CN102121195A - Antibacterial finishing agent and preparation method thereof - Google Patents
Antibacterial finishing agent and preparation method thereof Download PDFInfo
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- CN102121195A CN102121195A CN2010106199190A CN201010619919A CN102121195A CN 102121195 A CN102121195 A CN 102121195A CN 2010106199190 A CN2010106199190 A CN 2010106199190A CN 201010619919 A CN201010619919 A CN 201010619919A CN 102121195 A CN102121195 A CN 102121195A
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Abstract
The invention relates to an antibacterial finishing agent, wherein the antibacterial finishing agent is prepared through the following steps: copolymerizing an alkenyl amine monomer and an acrylic ester monomer; then adding a functional cross-linking monomer into the copolymer; preparing a copolymer emulsion by means of emulsion polymerization in the presence of a radical initiator; and complexing the copolymer emulsion with silver ions. The antibacterial finishing agent in the invention has perfect molding property so that the antibacterial property is last, and the antibacterial property of a fabric can be effectively improved.
Description
Technical field
The present invention relates to a kind of antibacterial finishing agent, belong to the TEXTILE CHEMICALS field.
Background technology
The antiseptic of textiles use at present generally is divided into natural antibacterial agent, organic antibacterial agent and inorganic antiseptic three classes.
Organic antibacterial agent is based on synthetic organic articles such as phenolic ether class, phenol, biguanides, isothiazole classes, have characteristics such as sterilization speed is fast, antibacterial range is wide, anti-mold effect is good, but have shortcomings such as toxicity is big, heat resistance is relatively poor, duration of efficacy is short simultaneously.
Natural antibacterial agent is the extraction of substance of natural plants, as mustard extract, wasabi essential oil, Tea Polyphenols etc., its antimicrobial efficiency height, safety non-toxic, but poor heat resistance, short, the processing difficulties of duration of efficacy, large-scale commercial at present also is unrealized.In addition, shitosan and derivative thereof by extensive concern, although carried out a large amount of action oriented researchs aspect textile finishing, still also are in laboratory stage as antiseptic basically in recent years.
Inorganic antiseptic is meant that mainly silver, copper, zinc etc. itself are had the metal of antibacterial ability or metal ion is carried on preparation on the inorganic matter carrier.And silver sterilizing ability than copper, the big manyfold of zinc, the sterilizing ability of metal ion is in proper order: Ag
+＞Cu
2+＞Fe=Sn
2+＞Al
3+Therefore commercial at present inorganic antiseptic is silver-series antibacterial agent mostly, as silver zeolite anti-bacterial fibre (U.S.'s fiber and non-weaving cloth manufacturer Foss company), silver-containing inorganic zeolite (AgION) is embedded polyester, form the Fossfiber bicomponent fibers, make AgION only be distributed in skin of fiber, to harmful bacteria contact-making surface optimization.But general carrying silver antimicrobials in medium uniformly dispersed problem, permanent ageing problem, antibacterial components (silver ion) in carrier from animal migration and slow release problem.These problems mainly are to be caused by the absorption property of inorganic mineral carrier, specific area and the proper properties such as dispersiveness in other material of main parts.The outstanding characteristics of inorganic antibacterial preparation are durability and safe, good heat resistance, antibacterial range is wide, the term of validity is long, is main developing direction from now on.Begin to research and develop the eighties in 20th century novel inorganic class antiseptic, have advantages such as heat-resisting, lasting, continuity and security height; Comprise that mainly ion-type and nano titanium oxide, zinc oxide are the photocatalyst-type anti-biotic agent two big classes of representative.The ion-type antiseptic mainly is that the metal ion that will have antibacterial action is carried on certain carrier, and by slow release metal ions performance antibacterial action, but its shortcoming is also more obvious, as mildew-resistant, antifungic action a little less than, cost is higher, and is easy to change etc.; The photocatalyst-type anti-biotic agent mainly reaches antibiotic purpose by catalytic oxidation in the presence of ultraviolet ray and oxygen, but need the solution nano antibacterial agent in dressing liquid even scattering problem and with the problem that combines of fiber.
