CN100521943C - Inorganic/organic nano composite antibacterial agent and its fabric product application - Google Patents
Inorganic/organic nano composite antibacterial agent and its fabric product application Download PDFInfo
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Abstract
The invention relates to an inorganic/organic nano-composite antibacterial and application of fiber product thereof. 0.01-20 proportions of inorganic antibacterial, 0.01-35 proportions of organic antibacterial, 0.0001-0.4 proportion of inorganic/organic antibacterial compatibility finishing agent, 0.05-40 proportions of macromolecule bond, 0.0001-0.4 proportion of stabilizer that prevents color change of the inorganic antibacterial, 0.1-30 proportions of high efficiency emulsifying agent and 100 proportions of distilled water are added in sequence by weight proportion, wetted, dispersed, ground, dispersed at high-speed, stirred, etc., so as to acquire the nano-composite antibacterial. The antibacterial can process the fiber product by a dip-dye method, a roll-dye method, a spray method, etc. Dresses, socks and socks, blankets, beddings, gowns, patient wears, masks, medicinal gauzes, air filtering nettings, etc., made from the inorganic/organic nano-composite antibacterial of the invention are characterized by high antibacterial efficiency, rapid antibacterial function, long lasting antibacterial performance, laundering durability, etc., and the inorganic/organic nano-composite antibacterial of the invention is applicable to life, medical care, etc., and has the functions of preventing the occurrence and transmission of diseases, protecting the health of people and improving life quality.
Description
Technical field:
The present invention relates to a kind of inorganic/organic nano composite antibacterial agent, particularly rapid the and antibiotic property of antibacterial action endurable inorganic/organic nano composite antibacterial agent and the application in fibre thereof.
Background technology:
Antibiotic be meant to have suppress and action of microorganisms such as kill bacteria, comprise sterilization, antibacterial, sterilization, sterilization, mildew-resistant, anticorrosion etc. acting on (the new function plastic additive, chapter 2, antibacterial agent, 2003:25).Antibacterial agent is the extremely responsive material of microorganism, and minute quantity promptly can play the effect that suppresses growth of microorganism and kill microorganisms.Antibacterial agent is applied to fibre, can process to make antibacterial fiber product.Antibacterial fiber product have kill that it touches and stick to microorganisms such as bacterium on the fabric, and/or suppress the performance of growth of microorganism breeding.
The mankind have just used antimicrobial agent from ancient times.Just have in early days in China and to utilize the plant maceration extract to make the deed record that antimicrobial article carries out antibiotic diseases prevention.German army has begun the practicability (modern industry 1998 (4): 54) of modern anti-biotic material owing to wearing the bacterial infection that has reduced the wounded through the military uniform of antibiotic processing in the World War II.
Antibacterial agent mainly includes machine antibacterial agent, inorganic antiseptic, natural antibacterial agent (containing the Chinese medicine extract) three major types.Natural antibacterial agent derives from natural organic-compound or natural minerals mostly, therefore can also distinguish merger in organic antibacterial agent and inorganic antiseptic.Because the antibacterial action mechanism difference of various antibacterial agents, its antibiotic behavior and effect that shows also is not quite similar.For example, the antibacterial agent that has has quick-acting bactericidal actions, as: iodine, alcohol, oxirane, so be usually used in sterilization and sterilization; The antibacterial agent that has has lasting antibiotic stability, and its lasting effect is several months, several years until many decades, as triclosan, silver base inorganic antibacterial agent, zinc oxide, thus be used for the production of embedded type anti-biotic material and goods, as antibiotic plastic, anti-bacteria ceramic.
It is rapid that organic antibacterial agent generally has an antibacterial action, the advantage that antimicrbial power is strong, but fast, the antibiotic term of validity of stripping is lacked (poor durability), weather resistance is relatively poor, antibiotic stability is lower, and the part antibacterial agent is big to skin irritation, antimicrobial spectrum is narrower, and chronic administration also may cause the appearance of antibody-resistant bacterium.Inorganic antiseptic is the compound of inorganic carried silver, zinc, copper ion mostly, belongs to the antibiotic mechanism of non-stripping property, and the antibiotic term of validity is long, has a broad antifungal spectrum, little to skin irritation, but the antibacterial action onset is later, and the minimal inhibitory concentration value to fungi is bigger, and antimycotic efficient is lower.But the nanometer grade inorganic antibacterial agent that develops rapidly is in recent years improved a lot than the antimicrbial power of common inorganic antiseptic.
In many occasions of daily life, people need and wish to use to have good, the safe and harmless fibre of anti-microbial property, as textile, mouth mask, carpet etc. on underwear, the bed.Also have, particularly in places such as hospitals, the antibacterial fiber product that antimicrbial power is strong, quick-acting, anti-microbial property is durable, washable, safe is the good articles for use that prevent patient's nosocomial infection and protection medical worker health.
When using the antibacterial agent preparation to have the fibre of anti-microbial property, existing manufacture method mainly contains following two technology paths.One, in the processing antibacterial agent is fused into (or dissolving in) fibrous polymeric materials inside, i.e. blending antibacterial agent and it is retained in the polymeric matrix in fibre-forming polymer, the kinds of fibers of being produced comprises antibiotic polypropylene fibre (96118358.6 1 kinds of bacteriostatic PP fibers of Chinese invention patent and manufacture method thereof), antibacterial dacron (Chinese invention patent application 01113772.X nano Polyester short fibre and manufacture method thereof), antibacterial viscose fiber (manufacturing process and the goods of Chinese invention patent 02160199.2 modified chitin-chitosan and viscose spinning dope intermingling material), be called the spinning antimicrobial technology, be mainly used in the manufacturing of antibacterial synthetic.Two, antibacterial agent is put on the superficial layer of fiber, promptly infiltrate into the top layer of fiber certain depth, or adhere to the surface of fiber, to keep coexisting of itself and fiber, thereby also make fiber have the antibiotic property of certain enduring quality, be called back arrangement antimicrobial technology, can be applicable to nearly all fibre, comprise that (Chinese invention patent 01807542 is used for the antibacterial agent and the antibiotic property textile of fiber for natural fibre products and synthetic fibers goods, 01815672.X the antibacterial processing method of fibrous material, the processing method of 02104252.7 product of functional animal fiber knitted down and product).
When adopting back arrangement antimicrobial technology to prepare antibacterial fiber product, the easy leachability of organic antibacterial agent causes its antibiotic timeliness short, though can partly remedy not enough this problem of antibiotic chronicity that runs off and bring and strengthen the organic antibacterial agent consumption, incident is that too high antibiotic dosage has certain threat to human safety.Organic antibacterial agent also has the shortcoming of degradation failure under environmental condition.The inorganic antiseptic onset is slow, generally needs to act on bacterium through a few hours, just can show antibacterial effect, can not satisfy the requirement of quick sterilization.
Be understood that,, bring into play both advantages separately, might prepare high performance antibacterial fiber product by using inorganic antiseptic and organic antibacterial agent simultaneously.Chinese patent application 200410067284 discloses a kind of polycomponent fiber product composite nano antibacterial agent, and its component comprises reactive organic antibacterial agent, nano inorganic antimicrobial agent, cation dispersion aids, distilled water.It is said that with the underwear of this antiseptic prescription arrangement, antibiotic persistence and washing fastness are good.Antibacterial underwear is through washing front and back 100 times, and the antibiotic rate that contacts with Escherichia coli, staphylococcus aureus, Candida albicans after 24 hours can reach respectively more than 99.99% and 99%.But this invention does not relate to the quick-acting antibiotic and sterilizing performances of this complex antimicrobials and antibiotic finish fabric thereof.
