CN101781851A - Polyurethane antibiotic soft coating agent and method for preparing same - Google Patents
Polyurethane antibiotic soft coating agent and method for preparing same Download PDFInfo
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Abstract
The invention relates to a polyurethane antibiotic soft coating agent and a method for preparing the same, and belongs to the field of chemistry. The coating agent is prepared by using a reaction of carboxylic acid-containing waterborne polyurethane emulsion, silver-ammonia solution and a reducer. In particular, isocyanate, polyhydric alcohol compounds and hydroxy silicone oil are reacted to form a isocyanate-terminated prepolymer; a carboxy-containing chain extender is added into the isocyanate-terminated prepolymer to undergo a chain extension reaction to form the waterborne polyurethane emulsion; the waterborne polyurethane emulsion is added into the silver-ammonia solution, and under an action of the reducer, silver ions are reduced in situ on the surface of the polyurethane and the silver particles are deposited on the surface of the polyurethane; and thus, the polyurethane antibiotic soft coating agent having the sustainable antibiotic property is prepared.
Description
Technical field
The present invention relates to a kind of polyurethane antibiotic soft coating agent and preparation method thereof, belong to chemical field.
Background technology
The fabric coating finishing agent is coating adhesive again, is a kind of macromolecule compound of evenly coating fabric face.It forms one or more layers film at fabric face by adhesive effect, makes fabric improve look and feel, increases additional function, has antibiotic, waterproof, specific function such as saturating wet, fire-retardant.The polyurethane full name is a polyurethanes, is to contain in the molecular structure-macromolecular compound of NHCOO-unit.Before and after nineteen fifty, PU occurs in Europe as textile finshing agent, is used for the dry type top finish but mostly be the solvent-borne type product greatly.The sixties in 20th century, because the enhancing of people's environmental consciousness and the appearance of government's environmental regulation, water-based PU coating is arisen at the historic moment.After the seventies, water-based PU coating develops rapidly, the extensive use of PU coated fabric.Aqueous polyurethane (WPU) is meant with water to replace organic solvent and does not contain or to contain the polyurethane of minute quantity organic solvent in its dispersion liquid as decentralized medium.It is filmed to have and advantage such as is not fired, nontoxic, free from environmental pollution, energy-conservation, have simultaneously general polyurethane resin intrinsic high strength, excellent properties such as wear-resistant, therefore obtained to use widely.Since the eighties, breakthrough has appearred in research and the application technology of PU.Polyurethane coating agent is the main kind of current development, and its advantage is: (1) coating is soft and flexible; (2) strength of coating is good, can be used for very thin coating; (3) coating porous has wet and venting capability; (4) wear-resisting, moisture-proof, anti-dry-cleaning.
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
3+=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
The object of the present invention is to provide a kind of polyurethane antibiotic soft coating agent and preparation method thereof, the present invention reacts by in-situ reducing, make silver-colored particle deposition at polyurethane surface, overcome the migration shortcoming of above-mentioned silver, promoted the anti-microbial property and the durability of silver antibacterial agent as antiseptic.
To achieve these goals, the technical solution adopted in the present invention is:
A kind of polyurethane antibiotic soft coating agent is made by the aqueous polyurethane emulsion that contains carboxylic acid, silver ammino solution, reductant reaction, wherein contains 78～146 parts of the aqueous polyurethane emulsions of carboxylic acid, 12～37 parts of silver ammino solutions, 3～24 parts of reductants.
Described reductant is aldehydes, formic acid esters, contain in the sugar and the fructose of aldehyde radical, the organic salt that reducibility is arranged, hydrazine, the alpha-Naphthol any one.
Described aldehydes is any one shown in the formula 1
In the formula 1, R is an alkyl;
Formic acid esters is any one shown in the formula 2
In the formula 2, R is an alkyl; The sugar that contains aldehyde radical is any one in glucose, maltose, rhamnose, fucose, arabinose, wood sugar, mannose, galactolipin and the aldotriose; The organic salt that reducibility is arranged is any one in tartrate, trisodium citrate, the sodium lactate.