Summary of the invention
Present situation according to textiles antibacterial finishing agent properties of product deficiency, the invention provides the antibacterial finishing agent that a kind of amine and silver ion complexation mode form, overcome the migration shortcoming of above-mentioned silver, promoted the anti-microbial property and the durability of silver-colored antibacterial finishing agent as antiseptic.
For achieving the above object, product of the present invention is finished by following two steps:
The first step: contain the synthetic of amine copolymer thing emulsion
The described amine copolymer thing emulsion that contains is by comprising that at least thiazolinyl amine monomer, acrylic ester monomer, cross-linking monomer, emulsifying agent, initator, deionized water make through emulsion polymerisation process.
Described thiazolinyl amine monomer comprises alkenyl amine, diallylamine, triallylamine.
Described acrylic ester monomer comprises one or more the combination in acrylic acid, methacrylic acid, methyl methacrylate, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, hydroxy propyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxy butyl ester, the own ester of acrylic acid hydroxyl, the 2-EHA.
Described cross-linking monomer comprises one or more the combination in oneself two hydrazines of diacetone acrylamide/adipic acid, gamma-methyl allyl acyloxypropyl trimethoxysilane, acryloyl-oxy propyl trimethoxy silicane, gamma-methyl allyl acyloxypropyl three second methoxy silane, acryloyl-oxy propyl-triethoxysilicane, gamma-methyl allyl acyloxypropyl three isopropoxy silane, acryloyl-oxy propyl group three isopropoxy silane, the methyl propenoic acid glycidyl ether.
Described initator comprises one or more combinations in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, the benzoyl peroxide.
Described emulsifying agent is made up of non-ionic surface active agent, anion surfactant and low mass molecule alcohol compounds, and wherein anion surfactant is that lauryl sodium sulfate, alkyl number are one or both in 8～9 the alkyl phenol ether sulfosuccinic acid ester sodium salt; Non-ionic surface active agent is that fatty alcohol-polyoxyethylene ether, the alkyl number of molecular weight 400～800 is 8～9 alkylphenol polyoxyethylene and in the polyethylene glycol one or more, and the low mass molecule alcohol compounds is a glycerine.
In emulsifying agent, the weight of anion surfactant is 2～8 parts by umber, and the weight of non-ionic surface active agent is 4～14 parts by umber, and the weight of low mass molecule alcohol compounds is pressed 1～5 part of umber.
In the above-mentioned component, thiazolinyl amine monomer consumption is 15～28 parts by umber, the acrylic ester monomer consumption is 80～200 parts by umber, amount ofthe cross-linking monomer is 3～12 parts by umber, the consumption of emulsifying agent is 5～20 parts by umber, initiator amount is 0.2～0.5 part by umber, and the deionized water consumption is 400～700 parts by umber, and described consumption is weight.
The concrete steps of preparation antibacterial finishing agent are as follows:
A, in reactor, add 5～20 parts of emulsifying agents and 350～610 parts of water, heat up, stir, treat emulsifiers dissolve, be cooled to below 50 ℃;
B, 40～80 parts of acrylic ester monomers of adding, 15～28 parts of thiazolinyl amine monomers, emulsification 40min, add 0.07～0.15 part of initator, initator is warming up to 60～65 ℃ of initiation reactions with 20～40 parts of water-soluble, carrying out along with polymerisation, reaction temperature rises to 70～85 ℃ gradually, and the reaction time is 2～3h, and emulsion presents light blue;
After c, question response temperature in the kettle fall after rise, emulsion temperature is adjusted into 70 ℃, and insulation 0.5h;
D, under 70～75 ℃ of temperature, drip 40～120 parts of acrylic ester monomers then, 3～12 parts of cross-linking monomers, and 0.13～0.35 part of initator, initator is with 30～50 parts of water-soluble, the dropping time is 1～1.5h, drips follow-up continuation of insurance temperature 1h, is cooled to below 50 ℃, regulate pH value to 7 with ammoniacal liquor, promptly obtain containing amine copolymer thing emulsion.