In addition, for the anti-microbial property that the fibre that makes the back arrangement in use maintains a long-term stability, people study and use adhesive to solve the loss of antibacterial agent and the problem that comes off.But adhesive has often weakened the antibacterial effect of antibacterial agent, makes the anti-microbial property of anti-bacterial fibre fabric relatively poor.This just needs comprehensively to solve by reasonably filling a prescription, and keeps the performance of antibacterial agent well to be brought into play.
The present invention adopts the antibiotic finish technology, utilization inorganic antiseptic/organic antibacterial agent complex technique, constitute by rational antiseptic prescription, prepared efficient quick-acting composite nano germicide, and then realized antibioticization of fibre making fibre have the antibiotic quick-acting and antibiotic premium properties of holding effect concurrently.
Summary of the invention:
Inorganic/component that the organic nano composite antibacterial agent prescription is comprised of the present invention " a kind of inorganic/organic nano composite antibacterial agent and fibre thereof use " is:
Inorganic antiseptic: 0.01-20 part, organic antibacterial agent: 0.01-35 part, the compatible inorganic agent of inorganic/organic antibacterial agent: 0.0001-0.4 part, polymer binder: 0.05-40 part, the stabilizing agent of anti-inorganic antiseptic variable color: 0.0001-0.4 part, efficient emulsifier: 0.1-30 part, distilled water: 100 parts.
Described inorganic antiseptic is zeolite with carrying silver, copper-loaded zeolite, carries the zinc zeolite, carries the silver-bearing copper zeolite, carries silver-colored zinc zeolite, copper-loaded zinc zeolite; Silver-loaded zirconium phosphate, copper-loaded basic zirconium phosphate, year zinc basic zirconium phosphate, year silver-bearing copper basic zirconium phosphate, year silver-colored zinc basic zirconium phosphate, copper-loaded zinc basic zirconium phosphate; Carry silver-colored calcium phosphate, copper-loaded calcium phosphate, carry zinc calcium phosphate, carry silver-bearing copper calcium phosphate, carry silver-colored zinc calcium phosphate, copper-loaded zinc calcium phosphate; Carry silver-colored titanium phosphate, copper-loaded titanium phosphate, carry the zinc titanium phosphate, carry the silver-bearing copper titanium phosphate, carry silver-colored zinc titanium phosphate, copper-loaded zinc titanium phosphate; Carry silver-colored silica gel, copper-loaded silica gel, carry zinc silica gel, carry silver-bearing copper silica gel, carry silver-colored zinc silica gel, copper-loaded zinc silica gel; Carry silver-colored titanium dioxide, copper-loaded titanium dioxide, carry zinc titanium dioxide, carry silver-bearing copper titanium dioxide, carry silver-colored zinc titanium dioxide, copper-loaded zinc titanium dioxide; Carry silver-colored imvite, copper-loaded imvite, carry the zinc imvite, carry the silver-bearing copper imvite, carry silver-colored zinc imvite, copper-loaded zinc imvite; Carry the Ag-Cu-Zn soluble glass; Carry the Ag-Cu-Zn active carbon, or their two or more mixtures wherein.
Described organic antibacterial agent is a dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, the myristyl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzene oxygen ethyl ammonium bromide, myristyl-2-picoline ammonium bromide, cetyl pyridinium ammonium chloride, the cetyl pyridinium ammonium bromide, the two octyl group ammonium chlorides of dimethyl, the two octadecyl ammonium chloride of dimethyl, hexadecyltrimethylammonium chloride, OTAC, diisobutyl benzene oxygen ethyl dimethyl benzyl ammonium chloride, 3-(trimethoxy silylation) propyl group octadecyl alkyl dimethyl ammonium chloride, the lauryl amine ethyl glycine, 2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-n-octyl-4-isothiazoline-3-ketone, 4,5-two chloro-2-n-octyls-4-isothiazoline-3-ketone, 1, the 2-benzisothiazole-3-ketone, 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ethers, 2-(4-thiazolyl) benzimidazole, 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene, β-1,4-dextran amine (chitosan), 10,10 '-oxo Shuan phenoxazine, 2,4,5,6-tetrachloro-1,3-benzene dicarbonitrile, benzimidazolyl-2 radicals-methoxyl group methyl carbamate, 2-(4-thiazolyl) benzimidazole, hexamethylene, 1,6-two (just-to the chlorobenzene biguanides) hexane, or their two or more mixtures wherein.
Described inorganic/the compatible inorganic agent of organic antibacterial agent is silane coupler, titanate coupling agent, aluminate coupling agent, boric acid ester coupler, epoxy resin, and their two or more mixtures wherein.As, r-chloropropyl trimethoxyl silane, perfluoro n-heptyl methyl ether propyl-triethoxysilicane, perfluor isopropyl ether MTMS, MTMS, ethyl triethoxysilane, VTES, vinyltrimethoxy silane, propyl methacrylate base trimethoxy silane, N-amine ethylamine oxypropyl trimethyl silane, vinyl benzyl amine ethylamine propyl trimethoxy silicane hydrochloride, methyl chloride ethyl acrylate base dimethyl amido propyl trimethoxy silicane, the tolyl trimethoxy silane, the amine propyl trimethoxy silicane, toluene bromide base trimethoxy silane, epoxy propyl ether propyl trimethoxy silicane, the epoxycyclohexyl ethyl trimethoxy silane, phenyltrimethoxysila,e, mercaptopropyl trimethoxysilane, to the chlorobenzene ethyl trimethoxy silane, the bromophenyl trimethoxy silane, isopropyl three different hydroxyl acyl titanate esters, isopropyl three (dodecyl benzene sulfonyl) titanate esters, isopropyl three (dioctylphyrophosphoric acid ester) titanate esters, two (dioctyl phosphite ester) titanate esters of tetra isopropyl, two (two (dodecyl) phosphite ester) titanate esters of four octyl groups, four (2,2-two allyloxys-1-butyl) two (two (tridecyl) phosphite ester) titanate esters, two (dioctylphyrophosphoric acid ester) fluoroacetic acid ester titanate esters, isopropyl stearoyl two acryloyl titanate esters, isopropyl three (dioctyl phosphate) titanate esters, isopropyl two (dodecyl benzene sulfonyl)-4-amino-benzene sulfonyl titanate esters, isopropyl three (methacryl) titanate esters, dilauryl phosphorite type titanate esters, isopropyl stearoyl two (4-aminobenzoyl) titanate esters, isopropyl three acryloyl titanate esters, ethylene glycol boric acid monooctyl ester, stearoyl boric acid glycol ester, epoxy 628, epoxy E-51,1050,1051,4051, PEO, poly(propylene oxide), and their two or more mixtures wherein.
Described polymer binder is acrylic resin, the resinoid aqueous emulsion of polyurethane, and their two or more mixtures wherein.
The stabilizing agent of described anti-inorganic antiseptic variable color is sodium thiosulfate, potassium thiosulfate, sodium silicate, silicon potash fertilizer, waterglass, ammonia, fatty amine, aromatic amine, acrylic acid, methacrylic acid, and their two or more mixtures wherein.