A kind of preparation method of polyurethane antibiotic soft coating agent, comprise the steps: that the aqueous polyurethane emulsion that will contain carboxylic acid earlier is equipped with in the container of silver ammino solution slow the adding, and stir, then in this container, add reductant again, stirring reaction 1～2h under 40～60 ℃ bath temperature promptly gets polyurethane antibiotic soft coating agent; 78～146 parts of aqueous polyurethane emulsions that wherein contain carboxylic acid, 12～37 parts of silver ammino solutions, 3～24 parts of reductants.
The described preparation method who contains the aqueous polyurethane emulsion of carboxylic acid is, with hydroxy silicon oil 120 ℃ of vacuum dehydration 1h in reactor of 80～120 parts polyalcohols and 20～35 parts; Then in reactor, add 100～150 parts the isocyanates and the micromolecule organic solvents of 10～20 parts of adjusting viscosity, at 80～90 ℃ of reaction 1～3h; Be cooled to 60～70 ℃ then, add 10～15 parts of chain extension-crosslinking agent, 0.05～0.2 part of catalyst, 32～46 parts of micromolecule organic solvents, insulation reaction 3～4h; Be cooled to room temperature again, add 124～352 parts of deionized water and stirring emulsifications, vacuum removal micromolecule organic solvent promptly gets the aqueous polyurethane emulsion that contains carboxylic acid.
Described polyalcohol is that poly(ethylene oxide) ether dihydroxylic alcohols, poly(propylene oxide) ether dihydroxylic alcohols, PTMG dihydroxylic alcohols, adipic acid are one or more in polyester-diol, aromatic polyester polyol, polycaprolactone polyol, the PCDL; Hydroxy silicon oil is the terminal hydroxy group straight chain dimethicone of molecular weight 1000～6000; Isocyanates is a toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, naphthalene diisocyanate, PPDI, 1, the 4-cyclohexane diisocyanate, XDI, the cyclohexanedimethyleterephthalate vulcabond, trimethyl-1, the 6-hexamethylene diisocyanate, tetramethyl m-phenylenedimethylim-vulcabond, norbornene alkyl diisocyanate, the dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, in the polymethylene multi-phenenyl isocyanate one or more; The micromolecule organic solvent is one or more in ethyl acetate, butyl acetate, ethylene glycol ether acetate, dicarboxylic ester, MEK, acetone, cyclohexanone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, the ethylene glycol monobutyl ether; The chain extension-crosslinking agent is a kind of in dihydromethyl propionic acid, the dimethylolpropionic acid and 1,4-butanediol, ethylene glycol, diglycol, neopentyl glycol, 1,6-hexylene glycol, glycerine, trimethylolpropane, pentaerythrite, monoethanolamine, diethanol amine, triethanolamine, ethylenediamine, 1,3-propane diamine, 1,4-butanediamine, 1,6-hexamethylene diamine, isophorone diamine, diethylenetriamine, triethylene tetramine, 3,3 '-two chloro-4,4 '-diphenyl methane diamines, 3, one or more among 5-diethyl toluene diamine, the hydroquinone two hydroxy ethyl ether; Catalyst is one or more in triethylenediamine, two (dimethylaminoethyl) ether, cyclohexyl methyl tertiary amine, pentamethyl two alkylene triamine, tetramethyl Alkylenediamine, hydroxyl tertiary amine, dibutyl tin laurate, stannous octoate, isooctyl acid potassium, potassium acetate, the isooctyl acid zinc.
Described polyalcohol is poly(ethylene oxide) ether dihydroxylic alcohols, PTMG dihydroxylic alcohols; Isocyanates is toluene di-isocyanate(TDI), isophorone diisocyanate, hexamethylene diisocyanate.
Described aromatic polyester polyol is poly-phthalic acid diglycol esterdiol, poly-phthalic acid-1, any one in 6-hexylene glycol polyester-diol, poly-phthalic acid neopentyl glycol polyester-diol, the poly-phthalic acid neopentyl glycol hexylene glycol polyester-diol.
The collocation method of described silver ammino solution is: take by weighing an amount of AgNO
3Solution drips weak aqua ammonia in AgNO in the container of cleaning
3In the solution, the vibration while dripping is till the precipitation of initial generation is just dissolved.
Need to prove that at this above umber all refers to parts by mass.