Second step: the preparation of silver-carrying antibiotic finishing agent
Under pH neutral, on the nitrogen-atoms in the amido contained lone pair electrons can with Ag
+Ion forms stable complex compound, makes Ag
+Be fixed on the copolymer molecule chain.
In synthetic the containing in the amine copolymer thing emulsion of the first step, add 8～32 parts of silver nitrates, stirred 2～4 hours down at 16～25 ℃, make amido and Ag
+Fully complexing makes silver-carrying antibiotic finishing agent.
This finishing agent has good filming performance, does not need to add adhesive in use again, and silver ion is anchored on the polymer by coordinate bond, has avoided moving during use and weakens its anti-microbial property, thereby strengthened the endurance quality of antibacterial finishing agent.
The specific embodiment
Below by embodiment in detail the present invention is described in detail, but content of the present invention and scope are not limited to described embodiment, so those skilled in the art all should be contained within the interest field of the present invention all kinds of changes that the present invention makes according to spirit of the present invention.
Unless stated otherwise, following unit is parts by mass.
The concrete steps of antibacterial finishing agent of the present invention are:
Embodiment 1
(a) with following monomer
Butyl acrylate 120g
Methyl methacrylate 18g
Ethyl acrylate 24g
Acrylic acid 6g
Acryloyl-oxy propyl-triethoxysilicane 12g
Place in the 500ml reactor, stir, form the polymer monomer mixed liquor A.
(b) with following component
Fatty alcohol-polyoxyethylene ether (10) 3.2g
Emulsifier os 2.4g
Alkylphenol polyoxyethylene (30) 3.6g
Polyethylene glycol (molecular weight 400) 2.1g
Lauryl sodium sulfate 2.4g
Glycerine 1.1g
Deionized water 250g
Place the 500ml glass,, form stable emulsifier aqueous solution B in 50 ℃ of stirring and dissolving 40min.Form solution for standby with 75g deionized water dissolving 0.25g ammonium persulfate.
(c) under agitation, the polymer monomer mixed liquor A with 1/3 weight joins among the emulsifier aqueous solution B emulsion C of formation polymer monomer.
(d) in the 500ml four-hole boiling flask that thermometer, agitator are housed, add above-mentioned emulsion C.Under agitation, temperature in the bottle is risen to 60 ℃, add the ammonium persulfate solution of 1/3 weight with dropping funel, along with the carrying out of polymerisation, reaction temperature rises to 80 ℃ gradually, and emulsion presents light blue, after treating that a bottle interior temperature falls after rise, emulsion temperature is adjusted into 70 ℃, and insulation 0.5h.Under uniform temp, drip the polymer monomer mixed liquor A of 2/3 remaining weight and the ammonium persulfate solution of 2/3 weight then with 1h.After dripping, continue insulation 1h.Polymerized emulsion is cooled to below 50 ℃, with ammoniacal liquor adjustment pH value to 7, promptly obtains containing amine copolymer thing emulsion.
(e) in (d) solution for preparing, add the 8g silver nitrate, stirred 4 hours down, make amido and Ag at 18 ℃
+Fully complexing makes silver-carrying antibiotic finishing agent.
Embodiment 2
(a) with following monomer
Butyl acrylate 112g
Methyl methacrylate 23g
Isooctyl acrylate monomer 32g
Methacrylic acid 8g
Gamma-methyl allyl acyloxypropyl three isopropoxy silane 14g
Place in the 500ml reactor, stir, form the polymer monomer mixed liquor A.
