CN101565894A - Method for improving antibacterial property of wool by bio-enzymatic method - Google Patents
Method for improving antibacterial property of wool by bio-enzymatic method Download PDFInfo
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- CN101565894A CN101565894A CNA2009100315937A CN200910031593A CN101565894A CN 101565894 A CN101565894 A CN 101565894A CN A2009100315937 A CNA2009100315937 A CN A2009100315937A CN 200910031593 A CN200910031593 A CN 200910031593A CN 101565894 A CN101565894 A CN 101565894A
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Abstract
The invention provides a method for improving antibacterial property of wool by a bio-enzymatic method, which belongs to the field of textile biotechnology. The method utilizes the catalysis of transglutaminase (MTG) to graft some natural compounds which contain primary amine groups and have antibacterial property onto wool to improve the antibacterial property of the wool. The method comprises the following process flows: wool pretreatment, treatment with an MTG-containing antibacterial finishing agent, washing and drying. Wool yarn or fabric treated by the method not only has improvement on the antibacterial property but also correspondingly has improvement on some other properties and particularly has great improvement in low-temperature dyeing property. Meanwhile, the method improves the strength of the wool yarn or the fabric, thereby playing a role in restoring strength. The strength-restoring function is an outstanding advantage of the method compared with other antibacterial finishing agents or antibacterial finishing processes. In addition, compared with chemical finishing, the treatment process of the method is free from pollution, healthier and friendlier to environment by adopting a bio-enzyme technique.
Description
Technical field
The present invention relates to a kind ofly utilize the catalytic action of TGase that the natural materials that some have anti-microbial property is grafted on the wool, give the method for antibacterial property of wool, belong to field of textile biotechnology.
Background technology
Wool fibre and associated materials mainly are made of keratin, and keratin is the complex of sulfur-bearing protein.Although the disulfide bond of intermolecular existence, salt type bond and Van der Waals force make wool fibre for the hydrolysis of proteolytic enzyme stronger resistant function be arranged, but under suitable temperature and humidity condition, after its cast and human body sweat mix, for the growth and breeding of bacterium, mould provides abundant nutrition, make fabric very easily produce the degraded of going mouldy, and cause transmission of disease, restricted the application of wool fabric to a great extent as high-grade fabric, thereby it is carried out antibiotic finish, give its antibiotic property and have realistic meaning preferably.
At present, commonly used both at home and abroad is that the heavy metal substances such as Cu, Ag that will have antibacterial action are handled on the wool by the method for some physics or chemistry, wool is carried out antibiotic finish, but take in the process in dress, these heavy metal ion can discharge from fiber surface, and by infiltrating in the body with contact skin, bigger to human body harm, simultaneously, the discharge of wastewater contaminated environment after the arrangement, and the washing fastness of the fabric after the arrangement is poor.
Microbe-derived TGase (MTG) is a kind of transferase of catalyzing acyl transfer reaction; it can the catalysis glutamine and possesses numerous protein generation acyl group transfer reactions of primary amine; make the change that is applied material generation physicochemical properties; increase the function of material, so this enzyme has broad application prospects in industry such as food, medicine, weavings.It utilizes the γ-formamido of the glutamine residue on the peptide chain as acry radical donor; acceptor can be lysine residue on the protein peptide chain and the amino-compound that has primary amine groups; when not having above two kinds of acceptors; hydrone then serves as the acceptor of acyl group transfer reaction; MTG reaches the intermolecular covalent cross-linking in acyl group transfer reaction formation molecule can take place, the isopeptide bond in all right catalyzing hydrolysis polypeptide chain.Its mechanism is as follows:
(a)R-Glu-CO-NH
2+NH
2-Lys-R′→R-Glu-CO-NH-Lys-R′+NH
3
(b)R-Glu-CO-NH
2+NH
2-R′→R-Glu-CO-NH-R′+NH
3
(c)R-Glu-CO-NH
2+H
2O→R-Glu-CO-OH+NH
3
(d)R-Glu-CO-NH-Lys-R′→R-Glu-+R′-Lys-