The preparation method of polyurethane antibiotic soft coating agent of the present invention is with isocyanates, polyol compound, hydroxy silicon oil reaction, generates the performed polymer of isocyanate terminated base, carries out chain extending reaction with containing the carboxyl chain extender again, forms aqueous polyurethane emulsion; The polyaminoester emulsion that makes is joined in the silver ammino solution, under the effect of reductant, make silver ion make silver-colored particle deposition at polyurethane surface, generate polyurethane antibiotic soft coating agent with durable antibiotic performance in the polyurethane surface in-situ reducing.
Traditional antibiotic finish generally is that the material interpolation that will have antibiotic property is distributed in the arrangement mixed liquor, and then puts in order on the textiles by methods such as flooding, pad.Such method for sorting exists finishing agent and be difficult to homodisperse problem in dressing liquid; Simultaneously, antibiotic property material and dressing liquid belong to out-phase, exist the unsettled risk of dressing liquid.And polyurethane antibiotic soft coating agent of the present invention be silver ion through the in-situ reducing uniform deposition in polyurethane surface, good stability is also conveniently preserved and is used.
In a word, beneficial effect of the present invention: 1), make silver in the polyurethane surface deposition, avoided silver-colored transport phenomena, strengthened its antibiotic persistence, formed a kind of developing thought of new antibacterial finishing agent by in-situ reducing reaction; 2), in the mode of surface reduction load, make silver distribution more evenly, stable, simultaneously, the filming performance that polyurethane is good makes antibiotic more long-acting.
The specific embodiment
The invention will be further described below by specific embodiment, but the present invention is not limited by following examples.
Embodiment one
A kind of polyurethane antibiotic soft coating agent is made by the aqueous polyurethane emulsion that contains carboxylic acid, silver ammino solution, reductant reaction, wherein contains 78 parts of the aqueous polyurethane emulsions of carboxylic acid, 12 parts of silver ammino solutions, 3 parts of reductants.Wherein, reductant is a glyoxal.
The preparation method of above-mentioned polyurethane antibiotic soft coating agent comprises the steps:
The aqueous polyurethane emulsion that will contain carboxylic acid earlier is equipped with in the container of silver ammino solution slow the adding, and stirs, and then adds reductant again in this container, and stirring reaction 2h under 40 ℃ bath temperature promptly gets polyurethane antibiotic soft coating agent.
The preparation method who contains the aqueous polyurethane emulsion of carboxylic acid is, with hydroxy silicon oil 120 ℃ of vacuum dehydration 1h in reactor of 80 parts polyalcohols and 20 parts; Then in reactor, add 100 parts the isocyanates and the micromolecule organic solvents of 10 parts of adjusting viscosity, at 80 ℃ of reaction 3h; Be cooled to 60 ℃ then, add 10 parts of chain extension-crosslinking agent, 0.05 part of catalyst, 32 parts of same micromolecule organic solvents, insulation reaction 4h; Be cooled to room temperature again, add 124 parts of deionized water and stirring emulsifications, vacuum removal micromolecule organic solvent promptly gets the aqueous polyurethane emulsion that contains carboxylic acid.
Wherein, polyalcohol is poly(ethylene oxide) ether dihydroxylic alcohols, PTMG dihydroxylic alcohols; Hydroxy silicon oil is the terminal hydroxy group straight chain dimethicone of molecular weight 1000～6000; Isocyanates is toluene di-isocyanate(TDI), isophorone diisocyanate, hexamethylene diisocyanate; The micromolecule organic solvent is an ethyl acetate; The chain extension-crosslinking agent is dihydromethyl propionic acid, ethylene glycol; Catalyst is a triethylenediamine.
The collocation method of silver ammino solution is: take by weighing an amount of AgNO
3Solution drips weak aqua ammonia in AgNO in the container of cleaning
3In the solution, the vibration while dripping is till the precipitation of initial generation is just dissolved.
Embodiment two
A kind of polyurethane antibiotic soft coating agent is made by the aqueous polyurethane emulsion that contains carboxylic acid, silver ammino solution, reductant reaction, wherein contains 95 parts of the aqueous polyurethane emulsions of carboxylic acid, 20 parts of silver ammino solutions, 10 parts of reductants.Wherein, reductant is a propyl formate.
