 - 9.

8. The method according to claim 1, characterized in that, the colored wool fabric includes any one of wool woven fabrics, knitted fabrics, and non-woven fabrics, and the dyeing method of the colored wool fabric includes any one or a combination of direct dyeing, acid dyeing, acid mordant dyeing, neutral dyeing, and wool reactive dyeing.

9. A colored wool fabric finished by the method according to any one of claims 1 - 8.

Images