At present, the application of MTG in field of textiles main (b) carried out modification to wool and silk, improves its physical and mechanical properties.MTG reaches associating alternate manner associated treatment wool fabric and yarn separately, wool fabric and yarn are because the chemical damage that preliminary treatment caused, biological damage, the multiple damage of chemical/biological is all than to obtained very big reparation in the same old way, wool yarn and fabric strength with the highlyest increase by 25% to compare in the same old way, thereby remedy effectively MTG handle before the fibre damage that caused of various chemistry and Biological Pretreatment.The dyeing wool product has improved the water-fast COLOR FASTNESS of washing of dyeing articles after MTG handles, effectively reduced fabric fading, simultaneously, has reduced the damaged degree (coming from the meta-alkalescence condition of cleaning solution and protease to degradation of fiber) of wool fibre itself.Worsted wool fabric after MTG handles, the DIMENSIONAL STABILITY of fabric, wrinkle resistance, pressure scald property etc. easily the nursing index all than to be improved to some extent in the same old way.Utilize preliminary treatment such as plasma, hydrogen peroxide oxidation, ultrasonic wave and MTG synergy that wool fabric enzyme process felt proofing is had certain synergistic effect.Ultrasonic synergistic protease---MTG composite finishing can significantly improve woolen felt proofing performance, and fabric strength remains unchanged substantially with the elongation performance; Patent CN1546783A discloses the method that a kind of MTG of utilization handles wool fabric, handle by MTG, strengthen the crosslinked action between wool albumen, made performances such as wool DIMENSIONAL STABILITY and wrinkle resistance be improved to some extent, reached the easy effect of nursing of wool fabric.Yet above-mentioned research shows simultaneously, utilizes MTG wool fibre itself to be carried out enzymatic is cross-linking modified only can can't give the wool greater functionality to the wool physical and mechanical properties as to brute force, felt proofing, crease-resistant etc. making moderate progress separately.
Summary of the invention
The purpose of this invention is to provide the bio-modification processing method that the low a kind of biological enzyme of a kind of environmental friendliness, environmental health, energy consumption improves antibacterial property of wool.It is good that the wool of handling through this method has antibiotic property, the powerful answer, and can promote advantage such as woolen dyed performance preferably.
Technical scheme of the present invention: a kind of biological enzyme improves the method for antibacterial property of wool, the natural antibacterial finishing agent that utilizes the catalytic action of TGase MTG will contain primary amine group and have an anti-microbial property is grafted on the wool, improve antibacterial property of wool, processing step:
A, wool preliminary treatment: pretreating process is selected for use: 1. KMnO
4Preliminary treatment; 2. H
2O
2Preliminary treatment; 3. Na
2SO
3Preliminary treatment; 4. NaClO preliminary treatment; 5. a kind of in the DCCNa DCCA preprocess method;
B, the antibacterial finishing agent that contains MTG are handled: the bulk fibre in wool fabric or its preceding road, wool top immerse in the buffer solution that contains MTG and natural antibacterial finishing agent to be handled, and selected enzyme is MTG, adds the polyoxyethylene-type non-ionic surface active agent in the treatment fluid and makes bleeding agent; Treatment fluid is formed: MTG 1～60U/g fabric, natural antibacterial finishing agent mass concentration 1%～6%, bleeding agent mass concentration 0.5%, treatment fluid pH 6.5～8.5, the weight bath raio of fabric and treatment fluid 1: 10～1: 30,30～50 ℃ of treatment temperatures, processing time 1～12h;
C, washing and oven dry.
Described biological enzyme improves the method for antibacterial property of wool, is fit to bulk fibre, the wool top in various types of all-wool cloths or its preceding road.
Described natural antibacterial finishing agent is selected α-polylysine, epsilon-polylysine, shitosan, lactoferrin, lysozyme or poly arginine for use.
Described bleeding agent is selected for use: alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or diisooctyl succinate sodium sulfonate.
The used cushioning liquid of preparation treatment fluid is selected sodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, sodium hydrogen phosphate-potassium phosphate buffer, tris-HCI buffer or boric acid-borate buffer solution for use.