Described efficient emulsifier is the APEO type, ester type nonionic emulsifier, the synthetic high polymer surfactant, natural polymeric surface active agent, as sorbitan mono-laurate (SPAN-20), anhydrous sorbitol monopalmitate (SPAN-40), sorbitan monostearate (SPAN-60), anhydrous sorbitol tristearate (SPAN-65), sorbitan monooleate (SPAN-80), sorbitan sesquioleate (SPAN-83), sorbitan trioleate (SPAN-85), (addition of ethylene oxide is counted n=20 to SPAN-20 ethylene oxide adduct (TWEEN-20), down together), SPAN-40 ethylene oxide adduct (TWEEN-40), SPAN-60 ethylene oxide adduct (TWEEN-60), SPAN-80 ethylene oxide adduct (TWEEN-80), SPAN-85 ethylene oxide adduct (TWEEN-85), SPAN-81 ethylene oxide adduct (TWEEN-81) (addition of ethylene oxide is counted n=5), polyox-yethylene-polyoxypropylene block copolymer, the benzyl phenyl APEO, styryl phenyl APEO, gelatin, and their two or more mixtures wherein.
The present invention is inorganic/and organic nano composite antibacterial agent follows these steps to preparation:
Be inorganic antiseptic 0.01-20 part of 20nm-15 μ m and stabilizing agent 0.0001-0.4 part of anti-inorganic antiseptic variable color with particle diameter earlier, moistening dispersion in 100 parts of distilled water, agitation grinding; Add the compatible inorganic agent 0.0001-0.4 of inorganic/organic antibacterial agent part, continue to grind; It is some to add organic antibacterial agent 0.01-35 part, filler etc., grinds again; Add efficient emulsifier 0.1-30 part, high speed dispersion; Add polymer binder 0.05-20 part, stir into stable suspension and emulsion mixture.The inorganic antiseptic particle surface has covered organic matter, and this surface coating also contains a certain amount of organic antibacterial agent simultaneously.Like this, inorganic antiseptic has reached the fine dispersion based on its particle size.Simultaneously, organic antibacterial agent is through grinding refinement, or through microemulsified, reaches nano-grade size, forms nano-complex.
Of the present invention inorganic/application method of organic nano antibacterial agent in fibre have dip method, pad dyeing method, spraying process etc., be described below respectively:
1, dip method: the first dyeing and finishing technology routinely of pending fabric is carried out preceding road handle, promptly float, dye, or select the useful fiber fabric substrate.Then, it is 1:15 to 1:40 that the adjustment water yield makes bath raio, bathes warm 40-95 ℃.Simultaneously, get a certain amount of inorganic/organic nano composite antibacterial agent, available in case of necessity a small amount of soft water is dilution earlier, and is disposable then or divide and add in the balneation for 2-5 time, stirred 2-30 minute, and antibacterial agent is fully contacted with fabric, reaches even combination.At last, will bathe temperature drop after 20-40 ℃, dry, the weight of antibacterial agent in fabric finally by the 0.1-7% of processing fabric weight.
If needed, this antibiotic fabric also can continue to do soft finish.Shaping and drying.
2, pad dyeing method: the first dyeing and finishing technology routinely of pending fabric is carried out preceding road handle, promptly float, dye, or select the useful fiber fabric substrate.Then, with this fabric by containing of preparing in advance above-mentioned inorganic/antibiotic finish of organic nano composite antibacterial agent 2-70g/1 bathes.Bathe warm 40-95 ℃, pick-up is 110%-40%.Oven dry.In case of necessity, also can pad secondary or repeatedly, to meet the requirements of antibacterial agent binding capacity and anti-microbial property.Shaping and drying.
3, spraying process: the first dyeing and finishing technology routinely of pending fabric is carried out preceding road handle, promptly float, dye, or select the useful fiber fabric substrate.Then, with using distilled water diluting 5-200 above-mentioned inorganic/organic nano composite antibacterial agent doubly in advance, use the high-pressure atomization spray gun, evenly spray this antibacterial agent on the fabric face of stent, typing is dry.The antibacterial agent dry weight accounts for the 0.1-4.0% of fibre dry weight.
The present invention is directed to preparation and have antibiotic quick-acting and antibiotic inorganic/organic nano composite antibacterial agent and this requirement of antibacterial fiber product thereof of imitating these two big characteristics of holding concurrently, made up inorganic/organic antibacterial agent compound prescription.Contain the stabilizing agent of inorganic antiseptic, organic antibacterial agent, the compatible inorganic agent of inorganic/organic antibacterial agent, polymer binder, anti-inorganic antiseptic variable color, efficient emulsifier, water etc. in this antiseptic prescription, each component synergy, thereby satisfy each compatibility between components and matching, given full play to inorganic antiseptic and the organic antibacterial agent advantage separately in prescription.
The present invention selects the nanometer technology preparation to be used for the high-performance inorganic/organic composite antibiotic agent of fibre antimicrobial treatment.This technical characterstic is, uses or processing and preparing goes out particle diameter and is inorganic antiseptic below the 100nm and/or organic antibacterial agent as recipe ingredient, and realizes fine dispersion.With this inorganic/organic composite antibiotic agent that the nanometer state exists, its antibiotic quick-acting excellent performances are much higher than the antibiotic quick-acting performances of micron particles.
Applying nano technology of the present invention improves another angle of antibiotic quick-acting performances, is the microemulsion that has prepared nano-grade size.Because small-size effect, antibiotic quick-acting performances are good.
The present invention realizes good long-lasting of complex antimicrobials, the one, by in prescription, using long-lasting good inorganic antiseptic; The 2nd,, of the present invention inorganic/the formed antibiotic microemulsion of organic anti-bacterial agent prescription, be applied to form antibiotic microcapsules behind the fibre.These microcapsules have slow releasing function, make the dissolution rate of organic antibacterial agent component controlled, reach long-acting.
The present invention is to the discoloration problem of inorganic antiseptic, adopt the stabilizing agent of anti-variable color to be controlled, prevent because the oxidisability of the silver ion that contained chemical activity is high in the antibacterial agent causes the variable color of antibacterial agent and antibacterial fiber product thereof, and influence the products appearance quality and anti-microbial property low.
Of the present invention inorganic/organic nano composite antibacterial agent, when fibre is carried out antimicrobial treatment, can use technical applications such as dip-dye, pad dyeing, spraying respectively, manufacturability is good, realize good antibacterial fiber product outward appearance, finally obtained the fibre of high-quality inorganic/organic nano composite antibacterial agent arrangement.
The present invention also can adopt antibiotic finish and the antibiotic spinning technology of combining to be implemented, and promptly a kind of antibacterial agent or complex antimicrobials can be built in the synthetic fibers by spinning technique earlier, then the anti-bacterial fibre that generates with antibiotic finish technology arrangement spinning.This not only can overcome two class antibacterial agents weakness separately, reaches excellent comprehensive performances, and can further reduce the degree that antibacterial agent comes off, and it is longer to hold effect.
The antibacterial fiber product that the present invention obtains has excellent comprehensive performances such as safe, washable, durable.
The material category of the antibacterial fiber product of the present invention preparation comprises one or more blending, mixed fabric of synthetic fibers such as native fiber such as cotton, hair, real silk, fiber crops, polypropylene fibre, terylene, nylon, polyethylene fibre, viscose rayon.