(b) with following component
Fatty alcohol-polyoxyethylene ether (10) 2.8g
Emulsifier os 2.9g
Alkylphenol polyoxyethylene (30) 3.2g
Polyethylene glycol (molecular weight 400) 2.4g
Lauryl sodium sulfate 2.7g
Glycerine 1.3g
Deionized water 250g
Place the 500ml glass,, form stable emulsifier aqueous solution B in 50 ℃ of stirring and dissolving 40min.Form solution for standby with 75g deionized water dissolving 0.326g ammonium persulfate.
(c) under agitation, the polymer monomer mixed liquor A with 1/3 weight joins among the emulsifier aqueous solution B emulsion C of formation polymer monomer.
(d) in the 500ml four-hole boiling flask that thermometer, agitator are housed, add above-mentioned emulsion C.Under agitation, temperature in the bottle is risen to 60 ℃, add the ammonium persulfate solution of 1/3 weight with dropping funel, along with the carrying out of polymerisation, reaction temperature rises to 80 ℃ gradually, and emulsion presents light blue, after treating that a bottle interior temperature falls after rise, emulsion temperature is adjusted into 72 ℃, and insulation 0.5h.Under uniform temp, drip the polymer monomer mixed liquor A of 2/3 remaining weight and the ammonium persulfate solution of 2/3 weight then with 1h.After dripping, continue insulation 1h.Polymerized emulsion is cooled to below 50 ℃, with ammoniacal liquor adjustment pH value to 7, promptly obtains containing amine copolymer thing emulsion.
(e) in (d) solution for preparing, add the 10g silver nitrate, stirred 4 hours down, make amido and Ag at 20 ℃
+Fully complexing makes silver-carrying antibiotic finishing agent.
Embodiment 3
(a) with following monomer
Butyl acrylate 112g
Ethyl methacrylate 19g
Propyl acrylate 34g
Acrylic acid 6g
Acryloyl-oxy propyl group three isopropoxy silane 12g
Place in the 500ml reactor, stir, form the polymer monomer mixed liquor A.
(b) with following component
Fatty alcohol-polyoxyethylene ether (10) 2.2g
Emulsifier os 4.1g
Alkylphenol polyoxyethylene (30) 3.2g
Polyethylene glycol (molecular weight 400) 1.6g
Lauryl sodium sulfate 2.7g
Glycerine 1.5g
Deionized water 250g
Place the 500ml glass,, form stable emulsifier aqueous solution B in 50 ℃ of stirring and dissolving 40min.Form solution for standby with 75g deionized water dissolving 0.364g ammonium persulfate.
(c) under agitation, the polymer monomer mixed liquor A with 1/3 weight joins among the emulsifier aqueous solution B emulsion C of formation polymer monomer.
(d) in the 500ml four-hole boiling flask that thermometer, agitator are housed, add above-mentioned emulsion C.Under agitation, temperature in the bottle is risen to 60 ℃, add the ammonium persulfate solution of 1/3 weight with dropping funel, along with the carrying out of polymerisation, reaction temperature rises to 80 ℃ gradually, and emulsion presents light blue, after treating that a bottle interior temperature falls after rise, emulsion temperature is adjusted into 75 ℃, and insulation 0.5h.Under uniform temp, drip the polymer monomer mixed liquor A of 2/3 remaining weight and the ammonium persulfate solution of 2/3 weight then with 1h.After dripping, continue insulation 1h.Polymerized emulsion is cooled to below 50 ℃, with ammoniacal liquor adjustment pH value to 7, promptly obtains containing amine copolymer thing emulsion.
(e) in (d) solution for preparing, add the 11g silver nitrate, stirred 4 hours down, make amido and Ag at 18 ℃
+Fully complexing makes silver-carrying antibiotic finishing agent.
Embodiment 4
(a) with following monomer
Butyl acrylate 96g
Methyl methacrylate 22g
Ethyl acrylate 28g
Isooctyl acrylate monomer 14g
Acrylic acid 6g
Methyl propenoic acid glycidyl ether 13g
Place in the 500ml reactor, stir, form the polymer monomer mixed liquor A.