The preparation method of above-mentioned polyurethane antibiotic soft coating agent comprises the steps:
The aqueous polyurethane emulsion that will contain carboxylic acid earlier is equipped with in the container of silver ammino solution slow the adding, and stirs, and then adds reductant again in this container, and stirring reaction 1.8h under 45 ℃ bath temperature promptly gets polyurethane antibiotic soft coating agent.
The preparation method who contains the aqueous polyurethane emulsion of carboxylic acid is, with hydroxy silicon oil 120 ℃ of vacuum dehydration 1h in reactor of 90 parts polyalcohols and 24 parts; Then in reactor, add 115 parts the isocyanates and the micromolecule organic solvents of 12 parts of adjusting viscosity, at 82 ℃ of reaction 2.5h; Be cooled to 62 ℃ then, add 11 parts of chain extension-crosslinking agent, 0.08 part of catalyst, 36 parts of same micromolecule organic solvents, insulation reaction 3.8h; Be cooled to room temperature again, add 180 parts of deionized water and stirring emulsifications, vacuum removal micromolecule organic solvent promptly gets the aqueous polyurethane emulsion that contains carboxylic acid.
Wherein, polyalcohol is poly-phthalic acid diglycol esterdiol; Hydroxy silicon oil is the terminal hydroxy group straight chain dimethicone of molecular weight 1000～6000; Isocyanates is the cyclohexanedimethyleterephthalate vulcabond; The micromolecule organic solvent is an ethylene glycol ether acetate; The chain extension-crosslinking agent is a dimethylolpropionic acid, 1,3-propane diamine, 1,4-butanediamine; Catalyst is the cyclohexyl methyl tertiary amine.
The collocation method of silver ammino solution is: take by weighing an amount of AgNO
3Solution drips weak aqua ammonia in AgNO in the container of cleaning
3In the solution, the vibration while dripping is till the precipitation of initial generation is just dissolved.
Embodiment three
A kind of polyurethane antibiotic soft coating agent is made by the aqueous polyurethane emulsion that contains carboxylic acid, silver ammino solution, reductant reaction, wherein contains 115 parts of the aqueous polyurethane emulsions of carboxylic acid, 25 parts of silver ammino solutions, 15 parts of reductants.Wherein, reductant is a maltose.
The preparation method of above-mentioned polyurethane antibiotic soft coating agent comprises the steps:
The aqueous polyurethane emulsion that will contain carboxylic acid earlier is equipped with in the container of silver ammino solution slow the adding, and stirs, and then adds reductant again in this container, and stirring reaction 1.5h under 50 ℃ bath temperature promptly gets polyurethane antibiotic soft coating agent.
The preparation method who contains the aqueous polyurethane emulsion of carboxylic acid is, with hydroxy silicon oil 120 ℃ of vacuum dehydration 1h in reactor of 100 parts polyalcohols and 28 parts; Then in reactor, add 125 parts the isocyanates and the micromolecule organic solvents of 15 parts of adjusting viscosity, at 85 ℃ of reaction 2.0h; Be cooled to 65 ℃ then, add 12 parts of chain extension-crosslinking agent, 0.12 part of catalyst, 42 parts of same micromolecule organic solvents, insulation reaction 3.5h; Be cooled to room temperature again, add 240 parts of deionized water and stirring emulsifications, vacuum removal micromolecule organic solvent promptly gets the aqueous polyurethane emulsion that contains carboxylic acid.
Wherein, polyalcohol is that adipic acid is a polyester-diol; Hydroxy silicon oil is the terminal hydroxy group straight chain dimethicone of molecular weight 1000～6000; Isocyanates is a norbornene alkyl diisocyanate; The micromolecule organic solvent is glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether; The chain extension-crosslinking agent is dimethylolpropionic acid, glycerine; Catalyst is a dibutyl tin laurate.
The collocation method of silver ammino solution is: take by weighing an amount of AgNO
3Solution drips weak aqua ammonia in AgNO in the container of cleaning
3In the solution, the vibration while dripping is till the precipitation of initial generation is just dissolved.
Embodiment four
A kind of polyurethane antibiotic soft coating agent is made by the aqueous polyurethane emulsion that contains carboxylic acid, silver ammino solution, reductant reaction, wherein contains 130 parts of the aqueous polyurethane emulsions of carboxylic acid, 32 parts of silver ammino solutions, 20 parts of reductants.Wherein, reductant is a tartrate.