The fabric types of the antibacterial fiber product of the present invention's preparation comprises yarn, wool top, woven, knitted fabric, nonwoven, porous membrane etc.
The antibacterial fiber product of the present invention's preparation comprises interior outerwear trousers, sportswear, socks, shoe-pad, gloves, muffler, cap, carpet, curtain, the tablecloth, shower curtain, bedding, seat cushion, automotive trim fabric, mouth mask, hospital gauze, the medical cloth that stretches tight, operation dress, curative activity clothes, johnny, airstrainer, diaper, sanltary towel etc.
Embodiment:
Embodiment 1 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add 10g1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 1# inorganic/organic nano composite antibacterial agent.
Embodiment 2 with heavy 6g silver content be 3.0%, zinc content is 8.0%, average grain diameter is 1.2 μ m, maximum particle diameter is less than the silica gel type inorganic antiseptic of 5 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, improve rotating speed, grind 5min to 3000rpm.Add 10g1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material after this grinds, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky white suspension at 100rpm, obtain 2# inorganic/organic nano composite antibacterial agent.
Embodiment 3 with heavy 6g silver content be 3.1%, average grain diameter is 3 μ m, maximum particle diameter is less than the soluble glass type inorganic antiseptic of 10 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 1mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, improve rotating speed, grind 5min to 3000rpm.Add 10g 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material after this grinds, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky white suspension at 100rpm, obtain 3# inorganic/organic nano composite antibacterial agent.
Embodiment 4 with heavy 3g silver content be 2.5%, primary particle diameter mean value is 20nm TiO 2 carrying silver type inorganic antiseptic, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add 10g 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 4# inorganic/organic nano composite antibacterial agent.
Embodiment 5 with heavy 6g copper content be 6.0%, zinc content is 12.0% copper-loaded zinc imvite type inorganic antiseptic, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, improve rotating speed, grind 5min to 3000rpm.Add 10g 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material after this grinds, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky white suspension at 100rpm, obtain 5# inorganic/organic nano composite antibacterial agent.
Embodiment 6 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add 10g 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ethers, grind 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 6# inorganic/organic nano composite antibacterial agent.
Embodiment 7 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add 10g2-n-octyl-4-isothiazoline-3-ketone, grind 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 7# inorganic/organic nano composite antibacterial agent.
Embodiment 8 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add 10g 4,5-two chloro-2-n-octyls-4-isothiazoline-3-ketone grind 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 8# inorganic/organic nano composite antibacterial agent.
Embodiment 9 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add 2g 10,10 '-oxo Shuan phenoxazine grinds 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 9# inorganic/organic nano composite antibacterial agent.
Embodiment 10 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add 10g benzimidazolyl-2 radicals-methoxyl group methyl carbamate, grind 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0,5g TWEEN-80 disperses 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 10# inorganic/organic nano composite antibacterial agent.
Embodiment 11 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add the 25g dodecyl benzyl dimethyl ammonium chloride, 5g 1, and two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 15g aqueous polyurethane emulsion UR309 (Wenzhou City whole world macromolecular material Co., Ltd), stir 10min, become milky suspension liquid at 100rpm, obtain 11# inorganic/organic nano composite antibacterial agent.
Embodiment 12 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add the 25g dodecyl benzyl dimethyl ammonium chloride, 5g2,4,4 '-three chloro-2 '-dihydroxy diphenyl ethers grind 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 15g aqueous polyurethane emulsion UR309 (Wenzhou City whole world macromolecular material Co., Ltd), stir 10min, become milky suspension liquid at 100rpm, obtain 12# inorganic/organic nano composite antibacterial agent.
Embodiment 13 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add the 25g dodecyl benzyl dimethyl ammonium chloride, 5g2-n-octyl-4-isothiazoline-3-ketone grinds 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 15g aqueous polyurethane emulsion UR309 (Wenzhou City whole world macromolecular material Co., Ltd), stir 10min, become milky suspension liquid at 100rpm, obtain 13# inorganic/organic nano composite antibacterial agent.
Embodiment 14 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add the 25g dodecyl benzyl dimethyl ammonium chloride, 5g4,5-two chloro-2-n-octyls-4-isothiazoline-3-ketone grind 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5gTWEEN-80, disperse 5min at 4000rpm.Add 15g aqueous polyurethane emulsion UR309 (Wenzhou City whole world macromolecular material Co., Ltd), stir 10min, become milky suspension liquid at 100rpm, obtain 14# inorganic/organic nano composite antibacterial agent.
Embodiment 15 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add the 25g dodecyl benzyl dimethyl ammonium chloride, 5g 10, and 10 '-oxo Shuan phenoxazine grinds 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 15g aqueous polyurethane emulsion UR309 (Wenzhou City whole world macromolecular material Co., Ltd), stir 10min, become milky suspension liquid at 100rpm, obtain 15# inorganic/organic nano composite antibacterial agent.
Embodiment 16 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding the 0.05g silicon potash fertilizer, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Add 10g 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 16# inorganic/organic nano composite antibacterial agent.
Embodiment 17 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding the 0.05g silicon potash fertilizer, add 100ml distilled water, grind 5min at 2000rpm.Add two (dioctylphyrophosphoric acid ester) the fluoroacetic acid ester titanate esters of 0.05g, and improve rotating speed, grind 5min to 3000rpm.Add 10g1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 17# inorganic/organic nano composite antibacterial agent.
Embodiment 18 with heavy 6g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding the 0.05g silicon potash fertilizer, add 100ml distilled water, grind 5min at 2000rpm.Add two (dioctylphyrophosphoric acid ester) the fluoroacetic acid ester titanate esters of 0.05g, and improve rotating speed, grind 5min to 3000rpm.Add 10g 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add the 0.5g polyox-yethylene-polyoxypropylene block copolymer, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid at 100rpm, obtain 18# inorganic/organic nano composite antibacterial agent.
Embodiment 19 with heavy 20g silver content be 3.0%, zinc content is 8.0%, average grain diameter is 1.2 μ m, maximum particle diameter is less than the silica gel type inorganic antiseptic of 5 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.05g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, improve rotating speed, grind 5min to 3000rpm.Add the 5g nanometer grade calcium carbonate, 3000rpm grinds 5min.Add 4g 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are ground 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material after this grinds, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 30g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky white suspension at 100rpm, obtain 19# inorganic/organic nano composite antibacterial agent.
Embodiment 20 with heavy 0.1g silver content be 3.0%, zinc content is 8.0%, average grain diameter is 1.2 μ m, maximum particle diameter is less than the silica gel type inorganic antiseptic of 5 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.05g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, improve rotating speed, grind 5min to 3000rpm.Add 10g 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene, 10g2,4,4 '-three chloro-2 '-dihydroxy diphenyl ethers, 15g 2-n-octyl-4-isothiazoline-3-ketone grinds 5min at 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material after this grinds, add 1.5g TWEEN-80, disperse 5min at 4000rpm.Add 40g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky white suspension at 100rpm, obtain 20# inorganic/organic nano composite antibacterial agent.