The present invention is described in detail as follows:
1. wool preliminary treatment:
Wool fibre has very strong resistance because the top layer has hydrophobic lipoid layer to the effect of enzyme; And, in the skin of wool scale, there are two a large amount of sulphur interlinkages, cause the big molecules align of wool fibre tight, the molecular weight of MTG is bigger in addition, and this just causes MTG to be difficult to diffuse into fiber inner cortex layer and carries out effective function.So utilize MTG to handle separately, effect is also not obvious.If earlier wool is carried out suitable preliminary treatment, the cystine that destroys wool surface hydrophobicity layer and fibrous inside in advance is crosslinked.Just help the effect of MTG to cortex of wool protein.The selected pretreating scheme of the present invention can be selected for use: 1. KMnO
4Preliminary treatment; 2. H
2O
2Preliminary treatment; 3. Na
2SO
3Preliminary treatment; 4. NaClO preliminary treatment; 5. DCCA (DCCNa) preliminary treatment.
1. KMnO
4Preliminary treatment: wool Hot water immersion, liquor potassic permanganate oxidation (KMnO
42%～4%owf, bleeding agent 0.5-1g/L, pH 3～5,35～45 ℃ of temperature, time 25-35min, bath raio 1: 20), soap (45 ℃, 15～20min), (soda ash 2%～3%owf), flushing with clean water, 50 ℃ of oven dry, decolouring (NaHSO are cleaned in neutralization
34%～6%owf, HAc mass fraction 1%, 35～45 ℃ of temperature, time 15～30min, bath raio 1: 20), washing and oven dry.
2. H
2O
2Preliminary treatment: wool Hot water immersion, hydrogen peroxide oxidation (H
2O
220～40mL/L, Na
2SiO
43～5g/L, Na
2CO
30.1%～0.2%owf, bleeding agent 0.5-1g/L, pH 8～8.5,40～50 ℃ of temperature, time 40～60min, bath raio 1: 20), washing and oven dry.
3. Na
2SO
3Preliminary treatment: textile impregnation reducing solution (Na
2SO
32%～3%owf, pH 8～8.5,35～40 ℃ of temperature, time 30～45min, bath raio 1: 20), washing and oven dry.
4. NaClO preliminary treatment: wool Hot water immersion, liquor natrii hypochloritis's oxidation (NaClO 1%～2%owf, pH 5～6,35～45 ℃ of temperature, time 15～25min, bath raio 1: 30), flushing, 50 ℃ of oven dry, dechlorination (NaHSO
32%～3%owf, pH 3.5～5,25～30 ℃ of temperature, time 20～30min, bath raio 1: 20), washing and oven dry.
5. DCCA preliminary treatment: wool cold water dipping, DCCA chloridized (pH 3.5～4.0 for DCCA 2%～6%owf, bleeding agent 0.5～1g/L, 20～25 ℃ of temperature, time 20～30min, bath raio 1: 20), 40 ℃ of warm water wash rinse, dechlorination (NaHSO
34%～6%owf, pH 3.5～4.0,30～40 ℃ of temperature, time 15～20min, bath raio 1: 20), washing, adjust pH (Tris-HCl pH 8～9,30～40 ℃ of temperature, time 15～20min, bath raio 1: 25), washing and oven dry.
2. the natural antibacterial finishing agent that contains MTG is handled:
Fabric immerses handles in the buffer solution contain MTG and natural antibacterial finishing agent that (the MTG consumption is 1～60U/g fabric; The natural antibacterial finish content is 1%～6%owf; Bleeding agent content is 0.5%owf; The pH 6.5～8.5 of treatment fluid, the weight bath raio of fabric and treatment fluid 1: 10～1: 30,30～50 ℃ of treatment temperatures, processing time 1～12h).
Beneficial effect of the present invention: utilize biology enzyme MTG catalytic antimicrobial class material grafted wool to carry out antibiotic finish first, compare with traditional wool antibacterial finishing process, the present invention has the following advantages:
1. utilize biology enzyme that wool is carried out finishing functions, meet the requirement of modern green ecological, health environment-friendly.
2. utilize biology enzyme to make the graft reaction catalyst, the catalytic efficiency height, consumption is few, the reaction condition gentleness.