(b) with following component
Fatty alcohol-polyoxyethylene ether (10) 3.5g
Emulsifier os 1.9g
Alkylphenol polyoxyethylene (30) 4.1g
Polyethylene glycol (molecular weight 400) 1.4g
Lauryl sodium sulfate 2.3g
Glycerine 2.2g
Deionized water 250g
Place the 500ml glass,, form stable emulsifier aqueous solution B in 50 ℃ of stirring and dissolving 40min.Form solution for standby with 75g deionized water dissolving 0.25g ammonium persulfate.
(c) under agitation, the polymer monomer mixed liquor A with 1/3 weight joins among the emulsifier aqueous solution B emulsion C of formation polymer monomer.
(d) in the 500ml four-hole boiling flask that thermometer, agitator are housed, add above-mentioned emulsion C.Under agitation, temperature in the bottle is risen to 60 ℃, add the ammonium persulfate solution of 1/3 weight with dropping funel, along with the carrying out of polymerisation, reaction temperature rises to 80 ℃ gradually, and emulsion presents light blue, after treating that a bottle interior temperature falls after rise, emulsion temperature is adjusted into 76 ℃, and insulation 0.5h.Under uniform temp, drip the polymer monomer mixed liquor A of 2/3 remaining weight and the ammonium persulfate solution of 2/3 weight then with 1h.After dripping, continue insulation 1h.Polymerized emulsion is cooled to below 50 ℃, with ammoniacal liquor adjustment pH value to 7, promptly obtains containing amine copolymer thing emulsion.
(e) in (d) solution for preparing, add the 11g silver nitrate, stirred 4 hours down, make amido and Ag at 18 ℃
+Fully complexing makes silver-carrying antibiotic finishing agent.
Embodiment 5
(a) with following monomer
Butyl acrylate 106g
Methyl methacrylate 21g
Ethyl acrylate 17g
Methyl acrylate 15g
Acrylic acid 5g
Gamma-methyl allyl acyloxypropyl trimethoxysilane 14g
Place in the 500ml reactor, stir, form the polymer monomer mixed liquor A.
(b) with following component
Fatty alcohol-polyoxyethylene ether (10) 1.8g
Emulsifier os 2.3g
Alkylphenol polyoxyethylene (30) 3.4g
Polyethylene glycol (molecular weight 400) 1.8g
Lauryl sodium sulfate 2.2g
Glycerine 1.4g
Deionized water 250g
Place the 500ml glass,, form stable emulsifier aqueous solution B in 50 ℃ of stirring and dissolving 40min.Form solution for standby with 75g deionized water dissolving 0.25g ammonium persulfate.
(c) under agitation, the polymer monomer mixed liquor A with 1/3 weight joins among the emulsifier aqueous solution B emulsion C of formation polymer monomer.
(d) in the 500ml four-hole boiling flask that thermometer, agitator are housed, add above-mentioned emulsion C.Under agitation, temperature in the bottle is risen to 60 ℃, add the ammonium persulfate solution of 1/3 weight with dropping funel, along with the carrying out of polymerisation, reaction temperature rises to 80 ℃ gradually, and emulsion presents light blue, after treating that a bottle interior temperature falls after rise, emulsion temperature is adjusted into 78 ℃, and insulation 0.5h.Under uniform temp, drip the polymer monomer mixed liquor A of 2/3 remaining weight and the ammonium persulfate solution of 2/3 weight then with 1h.After dripping, continue insulation 1h.Polymerized emulsion is cooled to below 50 ℃, with ammoniacal liquor adjustment pH value to 7, promptly obtains containing amine copolymer thing emulsion.
(e) in (d) solution for preparing, add the 8g silver nitrate, stirred 4 hours down, make amido and Ag at 18 ℃
+Fully complexing makes silver-carrying antibiotic finishing agent.
Claims (11)
1. antibacterial finishing agent is characterized in that: this finishing agent is by containing amine copolymer thing emulsion and the silver salt complexing forms, wherein, containing 128～346 parts of amine copolymer thing emulsions, 8～32 parts of silver salt.