Reference examples 1 with heavy 10g silver content be 3.5%, primary particle diameter mean value is that 35nm, the apparent average grain diameter of aggregate are the basic zirconium phosphate type inorganic antiseptic of 1.6 μ m, move in the 150ml body of stainless steel of liner polyurethane resin of sand mill in the bucket.Be placed with the 100g zirconium oxide bead of Φ 0.5mm in this barrel in advance.After adding 0.003g sodium thiosulfate, add 100ml distilled water, grind 5min at 2000rpm.Add 0.05g N-amine ethylamine oxypropyl trimethyl silane, and improve rotating speed, grind 5min to 3000rpm.Isolate zirconium oxide bead with 325 mesh sieves.Then, in the mixing material that sieves, add 0.5g TWEEN-80, disperse 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid, obtain 1# contrast antibacterial agent (inorganic antiseptic) at 100rpm.
Reference examples 2 in the bucket, is placed with the 100g zirconium oxide bead of Φ 0.5mm in advance in the 150ml body of stainless steel of the liner polyurethane resin of sand mill.Add 100ml distilled water, add 0.5g TWEEN-80, add 10g1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene are disperseed 5min at 4000rpm.Add 10g polyacrylate emulsion HB959 (mutual beneficial chemical plant, Beijing), stir 10min, become milky suspension liquid, obtain 2# contrast antibacterial agent (organic antibacterial agent) at 100rpm.
Dip method:
It is 105g/m that embodiment 21 gets 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing, in centrifuge, dewater, wet cloth heavily is 200g.Earlier with 120g 1# inorganic/organic nano composite antibacterial agent slowly adds in the 5000ml beaker that fills 3000ml soft water, 50 ℃ of water temperatures stir.The cloth that will wet is put into beaker, upset, 15min.After bathing temperature drop to 35 ℃, centrifugal dehydration, the cloth weight in wet base is 200g.Then, tentering, drying, typing in 105 ℃ of convection oven are 1# anti-bacteria cloth (white antibacterial cotton cloth).
It is 110g/m that embodiment 22 gets 100g thickness
2Nylon knitting cloth bleaching and dyeing processing, in centrifuge, dewater, wet cloth heavily is 160g.Earlier with 120g 1# inorganic/organic nano composite antibacterial agent slowly adds in the 5000ml beaker that fills 3000ml soft water, 50 ℃ of water temperatures stir.The cloth that will wet is put into beaker, upset, 15min.After bathing temperature drop to 35 ℃, centrifugal dehydration, the cloth weight in wet base is 160g.Then, tentering, drying, typing in 105 ℃ of convection oven are 2# anti-bacteria cloth (anti-bacteria nylon looped fabric).
It is 90g/m that embodiment 23 gets 100g thickness
265/35T/C polyester-cotton blend plain weave cloth bleaching and dyeing processing, in centrifuge, dewater, wet cloth heavily is 180g.Earlier with 120g1# inorganic/organic nano composite antibacterial agent slowly adds in the 5000ml beaker that fills 3000ml soft water, 50 ℃ of water temperatures stir.The cloth that will wet is put into beaker, upset, 15min.After bathing temperature drop to 35 ℃, centrifugal dehydration, the cloth weight in wet base is 180g.Then, tentering, drying, typing in 105 ℃ of convection oven are by 3# anti-bacteria cloth (antibiotic polyester-cotton blend plain weave cloth).
It is 105g/m that embodiment 24-embodiment 42 gets 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing, in centrifuge, dewater, wet cloth heavily is 200g.Respectively earlier with 120g 2#-20# inorganic/organic nano composite antibacterial agent slowly adds in the 5000ml beaker that fills 3000ml soft water, 50 ℃ of water temperatures stir.The cloth that will wet is put into beaker, upset, 15min.After bathing temperature drop to 35 ℃, centrifugal dehydration, the cloth weight in wet base is 200g.Then, tentering, drying, typing in 105 ℃ of convection oven are 4#-22# anti-bacteria cloth (white antibacterial cotton cloth).
It is 105g/m that reference examples 3 is got 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing, in centrifuge, dewater, wet cloth heavily is 200g.Then, in 105 ℃ of tenterings, drying, typing, be by blank cloth specimen 0# (the blank sample of white cotton).
It is 105g/m that reference examples 4 is got 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing, in centrifuge, dewater, wet cloth heavily is 200g.Earlier 120g 1# contrast antibacterial agent (pure inorganic antiseptic) is slowly added in the 5000ml beaker that fills 3000ml soft water, 50 ℃ of water temperatures stir.The cloth that will wet is put into beaker, upset, 15min.After bathing temperature drop to 35 ℃, centrifugal dehydration, the cloth weight in wet base is 200g.Then, tentering, drying, typing in 105 ℃ of convection oven are 1# contrast anti-bacteria cloth (white antibacterial cotton cloth).
It is 105g/m that reference examples 5 is got 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing, in centrifuge, dewater, wet cloth heavily is 200g.Earlier 120g 2# contrast antibacterial agent (pure organic antibacterial agent) is slowly added in the 5000ml beaker that fills 3000ml soft water, 50 ℃ of water temperatures stir.The cloth that will wet is put into beaker, upset, 15min.After bathing temperature drop to 35 ℃, centrifugal dehydration, the cloth weight in wet base is 200g.Then, tentering, drying, typing in 105 ℃ of convection oven are 2# contrast anti-bacteria cloth (white antibacterial cotton cloth).
The pad dyeing method:
It is 105g/m that embodiment 43 gets 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing, then, by contain 1# inorganic/antibiotic finish of organic nano composite antibacterial agent 50g/1 bathes, and bathes 55 ℃ of temperature, pick-up is 106%.Dry in 105 ℃ of convection oven, typing is 23# anti-bacteria cloth (white antibacterial cotton cloth).
It is 110g/m that embodiment 44 gets 100g thickness
2Nylon knitting cloth bleaching and dyeing processing, then, by contain 1# inorganic/antibiotic finish of organic nano composite antibacterial agent 50g/l bathes, and bathes 55 ℃ of temperature, pick-up is 80%.Dry in 105 ℃ of convection oven, typing is 24# anti-bacteria cloth (anti-bacteria nylon looped fabric).
It is 90g/m that embodiment 45 gets 100g thickness
265/35T/C polyester-cotton blend plain weave cloth bleaching and dyeing processing, then, by contain 1# inorganic/antibiotic finish of organic nano composite antibacterial agent 50g/l bathes, and bathes 55 ℃ of temperature, pick-up is 80%.Dry in 105 ℃ of convection oven, typing is by 25# anti-bacteria cloth (antibiotic polyester-cotton blend plain weave cloth).
It is 105g/m that reference examples 6 is got 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing, then, bathe by the antibiotic finish that contains contrast 1# antibacterial agent (pure inorganic antiseptic) 50g/l, bathe 55 ℃ of temperature, pick-up is 106%.Dry in 105 ℃ of convection oven, typing is 3# contrast anti-bacteria cloth (white antibacterial cotton cloth).
It is 105g/m that reference examples 7 is got 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing, then, bathe by the antibiotic finish that contains contrast 2# antibacterial agent (pure organic antibacterial agent) 50g/l, bathe 55 ℃ of temperature, pick-up is 106%.Dry in 105 ℃ of convection oven, typing is 4# contrast anti-bacteria cloth (white antibacterial cotton cloth).