The preparation method of above-mentioned polyurethane antibiotic soft coating agent comprises the steps:
The aqueous polyurethane emulsion that will contain carboxylic acid earlier is equipped with in the container of silver ammino solution slow the adding, and stirs, and then adds reductant again in this container, and stirring reaction 1.2h under 55 ℃ bath temperature promptly gets polyurethane antibiotic soft coating agent.
The preparation method who contains the aqueous polyurethane emulsion of carboxylic acid is, with hydroxy silicon oil 120 ℃ of vacuum dehydration 1h in reactor of 110 parts polyalcohols and 33 parts; Then in reactor, add 135 parts the isocyanates and the micromolecule organic solvents of 18 parts of adjusting viscosity, at 87 ℃ of reaction 1.5h; Be cooled to 67 ℃ then, add 14 parts of chain extension-crosslinking agent, 0.17 part of catalyst, 44 parts of same micromolecule organic solvents, insulation reaction 3.2h; Be cooled to room temperature again, add 300 parts of deionized water and stirring emulsifications, vacuum removal micromolecule organic solvent promptly gets the aqueous polyurethane emulsion that contains carboxylic acid.
Wherein, polyalcohol is a polycaprolactone polyol; Hydroxy silicon oil is the terminal hydroxy group straight chain dimethicone of molecular weight 1000～6000; Isocyanates is a Methylcyclohexyl diisocyanate; The micromolecule organic solvent is a dicarboxylic ester; The chain extension-crosslinking agent is dihydromethyl propionic acid, diethylenetriamine, triethylene tetramine; Catalyst is a potassium acetate.
The collocation method of silver ammino solution is: take by weighing an amount of AgNO
3Solution drips weak aqua ammonia in AgNO in the container of cleaning
3In the solution, the vibration while dripping is till the precipitation of initial generation is just dissolved.
Embodiment five
A kind of polyurethane antibiotic soft coating agent is made by the aqueous polyurethane emulsion that contains carboxylic acid, silver ammino solution, reductant reaction, wherein contains 146 parts of the aqueous polyurethane emulsions of carboxylic acid, 37 parts of silver ammino solutions, 24 parts of reductants.Wherein, reductant is an alpha-Naphthol.
The preparation method of above-mentioned polyurethane antibiotic soft coating agent comprises the steps:
The aqueous polyurethane emulsion that will contain carboxylic acid earlier is equipped with in the container of silver ammino solution slow the adding, and stirs, and then adds reductant again in this container, and stirring reaction 1.0h under 60 ℃ bath temperature promptly gets polyurethane antibiotic soft coating agent.
The preparation method who contains the aqueous polyurethane emulsion of carboxylic acid is, with hydroxy silicon oil 120 ℃ of vacuum dehydration 1h in reactor of 120 parts polyalcohols and 35 parts; Then in reactor, add 150 parts the isocyanates and the micromolecule organic solvents of 20 parts of adjusting viscosity, at 90 ℃ of reaction 1.0h; Be cooled to 70 ℃ then, add 15 parts of chain extension-crosslinking agent, 0.2 part of catalyst, 46 parts of same micromolecule organic solvents, insulation reaction 3.0h; Be cooled to room temperature again, add 352 parts of deionized water and stirring emulsifications, vacuum removal micromolecule organic solvent promptly gets the aqueous polyurethane emulsion that contains carboxylic acid.
Wherein, polyalcohol is a PCDL; Hydroxy silicon oil is the terminal hydroxy group straight chain dimethicone of molecular weight 1000～6000; Isocyanates is a polymethylene multi-phenenyl isocyanate; The micromolecule organic solvent is an ethylene glycol ether acetate; The chain extension-crosslinking agent is dihydromethyl propionic acid, hydroquinone two hydroxy ethyl ether; Catalyst is an isooctyl acid zinc.
The collocation method of silver ammino solution is: take by weighing an amount of AgNO
3Solution drips weak aqua ammonia in AgNO in the container of cleaning
3In the solution, the vibration while dripping is till the precipitation of initial generation is just dissolved.
The foregoing description only is used to the inventive concept of the present invention of explaining, but not to the qualification of rights protection of the present invention, allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should fall into protection scope of the present invention.