2. antibacterial finishing agent according to claim 1 is characterized in that: containing amine copolymer thing emulsion is by comprising that at least thiazolinyl amine monomer, acrylic ester monomer, cross-linking monomer, emulsifying agent, initator, deionized water make through emulsion polymerisation process.
3. antibacterial finishing agent according to claim 1 is characterized in that: described silver salt is a silver nitrate.
4. antibacterial finishing agent according to claim 2 is characterized in that: thiazolinyl amine monomer comprises one or more the combination in alkenyl amine, diallylamine, the triallylamine.
5. antibacterial finishing agent according to claim 2 is characterized in that: acrylic ester monomer comprises one or more the combination in acrylic acid, methacrylic acid, methyl methacrylate, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, hydroxy propyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxy butyl ester, the own ester of acrylic acid hydroxyl, the 2-EHA.
6. antibacterial finishing agent according to claim 2 is characterized in that: described cross-linking monomer comprises one or more the combination in oneself two hydrazines of diacetone acrylamide/adipic acid, gamma-methyl allyl acyloxypropyl trimethoxysilane, acryloyl-oxy propyl trimethoxy silicane, gamma-methyl allyl acyloxypropyl three second methoxy silane, acryloyl-oxy propyl-triethoxysilicane, gamma-methyl allyl acyloxypropyl three isopropoxy silane, acryloyl-oxy propyl group three isopropoxy silane, the methyl propenoic acid glycidyl ether.
7. antibacterial finishing agent according to claim 2 is characterized in that: described initator comprises one or more combinations in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, the benzoyl peroxide.
8. antibacterial finishing agent according to claim 1, it is characterized in that, described emulsifying agent is made up of non-ionic surface active agent, anion surfactant and low mass molecule alcohol compounds, and wherein anion surfactant is that lauryl sodium sulfate, alkyl number are one or both in 8～9 the alkyl phenol ether sulfosuccinic acid ester sodium salt; Non-ionic surface active agent is that fatty alcohol-polyoxyethylene ether, the alkyl number of molecular weight 400～800 is 8～9 alkylphenol polyoxyethylene and in the polyethylene glycol one or more, and the low mass molecule alcohol compounds is a glycerine.
9. antibacterial finishing agent according to claim 6, it is characterized in that in emulsifying agent, the weight of anion surfactant is 2～8 parts by umber, the weight of non-ionic surface active agent is 4～14 parts by umber, and the weight of low mass molecule alcohol compounds is pressed 1～5 part of umber.
10. antibacterial finishing agent according to claim 2, it is characterized in that: wherein thiazolinyl amine monomer consumption is 15～28 parts by umber, the acrylic ester monomer consumption is 80～200 parts by umber, amount ofthe cross-linking monomer is 3～12 parts by umber, the consumption of emulsifying agent is 5～20 parts by umber, and initiator amount is 0.2～0.5 part by umber, and the deionized water consumption is 400～700 parts by umber, the silver salt consumption is 8～17 parts by part, and described consumption is weight.
11. the preparation method of a kind of antibacterial finishing agent according to claim 1, its concrete steps are as follows:
A, in reactor, add 5～20 parts of emulsifying agents and 350～610 parts of water, heat up, stir, treat emulsifiers dissolve, be cooled to below 50 ℃;
B, 40～80 parts of acrylic ester monomers of adding, 15～28 parts of thiazolinyl amine monomers, emulsification 40min, add 0.07～0.15 part of initator, initator is warming up to 60～65 ℃ of initiation reactions with 20～40 parts of water-soluble, carrying out along with polymerisation, reaction temperature rises to 70～85 ℃ gradually, and the reaction time is 2～3h, and emulsion presents light blue;
After c, question response temperature in the kettle fall after rise, emulsion temperature is adjusted into 70 ℃, and insulation 0.5h;
D, under 70～75 ℃ of temperature, drip 40～120 parts of acrylic ester monomers then, 3～12 parts of cross-linking monomers, and 0.13～0.35 part of initator, initator is with 30～50 parts of water-soluble, the dropping time is 1～1.5h, drips follow-up continuation of insurance temperature 1h, is cooled to below 50 ℃, regulate pH value to 7 with ammoniacal liquor, promptly obtain containing amine copolymer thing emulsion.