3. the inventive method is grafted to antibacterial finishing agent and the wool formation covalent bonds on the wool, and fastness is good.
4. utilize this biological enzyme improve antibacterial property of wool can the time, can also improve the ultimate strength and the dyeability of wool, and to wool whiteness, feel influence less.
5. adopt biological enzyme technology, treatment process is safety and environmental protection more, less energy consumption and pollution-free.
The specific embodiment
Wool adopts the MTG biological enzyme antibiotic finish specific embodiment of different pretreating agents and natural antibacterial agent as follows:
Embodiment 1: the selected wool of this example is an all-wool valetin, and selected pretreatment mode is KMnO
4Preliminary treatment, selected finishing agent are epsilon-polylysine.
Get the 2.0g wool fabric and carry out preliminary treatment: wool fabric Hot water immersion, liquor potassic permanganate oxidation (KMnO by following technology
44%owf, bleeding agent 0.5g/L, pH 4.0,40 ℃ of temperature, time 30min, bath raio 1: 20), soaping, (45 ℃, 15min), (soda ash 2%owf) cleaned in neutralization, flushing with clean water, 50 ℃ of oven dry, decolouring (NaHSO
36%owf, HAc mass fraction 1%, 40 ℃ of temperature, time 30min, bath raio 1: 20), washing and oven dry.
Wool fabric after the above-mentioned preliminary treatment is handled as follows: fabric immerses cushioning liquid (MTG:20U/g fabric, epsilon-polylysine: 3%owf, the bleeding agent 0.5%owf that contains MTG and epsilon-polylysine, 45 ℃ of temperature, time 2h, bath raio 1: 30, pH 8.0), washing and oven dry.
Sample by after the above-mentioned technology arrangement has carried out following performance test respectively, the results are shown in Table 1:
Table 1 embodiment 1 antibiotic finish fabric property
| Press down staphylococcus aureus (%) | Press down Escherichia coli rate (%) | Broadwise ultimate strength (N) | Warp-wise ultimate strength (N) | 70 ℃ of dyeing K/S | 80 ℃ of dyeing K/S | |
| Blank sample | 0 | 0 | 206.2 | 253.1 | 16.9 | 23.1 |
| KMnO 4Preliminary treatment/MTG handles | 94.3 | 96.6 | 215.4 | 267.8 | 34.7 | 35.4 |
Embodiment 2: the selected wool of this example is an all-wool gabardine, and selected pretreatment mode is the DCCA preliminary treatment, and selected finishing agent is α-polylysine.
Get the 2.0g wool fabric and carry out preliminary treatment: cold water dipping, DCCA chloridized (pH 3.5 for DCCA4%owf, bleeding agent 1g/L, 25 ℃ of temperature, time 20min, bath raio 1: 20), 40 ℃ of warm water wash rinse, dechlorination (NaHSO by following technology
36%owf, pH 4.0,40 ℃ of temperature, time 20min, 1: 20), washing, adjust pH (Tris-HCl pH 8,30 ℃ of temperature, time 15min, bath raio 1: 25), washing oven dry.
Wool fabric after the above-mentioned preliminary treatment is handled as follows: fabric immerses cushioning liquid (MTG:30U/g fabric, α-polylysine: 2%owf, the bleeding agent 0.5%owf that contains MTG and α-polylysine, 50 ℃ of temperature, time 1h, bath raio 1: 20, pH 7.5), washing and oven dry.
Sample by after the above-mentioned technology arrangement has carried out following performance test respectively, the results are shown in Table 2:
Table 2 embodiment 2 antibiotic finish fabric properties
| Press down staphylococcus aureus (%) | Press down Escherichia coli rate (%) | Broadwise ultimate strength (N) | Warp-wise ultimate strength (N) | 70 ℃ of dyeing K/S | 80 ℃ of dyeing K/S | |
| Blank sample | 0 | 0 | 379.2 | 419.3 | 17.4 | 24.0 |
| DCCA preliminary treatment/MTG handles | 95.2 | 97.6 | 386.1 | 426.2 | 35.3 | 36.1 |
Embodiment 3: the selected wool of this example is a merino Australia wool top, and selected pretreatment mode is Na
2SO
3Preliminary treatment, selected finishing agent are epsilon-polylysine.