Claims (9)
1. polyurethane antibiotic soft coating agent, it is characterized in that making by the aqueous polyurethane emulsion that contains carboxylic acid, silver ammino solution, reductant reaction, 78～146 parts of aqueous polyurethane emulsions that wherein contain carboxylic acid, 12～37 parts of silver ammino solutions, 3～24 parts of reductants.
2. polyurethane antibiotic soft coating agent as claimed in claim 1 is characterized in that: described reductant is aldehydes, formic acid esters, contain in the sugar and the fructose of aldehyde radical, the organic salt that reducibility is arranged, hydrazine, the alpha-Naphthol any one.
3. polyurethane antibiotic soft coating agent as claimed in claim 2 is characterized in that: described aldehydes is any one shown in the formula 1
In the formula 1, R is an alkyl;
Formic acid esters is any one shown in the formula 2
In the formula 2, R is an alkyl; The sugar that contains aldehyde radical is any one in glucose, maltose, rhamnose, fucose, arabinose, wood sugar, mannose, galactolipin and the aldotriose; The organic salt that reducibility is arranged is any one in tartrate, trisodium citrate, the sodium lactate.
4. preparation method of polyurethane antibiotic soft coating agent according to claim 1, it is characterized in that comprising the steps: that the aqueous polyurethane emulsion that will contain carboxylic acid earlier is equipped with in the container of silver ammino solution slow the adding, and stir, then in this container, add reductant again, stirring reaction 1～2h under 40～60 ℃ bath temperature promptly gets polyurethane antibiotic soft coating agent; 78～146 parts of aqueous polyurethane emulsions that wherein contain carboxylic acid, 12～37 parts of silver ammino solutions, 3～24 parts of reductants.
5. the preparation method of polyurethane antibiotic soft coating agent as claimed in claim 4, it is characterized in that: the described preparation method who contains the aqueous polyurethane emulsion of carboxylic acid is, with hydroxy silicon oil 120 ℃ of vacuum dehydration 1h in reactor of 80～120 parts polyalcohols and 20～35 parts; Then in reactor, add 100～150 parts the isocyanates and the micromolecule organic solvents of 10～20 parts of adjusting viscosity, at 80～90 ℃ of reaction 1～3h; Be cooled to 60～70 ℃ then, add 10～15 parts of chain extension-crosslinking agent, 0.05～0.2 part of catalyst, 32～46 parts of micromolecule organic solvents, insulation reaction 3～4h; Be cooled to room temperature again, add 124～352 parts of deionized water and stirring emulsifications, vacuum removal micromolecule organic solvent promptly gets the aqueous polyurethane emulsion that contains carboxylic acid.
6. the preparation method of polyurethane antibiotic soft coating agent as claimed in claim 5 is characterized in that: described polyalcohol is that poly(ethylene oxide) ether dihydroxylic alcohols, poly(propylene oxide) ether dihydroxylic alcohols, PTMG dihydroxylic alcohols, adipic acid are one or more in polyester-diol, aromatic polyester polyol, polycaprolactone polyol, the PCDL; Hydroxy silicon oil is the terminal hydroxy group straight chain dimethicone of molecular weight 1000～6000; Isocyanates is a toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, naphthalene diisocyanate, PPDI, 1, the 4-cyclohexane diisocyanate, XDI, the cyclohexanedimethyleterephthalate vulcabond, trimethyl-1, the 6-hexamethylene diisocyanate, tetramethyl m-phenylenedimethylim-vulcabond, norbornene alkyl diisocyanate, the dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, in the polymethylene multi-phenenyl isocyanate one or more; The micromolecule organic solvent is one or more in ethyl acetate, butyl acetate, ethylene glycol ether acetate, dicarboxylic ester, MEK, acetone, cyclohexanone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, the ethylene glycol monobutyl ether; The chain extension-crosslinking agent is a kind of in dihydromethyl propionic acid, the dimethylolpropionic acid and 1,4-butanediol, ethylene glycol, diglycol, neopentyl glycol, 1,6-hexylene glycol, glycerine, trimethylolpropane, pentaerythrite, monoethanolamine, diethanol amine, triethanolamine, ethylenediamine, 1,3-propane diamine, 1,4-butanediamine, 1,6-hexamethylene diamine, isophorone diamine, diethylenetriamine, triethylene tetramine, 3,3 '-two chloro-4,4 '-diphenyl methane diamines, 3, one or more among 5-diethyl toluene diamine, the hydroquinone two hydroxy ethyl ether; Catalyst is one or more in triethylenediamine, two (dimethylaminoethyl) ether, cyclohexyl methyl tertiary amine, pentamethyl two alkylene triamine, tetramethyl Alkylenediamine, hydroxyl tertiary amine, dibutyl tin laurate, stannous octoate, isooctyl acid potassium, potassium acetate, the isooctyl acid zinc.