Spraying process:
It is 105g/m that embodiment 46 gets 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing.Then, with the 1# that uses 50 times of distilled water dilutings in advance inorganic/organic nano composite antibacterial agent, use the high-pressure atomization spray gun, even this antibacterial agent of spraying on the fabric face of stent.In 105 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 0.8% of textile cloth dry weight, is 26# anti-bacteria cloth (white antibacterial cotton cloth).
It is 110g/m that embodiment 47 gets 100g thickness
2Nylon knitting cloth bleaching and dyeing processing.Then, with the 1# that uses 50 times of distilled water dilutings in advance inorganic/organic nano composite antibacterial agent, use the high-pressure atomization spray gun, even this antibacterial agent of spraying on the fabric face of stent.In 105 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 0.8% of nylon knitting cloth dry weight, is 27# anti-bacteria cloth (anti-bacteria nylon looped fabric).
It is 90g/m that embodiment 48 gets 100g thickness
265/35T/C polyester-cotton blend plain weave cloth bleaching and dyeing processing.Then, with the 1# that uses 50 times of distilled water dilutings in advance inorganic/organic nano composite antibacterial agent, use the high-pressure atomization spray gun, even this antibacterial agent of spraying on the fabric face of stent.In 105 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 0.8% of polyester-cotton blend plain weave cloth dry weight, is by 28# anti-bacteria cloth (antibiotic polyester-cotton blend plain weave cloth).
It is 20g/m that embodiment 49 gets 100g thickness
2Polypropylene non-woven fabric.Then, with the 1# that uses 50 times of distilled water dilutings in advance inorganic/organic nano composite antibacterial agent, use the high-pressure atomization spray gun, even this antibacterial agent of spraying on the fabric face of stent.In 105 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 1% of polypropylene non-woven fabric dry weight, is 29# anti-bacteria cloth (antibacterial polypropylene nonwoven).
Embodiment 50 gets the polyethylene making hole film that 100g thickness is 15 μ m.Then, with 1# inorganic/organic nano composite antibacterial agent uses 50 times of distilled water dilutings in advance, uses the high-pressure atomization spray gun, even this antibacterial agent of spraying on the wide film of stent surface.In 65 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 1% of polyethylene making hole film dry weight, is 30# anti-bacteria cloth (antibacterial polyethylene making hole film).
It is 105g/m that reference examples 8 is got 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing.Then, with the 1# contrast antibacterial agent (pure inorganic antiseptic) of 50 times of distilled water dilutings, use the high-pressure atomization spray gun, on the fabric face of stent, evenly spray this antibacterial agent in advance.In 105 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 0.8% of textile cloth dry weight, is 5# contrast anti-bacteria cloth (white antibacterial cotton cloth).
It is 105g/m that reference examples 9 is got 100g thickness
2Pure cotton knitting cloth carry out oxygen and float processing.Then, with the 2# contrast antibacterial agent (pure organic antibacterial agent) of 50 times of distilled water dilutings, use the high-pressure atomization spray gun, on the fabric face of stent, evenly spray this antibacterial agent in advance.In 105 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 0.8% of textile cloth dry weight, is 6# contrast anti-bacteria cloth (white antibacterial cotton cloth).
It is 20g/m that reference examples 10 is got 100g thickness
2Polypropylene non-woven fabric.Then, with the 1# contrast antibacterial agent (pure inorganic antiseptic) of 50 times of distilled water dilutings, use the high-pressure atomization spray gun, on the fabric face of stent, evenly spray this antibacterial agent in advance.In 105 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 1% of polypropylene non-woven fabric dry weight, is 7# contrast anti-bacteria cloth (antibacterial polypropylene nonwoven).
It is 20g/m that reference examples 11 is got 100g thickness
2Polypropylene non-woven fabric.Then, with the 2# contrast antibacterial agent (pure organic antibacterial agent) of 50 times of distilled water dilutings, use the high-pressure atomization spray gun, on the fabric face of stent, evenly spray this antibacterial agent in advance.In 105 ℃ of convection oven, dry, typing, the antibacterial agent dry weight accounts for 1% of polypropylene non-woven fabric dry weight, is 8# contrast anti-bacteria cloth (antibacterial polypropylene nonwoven).
Decantation test: with reference to State Standard of the People's Republic of China GB8629-88 " home washings and the drying program that adopt during the textile test " (this standard adopting by reference international standard ISO 6330-1984 " textile---the home washings and the drying program that adopt during test " formulation) regulation, select Type B agitating type washing machine and washing procedure 8B for use, to the cloth specimen of 1#-30# anti-bacteria cloth and the cloth specimen of 1#-8# contrast anti-bacteria cloth, do carrying out washing treatment respectively.Wash time 5min, drying means are oven drying.One washes one driedly counts washing once.Each cloth specimen is measured the anti-microbial property of the cloth specimen after washing through washing 10 times, 20 times, 50 times.
Antibiotic endurance life test: the Water Resistance Test method and the light fastness test method of the Japanese antibacterial product of reference TIA.
1, light fastness test: cloth specimen normal temperature is down through uviol lamp (60W/m
2) shone the antibiotic property of cloth specimen after the mensuration illumination 10 hours.This condition test result reflection, the quality of the anti-bacteria cloth that in general indoor environment, uses aspect lasting maintenance anti-microbial property.
2, Water Resistance Test: cloth specimen soaks through 16h through 50 ℃ ± 5 ℃ distilled water, oven dry.Measure the antibiotic property of water logging bubble back cloth specimen.This condition test result reflects, often contacts the quality of anti-bacteria cloth aspect lasting maintenance anti-microbial property of water.
Anti-microbial property test: with reference to the test method of State Standard of the People's Republic of China GB15979-2002 " disposable use amenities sanitary standard " product anti-microbial property, test strain is a bacterium: staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 25922), fungi: Candida albicans (ATCC 10231).Specimen is that 1#-30# anti-bacteria cloth, 1#-8# contrast anti-bacteria cloth, and the sample cloth through washing.Blank cloth is 0# pure cotton knitting cloth.
Test organisms is made bacteria suspension, and (the bacteria suspension concentration of requirement is: drip on 2.0cm x 3.0cm blank cloth specimen with 0.10ml, reclaiming the bacterium number is 1 x 10
4～9 x 10
4The cfu/ piece), drip 0.10ml at every on by sample cloth and blank sample respectively, evenly distribute, pick up counting, effect 0 (very first time is carried out next step immediately after dripping), 1,2,5,10,20min, 1,2,6,18,24h, with aseptic nipper the sample input is contained 5ml PBS in vitro, fully mix, do suitably dilution, get wherein 2～3 dilution factors then, draw 0.5ml respectively, place two plates, nutrient agar (bacterium) or sabouraud's agar (fungi) 15ml with cold to 40～45 ℃ pour into, rotate plate, make it full and uniform, it is dull and stereotyped that agar solidifies the back upset, cultivate 48h (bacterium) or 72h (fungi), do the viable bacteria colony counting for 35 ℃ ± 2 ℃.
Test repeats 3 times, is calculated as follows antibiotic rate: X=(A-B)/A x 100%
In the formula: X---antibiotic rate, %;
A---the average clump count of blank cloth;
B---the average clump count of tested sample.
Judge: if antibiotic rate=50%～90%, cloth specimen has antibacterial action; If antibiotic rate 〉=90%, cloth specimen have strong antibacterial action.