Get the 2.0g wool top and carry out preliminary treatment: wool top dipping reducing solution (Na by following technology
2SO
33%owf, pH8.5,40 ℃ of temperature, time 30min, bath raio 1: 20), washing and oven dry.
Above-mentioned pretreated wool top is handled as follows: wool top immerses cushioning liquid (MTG:25U/g fabric, epsilon-polylysine: 3%owf, the bleeding agent 0.5%owf that contains MTG and epsilon-polylysine again, 40 ℃ of temperature, time 4h, bath raio 1: 20, pH 8), washing and oven dry.
Sample by above-mentioned technology arrangement has carried out following performance test respectively, the results are shown in Table 3:
Table 3 embodiment 3 antibiotic finish fabric properties
| Press down staphylococcus aureus (%) | Press down Escherichia coli rate (%) | Ultimate strength (N) | 70 ℃ of dyeing K/S | 80 ℃ of dyeing K/S | |
| Blank sample | 0 | 0 | 2.2 | 16.2 | 22.5 |
| Na 2SO 3Preliminary treatment/MTG handles | 96.3 | 98.2 | 2.5 | 34.2 | 35.4 |
Embodiment 4: the selected wool of this example is an all-wool valetin, and selected pretreatment mode is the NaClO preliminary treatment, and selected finishing agent is a lactoferrin.
Get the 2.0g wool fabric and carry out preliminary treatment: Hot water immersion, NaClO solution oxide (NaClO2%owf, pH 6,45 ℃ of temperature, time 15min, bath raio 1: 30), flushing, 50 ℃ of oven dry, dechlorination (NaHSO by following technology
33%owf, pH 5,30 ℃ of temperature, time 20min, bath raio 1: 20), washing and oven dry.
Above-mentioned pretreated wool fabric is handled as follows: fabric immerses cushioning liquid (MTG:30U/g fabric, lactoferrin: 4%owf, the bleeding agent 0.5%owf that contains MTG and lactoferrin, 50 ℃ of temperature, time 2h, bath raio 1: 20, pH 8.0), washing and oven dry.
Sample by above-mentioned technology arrangement has carried out the test of following performance respectively, the results are shown in Table 4:
Table 4 embodiment 4 antibiotic finish fabric properties
| Press down staphylococcus aureus (%) | Press down Escherichia coli rate (%) | Broadwise ultimate strength (N) | Warp-wise ultimate strength (N) | 70 ℃ of dyeing K/S | 80 ℃ of dyeing K/S | |
| Blank sample | 0 | 0 | 209.5 | 247.4 | 16.1 | 21.6 |
| NaClO preliminary treatment/MTG handles | 88.6 | 94.2 | 219.7 | 259.8 | 25.4 | 26.1 |
Embodiment 5: the selected wool of this example is an all-wool gabardine, and selected pretreatment mode is H
2O
2Preliminary treatment, selected finishing agent are shitosan.
Get the 2.0g wool fabric and carry out preliminary treatment: wool fabric Hot water immersion, hydrogen peroxide oxidation (H by following technology
2O
225mL/L, Na
2SiO
44g/L, Na
2CO
30.15%owf, bleeding agent 1g/L, pH 8.5,45 ℃ of temperature, time 50min, bath raio 1: 20), washing and oven dry.
Above-mentioned pretreated wool fabric is handled as follows: fabric immerses cushioning liquid (MTG:25U/g fabric, shitosan: 2%owf, the bleeding agent 0.5%owf that contains MTG and shitosan again, 42 ℃ of temperature, time 1.5h, bath raio 1: 20, pH 7.5), washing and oven dry.