E, in containing amine copolymer thing emulsion, add 8～32 parts of silver nitrates, stirred 2～4 hours down, make silver-carrying antibiotic finishing agent at 16～25 ℃.
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| CN103710965A (en) * | 2013-12-28 | 2014-04-09 | 杭州泛林科技有限公司 | Preparation method of natural silk functional textile |
| CN103741469A (en) * | 2013-11-08 | 2014-04-23 | 绍兴鼎翔纺织品贸易有限公司 | Antibiotic finishing agent |
| CN103881035A (en) * | 2013-11-08 | 2014-06-25 | 绍兴鼎翔纺织品贸易有限公司 | Anti-bacterial finishing agent for fabric |
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| CN103881035A (en) * | 2013-11-08 | 2014-06-25 | 绍兴鼎翔纺织品贸易有限公司 | Anti-bacterial finishing agent for fabric |
| CN103710965A (en) * | 2013-12-28 | 2014-04-09 | 杭州泛林科技有限公司 | Preparation method of natural silk functional textile |
| CN103710965B (en) * | 2013-12-28 | 2015-12-02 | 杭州泛林科技有限公司 | A kind of preparation method of natural silk functional textile |
| CN105111725B (en) * | 2015-09-23 | 2017-08-25 | 福建越特新材料科技有限公司 | A kind of antimicrobial form anion flexible polyurethane foams and preparation method thereof |
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| CN105463829A (en) * | 2016-01-12 | 2016-04-06 | 中山市绿浪助剂有限公司 | Oily textile finishing antibacterial auxiliary |
| CN105670043A (en) * | 2016-03-21 | 2016-06-15 | 苏州越湖海绵复合厂 | Nanometer antibacterial insole material and method for preparing same |
| CN106120337A (en) * | 2016-07-01 | 2016-11-16 | 潘明华 | A kind of environment-friendly type stiffening agent and preparation method thereof |
| CN107164961A (en) * | 2017-06-23 | 2017-09-15 | 华娜 | A kind of antibacterial finishing agent used for textiles and its production and use |
| CN108517695A (en) * | 2018-07-13 | 2018-09-11 | 合肥洁诺医疗用品有限公司 | A kind of medical non-woven fabrics complex antimicrobials |
| CN108517694A (en) * | 2018-07-13 | 2018-09-11 | 合肥洁诺医疗用品有限公司 | It is a kind of medical treatment paving non-woven fabrics is applied alone |
| CN109021477A (en) * | 2018-07-20 | 2018-12-18 | 张家港市六福新材料科技有限公司 | A kind of preparation method of argentiferous polyester anti-biotic material |
| CN111485422A (en) * | 2020-04-17 | 2020-08-04 | 苏州丝之源纺织科技有限公司 | Anti-mite antibacterial finishing agent and finishing method and application thereof |
| CN112726219A (en) * | 2020-12-28 | 2021-04-30 | 广东广油华丰科技研究有限公司 | Emulsion containing nano cuprous oxide/copper oxide/silver oxide for non-woven fabric and application thereof |
| CN114685714A (en) * | 2020-12-29 | 2022-07-01 | 上海朗亿功能材料有限公司 | Modified polymer, antibacterial composition, preparation method, fabric finishing and application |
| CN114685714B (en) * | 2020-12-29 | 2023-09-22 | 上海朗亿功能材料有限公司 | Modified polymer, antibacterial composition, preparation method, textile finishing and application |
| CN114753144A (en) * | 2022-04-26 | 2022-07-15 | 扬州锦茂新材料科技有限公司 | After-finishing method of high-color-stability antibacterial fabric |
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Application publication date: 20110713 |