After measured, the antibiotic cloth specimen of 1# sees Table 1 to the antibiotic rate of Escherichia coli, staphylococcus aureus, Candida albicans, and three kinds of representative test strain in Gram-negative bacteria, gram-positive bacteria, the fungi are shown good antibacterial property.
1# contrasts antibiotic cloth specimen the antibiotic rate of Escherichia coli, staphylococcus aureus, Candida albicans is seen Table 2, and is better to the antibiotic property of Escherichia coli, staphylococcus aureus, general to the oidiomycetic antibacterial effect of white, but effect is slower.
2# contrasts antibiotic cloth specimen the antibiotic rate of Escherichia coli, staphylococcus aureus, Candida albicans is seen Table 3, and freshly prepd cloth specimen is all better to the antibacterial action of Escherichia coli, staphylococcus aureus, Candida albicans.
The variation of antibacterial effect after washing of antibiotic cloth specimen and the antibiotic cloth specimen of contrast, to be example to colibacillary test, antibiotic rate the results are shown in Table 4-table 7.Changing Pattern to staphylococcus aureus and Candida albicans is close.
Each cloth specimen sees Table 8 to colibacillary antibiotic rate behind light fastness test.Changing Pattern to staphylococcus aureus and Candida albicans is close.
Each cloth specimen sees Table 9 to colibacillary antibiotic rate after Water Resistance Test.Changing Pattern to staphylococcus aureus and Candida albicans is close.
Adopt 1#-20# inorganic/the antibiotic cloth specimen of 1#-30# that organic nano composite antibacterial agent is handled promptly shows stronger antibiotic property (seeing Table 4), plays the effect of quick antibacterial in 0-20min.After washing, antibiotic property descends along with increasing of washing times, but still keeps good antibacterial effect (seeing Table 5-table 7) after 50 washings.Behind light fastness test, antibiotic property does not weaken (seeing Table 8).After Water Resistance Test, antibiotic property weakens not obvious (seeing Table 9).
(seeing Table 4) and washing back (seeing Table 5-table 7) before 1#, 3#, 5#, 7# contrast anti-bacteria cloth (handling with the 1# contrast inorganic antiseptic) washing, antibacterial action is all not strong in the 20min.Action time 18-24h, antibacterial effect is good.Contrast table 4 and table 5-table 7,1#, 3#, 5#, 7# contrast antibiotic certain washing fastness that is furnished with.Behind light fastness test, antibiotic property weakens (seeing Table 8).After Water Resistance Test, antibiotic property decrease (seeing Table 9).
And 2#, 4#, 6#, 8# contrast anti-bacteria cloth (handling with 2# contrast organic antibacterial agent), antibacterial action is stronger before the washing, and the time of working is very fast.After washing, the antibiotic property decay that contrasts antibiotic cloth specimen 2#, 4#, 6#, 8# is bigger.Behind light fastness test, antibiotic property decline is big (seeing Table 8).After Water Resistance Test, antibiotic property keeps relatively poor (seeing Table 9).
The invention effect:
Antibacterial products such as the antibacterial cotton cloth of the present invention contains inorganic/organic nano composite antibacterial agent, anti-bacteria nylon, antibiotic polyester-cotton blend, antibiotic nonwoven polypropylene fabric, antibiotic perforated film; have excellent properties such as rapid, durable stable, fast light, water-fast, the wash resistant of antibacterial action; be used in aspects such as life and medical treatment; preventable disease takes place and propagates; the protection human health is improved the quality of living.
Table 1, the antibiotic rate of the antibiotic cloth specimen of 1#
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Table 2,1# contrast the antibiotic rate of antibiotic cloth specimen
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Table 3,2# contrast the antibiotic rate of antibiotic cloth specimen
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Table 4 is without the antibiotic rate (Escherichia coli) of washing cloth specimen
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Table 5 is through the antibiotic rate (Escherichia coli) of 10 washing cloth specimens
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Table 6 is through the antibiotic rate (Escherichia coli) of 20 washing cloth specimens
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Table 7 is through the antibiotic rate (Escherichia coli) of 50 washing cloth specimens
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Table 8, the antibiotic rate of cloth specimen (Escherichia coli) behind light fastness test
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Table 9, the antibiotic rate of cloth specimen (Escherichia coli) after Water Resistance Test
Annotate: antibiotic rate " * * * ": 〉=99%; " * * ": 〉=90%; " * ": 〉=50%; "-":＜50%.
Claims (11)
1, a kind of inorganic/organic nano composite antibacterial agent, it is characterized in that the component and the weight portion thereof that are comprised are:
Inorganic antiseptic: 0.01-20 part, organic antibacterial agent: 0.01-35 part, the compatible inorganic agent of inorganic/organic antibacterial agent: 0.0001-0.4 part, polymer binder: 0.05-40 part, the stabilizing agent of anti-inorganic antiseptic variable color: 0.0001-0.4 part, efficient emulsifier: 0.1-30 part, distilled water: 100 parts
This inorganic/organic nano composite antibacterial agent follows these steps to be prepared:
Elder generation is with stabilizing agent 0.0001-0.4 part of inorganic antiseptic 0.01-20 part and anti-inorganic antiseptic variable color, moistening dispersion in 100 parts of distilled water, agitation grinding; Add the compatible inorganic agent 0.0001-0.4 of inorganic/organic antibacterial agent part, continue to grind; Add organic antibacterial agent 0.01-35 part, filler is some, grind again; Add efficient emulsifier 0.1-30 part, high speed dispersion; Add polymer binder 0.05-20 part, stir, realize that the inorganic antiseptic nanoscale disperses and form the inorganic/organic composite antibiotic agent of organic antibacterial agent nanoscale microemulsion structure, wherein the particle diameter of inorganic antiseptic is 20nm-15 μ m.
2, according to claim 1 a kind of inorganic/organic nano composite antibacterial agent, it is characterized in that described inorganic antiseptic is zeolite with carrying silver, copper-loaded zeolite, carries the zinc zeolite, carries the silver-bearing copper zeolite, carries silver-colored zinc zeolite, copper-loaded zinc zeolite; Silver-loaded zirconium phosphate, copper-loaded basic zirconium phosphate, year zinc basic zirconium phosphate, year silver-bearing copper basic zirconium phosphate, year silver-colored zinc basic zirconium phosphate, copper-loaded zinc basic zirconium phosphate; Carry silver-colored calcium phosphate, copper-loaded calcium phosphate, carry zinc calcium phosphate, carry silver-bearing copper calcium phosphate, carry silver-colored zinc calcium phosphate, copper-loaded zinc calcium phosphate; Carry silver-colored titanium phosphate, copper-loaded titanium phosphate, carry the zinc titanium phosphate, carry the silver-bearing copper titanium phosphate, carry silver-colored zinc titanium phosphate, copper-loaded zinc titanium phosphate; Carry silver-colored silica gel, copper-loaded silica gel, carry zinc silica gel, carry silver-bearing copper silica gel, carry silver-colored zinc silica gel, copper-loaded zinc silica gel; Carry silver-colored titanium dioxide, copper-loaded titanium dioxide, carry zinc titanium dioxide, carry silver-bearing copper titanium dioxide, carry silver-colored zinc titanium dioxide, copper-loaded zinc titanium dioxide; Carry silver-colored imvite, copper-loaded imvite, carry the zinc imvite, carry the silver-bearing copper imvite, carry silver-colored zinc imvite, copper-loaded zinc imvite; Carry the Ag-Cu-Zn soluble glass; Carry the Ag-Cu-Zn active carbon, or their two or more mixtures wherein.