Sample by above-mentioned technology arrangement has carried out the test of following performance respectively, the results are shown in Table 5:
Table 5 embodiment 5 antibiotic finish fabric properties
| Press down staphylococcus aureus (%) | Press down Escherichia coli rate (%) | Broadwise ultimate strength (N) | Warp-wise ultimate strength (N) | 70 ℃ of dyeing K/S | 80 ℃ of dyeing K/S | |
| Blank sample | 0 | 0 | 388.2 | 416.4 | 14.3 | 21.7 |
| H 2O 2Preliminary treatment/MTG handles | 92.3 | 86.5 | 398.1 | 427.5 | 33.6 | 34.3 |
By as can be known: handled wool fabric of technology of the present invention or wool top to above-mentioned case data analysis, not only anti-microbial property improves obviously, and other some performances have also obtained certain raising, particularly wool yarn and coloration of textile materials performance obtain bigger raising, the brute force of wool yarn and fabric has also obtained raising to a certain degree, plays powerful effect of repairing.
Claims (5)
1. a biological enzyme improves the method for antibacterial property of wool, it is characterized in that utilizing the catalytic action of TGase MTG will contain primary amine group and natural antibacterial finishing agent with anti-microbial property is grafted on the wool, improves antibacterial property of wool, processing step:
A, wool preliminary treatment: pretreating process is selected for use: 1. KMnO
4Preliminary treatment; 2. H
2O
2Preliminary treatment; 3. Na
2SO
3Preliminary treatment; 4. NaClO preliminary treatment; 5. a kind of in the DCCNa DCCA preprocess method;
B, the antibacterial finishing agent that contains MTG are handled: the bulk fibre in wool fabric or its preceding road, wool top immerse in the buffer solution that contains MTG and natural antibacterial finishing agent to be handled, and selected enzyme is MTG, adds the polyoxyethylene-type non-ionic surface active agent in the treatment fluid and makes bleeding agent; Treatment fluid is formed: MTG 1～60U/g fabric, natural antibacterial finishing agent mass concentration 1%～6%, bleeding agent mass concentration 0.5%, treatment fluid pH6.5～8.5, the weight bath raio of fabric and treatment fluid 1: 10～1: 30,30～50 ℃ of treatment temperatures, processing time 1～12h;
C, washing and oven dry.
2. the described biological enzyme of claim 1 improves the method for antibacterial property of wool, it is characterized in that being fit to bulk fibre, the wool top in various types of all-wool cloths or its preceding road.
3. the described biological enzyme of claim 1 improves the method for antibacterial property of wool, it is characterized in that described natural antibacterial finishing agent selects α-polylysine, epsilon-polylysine, shitosan, lactoferrin, lysozyme or poly arginine for use.
4. the described biological enzyme of claim 1 improves the method for antibacterial property of wool, it is characterized in that described bleeding agent selects for use: alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether or diisooctyl succinate sodium sulfonate.
5. the described biological enzyme of claim 1 improves the method for antibacterial property of wool, it is characterized in that preparing the used cushioning liquid of treatment fluid and selects sodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, sodium hydrogen phosphate-potassium phosphate buffer, tris-HCI buffer or boric acid-borate buffer solution for use.
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| CN108660767A (en) * | 2018-05-23 | 2018-10-16 | 江苏阳光股份有限公司 | A kind of preparation method of antibacterial mercerized wool fabric |
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| CN109610156A (en) * | 2018-12-04 | 2019-04-12 | 山东如意科技集团有限公司 | A kind of worsted cashmere facing anti-crease finishing technique |
| CN110331598A (en) * | 2019-07-12 | 2019-10-15 | 常熟市新光毛条处理有限公司 | A kind of dyeing and finishing processing method of non-shrinkable wool item |
| CN113233691A (en) * | 2020-07-13 | 2021-08-10 | 天津工业大学 | Shrink-proof treatment method for wool fiber or wool fiber fabric |
| CN112680974A (en) * | 2020-12-28 | 2021-04-20 | 江南大学 | Protein fiber biological antibacterial finishing method |
| CN112680974B (en) * | 2020-12-28 | 2022-07-22 | 江南大学 | Protein fiber biological method antibacterial finishing method |
| CN114622410A (en) * | 2022-03-04 | 2022-06-14 | 安徽德和织造有限公司 | Antibacterial, mothproof and anti-felting finishing method for cashmere fabric |
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