7. the preparation method of polyurethane antibiotic soft coating agent as claimed in claim 6, it is characterized in that: described polyalcohol is poly(ethylene oxide) ether dihydroxylic alcohols, PTMG dihydroxylic alcohols; Isocyanates is toluene di-isocyanate(TDI), isophorone diisocyanate, hexamethylene diisocyanate.
8. the preparation method of polyurethane antibiotic soft coating agent as claimed in claim 6, it is characterized in that: described aromatic polyester polyol is poly-phthalic acid diglycol esterdiol, poly-phthalic acid-1, any one in 6-hexylene glycol polyester-diol, poly-phthalic acid neopentyl glycol polyester-diol, the poly-phthalic acid neopentyl glycol hexylene glycol polyester-diol.
9. the preparation method of polyurethane antibiotic soft coating agent as claimed in claim 4, it is characterized in that: the collocation method of described silver ammino solution is: take by weighing an amount of AgNO
3Solution drips weak aqua ammonia in AgNO in the container of cleaning
3In the solution, the vibration while dripping is till the precipitation of initial generation is just dissolved.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103865373A (en) * | 2014-03-17 | 2014-06-18 | 同济大学 | Preparation method of anionic waterborne polyurethane nano-silver composite coating |
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2010
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| CN102330347A (en) * | 2011-07-27 | 2012-01-25 | 吴江市瑞丰织造有限公司 | Anti-fungus and mothproof coating for textiles |
| CN105636684A (en) * | 2013-08-21 | 2016-06-01 | 奎兹达阿格罗有限责任公司 | Method for production of concentrates of preferably water-soluble active agents |
| CN105636684B (en) * | 2013-08-21 | 2017-10-20 | 奎兹达阿格罗有限责任公司 | For the method for the concentrate for preparing preferred water-soluble active agent |
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| CN105935193B (en) * | 2015-03-02 | 2021-01-08 | Dmt株式会社 | Antibacterial cosmetic container with impregnated material therein |
| CN105935193A (en) * | 2015-03-02 | 2016-09-14 | Dmt株式会社 | Antimicrobial cosmetic container containing impregnating material |
| CN108468209A (en) * | 2018-03-16 | 2018-08-31 | 三元控股集团有限公司 | A kind of preparation method of the antibiotic fabric based on UV-curing technology |
| CN108530601A (en) * | 2018-03-30 | 2018-09-14 | 合肥科天水性科技有限责任公司 | A kind of nano silver aqueous polyurethane and preparation method thereof for from sterilization type thin-walled material |
| CN108642872A (en) * | 2018-05-23 | 2018-10-12 | 乔德（南通）纺织品有限公司 | A kind of anti-bacterial fibre and preparation process |
| CN111073266A (en) * | 2019-12-03 | 2020-04-28 | 江苏集萃先进高分子材料研究所有限公司 | Antibacterial polyurethane powder material for selective laser sintering 3D printing |
| CN111073266B (en) * | 2019-12-03 | 2021-08-06 | 江苏集萃先进高分子材料研究所有限公司 | Antibacterial polyurethane powder material for selective laser sintering 3D printing |
| CN112227083A (en) * | 2020-09-30 | 2021-01-15 | 京准化工技术(上海)有限公司 | Fabric water pressure resistance improver and preparation method thereof |
| CN114164566A (en) * | 2021-12-14 | 2022-03-11 | 南通大学 | Preparation method of antibacterial nanofiber membrane |
| CN114645459A (en) * | 2022-03-25 | 2022-06-21 | 武汉工程大学 | Stretchable conductive antibacterial modified polyamide and preparation method thereof |
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