3, according to claim 1 a kind of inorganic/organic nano composite antibacterial agent, it is characterized in that described organic antibacterial agent is a dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, the myristyl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzene oxygen ethyl ammonium bromide, myristyl-2-picoline ammonium bromide, cetyl pyridinium ammonium chloride, the cetyl pyridinium ammonium bromide, the two octyl group ammonium chlorides of dimethyl, the two octadecyl ammonium chloride of dimethyl, hexadecyltrimethylammonium chloride, OTAC, diisobutyl benzene oxygen ethyl dimethyl benzyl ammonium chloride, 3-(trimethoxy silylation) propyl group octadecyl alkyl dimethyl ammonium chloride, lauryl amine ethyl glycine, 2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-n-octyl-4-isothiazoline-3-ketone, 4,5-two chloro-2-n-octyls-4-isothiazoline-3-ketone, 1,2-benzisothiazole-3-ketone, 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether, 2-(4-thiazolyl) benzimidazole, 1, two [5-(4-chlorphenyl) biguanides] digluconate of 1 '-hexa-methylene, β-1,4-dextran amine (chitosan), 10,10 '-oxo Shuan phenoxazine, 2,4,5,6-tetrachloro-1, the 3-benzene dicarbonitrile, benzimidazolyl-2 radicals-methoxyl group methyl carbamate, 2-(4-thiazolyl) benzimidazole, hexamethylene, 1,6-two (just-to the chlorobenzene biguanides) hexane, or their two or more mixtures wherein.
4, according to claim 1 a kind of inorganic/organic nano composite antibacterial agent, it is characterized in that described inorganic/the compatible inorganic agent of organic antibacterial agent is silane coupler, titanate coupling agent, aluminate coupling agent, boric acid ester coupler, epoxy resin, or their two or more mixtures wherein.
5, according to claim 4 a kind of inorganic/organic nano composite antibacterial agent, it is characterized in that described inorganic/the compatible inorganic agent of organic antibacterial agent is a r-chloropropyl trimethoxyl silane, perfluoro n-heptyl methyl ether propyl-triethoxysilicane, perfluor isopropyl ether MTMS, MTMS, ethyl triethoxysilane, VTES, vinyltrimethoxy silane, propyl methacrylate base trimethoxy silane, N-amine ethylamine oxypropyl trimethyl silane, vinyl benzyl amine ethylamine propyl trimethoxy silicane hydrochloride, methyl chloride ethyl acrylate base dimethyl amido propyl trimethoxy silicane, the tolyl trimethoxy silane, the amine propyl trimethoxy silicane, toluene bromide base trimethoxy silane, epoxy propyl ether propyl trimethoxy silicane, the epoxycyclohexyl ethyl trimethoxy silane, phenyltrimethoxysila,e, mercaptopropyl trimethoxysilane, to the chlorobenzene ethyl trimethoxy silane, the bromophenyl trimethoxy silane, isopropyl three different hydroxyl acyl titanate esters, isopropyl three (dodecyl benzene sulfonyl) titanate esters, isopropyl three (dioctylphyrophosphoric acid ester) titanate esters, two (dioctyl phosphite ester) titanate esters of tetra isopropyl, two (two (dodecyl) phosphite ester) titanate esters of four octyl groups, four (2,2-two allyloxys-1-butyl) two (two (tridecyl) phosphite ester) titanate esters, two (dioctylphyrophosphoric acid ester) fluoroacetic acid ester titanate esters, isopropyl stearoyl two acryloyl titanate esters, isopropyl three (dioctyl phosphate) titanate esters, isopropyl two (dodecyl benzene sulfonyl)-4-amino-benzene sulfonyl titanate esters, isopropyl three (methacryl) titanate esters, dilauryl phosphorite type titanate esters, isopropyl stearoyl two (4-aminobenzoyl) titanate esters, isopropyl three acryloyl titanate esters, ethylene glycol boric acid monooctyl ester, stearoyl boric acid glycol ester, epoxy 628, epoxy E-51,1050,1051,4051, PEO, poly(propylene oxide), or their two or more mixtures wherein.
6, according to claim 1 a kind of inorganic/organic nano composite antibacterial agent, it is characterized in that described polymer binder is polyacrylate, the resinoid aqueous emulsion of polyurethane, or their two or more mixtures wherein.
7, according to claim 1 a kind of inorganic/organic nano composite antibacterial agent, the stabilizing agent that it is characterized in that described anti-inorganic antiseptic variable color is sodium thiosulfate, potassium thiosulfate, sodium silicate, silicon potash fertilizer, waterglass, ammonia, fatty amine, aromatic amine, acrylic acid, methacrylic acid, or their two or more mixtures wherein.
8, according to claim 1 a kind of inorganic/organic nano composite antibacterial agent, it is characterized in that described efficient emulsifier is APEO type, ester type nonionic emulsifier, synthetic high polymer surfactant or natural polymeric surface active agent.
9, according to claim 8 a kind of inorganic/organic nano composite antibacterial agent, it is characterized in that described efficient emulsifier is sorbitan mono-laurate (SPAN-20), anhydrous sorbitol monopalmitate (SPAN-40), sorbitan monostearate (SPAN-60), anhydrous sorbitol tristearate (SPAN-65), sorbitan monooleate (SPAN-80), sorbitan sesquioleate (SPAN-83), sorbitan trioleate (SPAN-85), the addition of ethylene oxide number is 20 SPAN-20 ethylene oxide adduct (TWEEN-20), the addition of ethylene oxide number is 20 SPAN-40 ethylene oxide adduct (TWEEN-40), the addition of ethylene oxide number is 20 SPAN-60 ethylene oxide adduct (TWEEN-60), the addition of ethylene oxide number is 20 SPAN-80 ethylene oxide adduct (TWEEN-80), the addition of ethylene oxide number is 20 SPAN-85 ethylene oxide adduct (TWEEN-85), the addition of ethylene oxide number is 5 SPAN-81 ethylene oxide adduct (TWEEN-81), polyox-yethylene-polyoxypropylene block copolymer, the benzyl phenyl APEO, styryl phenyl APEO, gelatin, or their two or more mixtures wherein.
10, according to claim 1 a kind of inorganic/application method of organic nano composite antibacterial agent, it is characterized in that antibiotic back finishing technique to fibre comprises to adopt dip method, pad dyeing method or spraying process.
11, according to claim 1 a kind of inorganic/organic nano composite antibacterial agent is textile products thus treated, the material category that it is characterized in that goods comprises native fiber cotton, hair, real silk or fiber crops, the blending of one or more in synthetic fibers polypropylene fibre, terylene, nylon, polyethylene fibre, the viscose rayon or mixed fabric; Wherein fabric types comprises yarn, wool top, woven, knitted fabric, nonwoven or porous membrane; Goods comprise interior outerwear trousers, sportswear, socks, shoe-pad, gloves, muffler, cap, carpet, curtain, the tablecloth, shower curtain, bedding, seat cushion, automotive trim fabric, mouth mask, hospital gauze, the medical cloth that stretches tight, operation dress, curative activity clothes, johnny, airstrainer, diaper or sanltary towel.
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