CN106566351A - Anti-static anti-microbial leather coating and preparation method thereof - Google Patents

Anti-static anti-microbial leather coating and preparation method thereof Download PDF

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Publication number
CN106566351A
CN106566351A CN201610975146.7A CN201610975146A CN106566351A CN 106566351 A CN106566351 A CN 106566351A CN 201610975146 A CN201610975146 A CN 201610975146A CN 106566351 A CN106566351 A CN 106566351A
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mentioned
coating
parts
added
stirred
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Chinese (zh)
Inventor
黄浩
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Wuhu Hongkun Auto Parts Co Ltd
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Wuhu Hongkun Auto Parts Co Ltd
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Priority to CN201610975146.7A priority Critical patent/CN106566351A/en
Publication of CN106566351A publication Critical patent/CN106566351A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00Surface finishing of leather
    • C14C11/003Surface finishing of leather using macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/04Antistatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses an anti-static anti-microbial leather coating. The anti-static anti-microbial leather coating is composed of, by weight, 0.1-0.3 parts of beta-hydroxyalkylamide, 1.7-2 parts of polyvinylpyrrolidone, 0.8-1 part of polyacrylamide, 1.6-2 parts of stannous chloride, 0.1-0.13 part of triethanolamine, 190-200 parts of methyl methacrylate, 3-4 parts of sodium dodecyl sulfate, 0.1-0.2 part of hexamethylenetetramine, 0.2-0.3 part of ammonium persulfate, 6-7 parts of formaldehyde solution with the concentrate being 20%-25%, 16-20 parts of zinc acetate, 4-7 parts of silver nitrate, 0.7-1 part of dodecyl dimethyl betaine, 0.8-1 part of phthalic anhydride, 0.1-2.8 parts of chlorthal-dimethyl, 0.3-1 part of copper 8-hydroxyquinoline, 0.2-0.3 part of sucrose acetate isobutyrate and 1-2 parts of polycarboxylic acid. The anti-static anti-microbial leather coating has good anti-bacterial property, excellent moisture permeability and excellent waterproof property. Leather coated with the obtained emulsion has good anti-microbial property and excellent hygiene performance.

Description

A kind of antistatic antibiotic leather coating and preparation method thereof
Technical field
The present invention relates to leather coating technical field, more particularly to a kind of antistatic antibiotic leather coating and its preparation side Method.
Background technology
Leather finishing agent/spinning coating agent is a kind of macromolecule compound for being spread evenly across leather/textile surface.It One or more layers thin film is formed in leather/fabric face by adhesive effect.Therefore, coating material quality, not only directly affects Product appearance, quality, and decides the performance of product to a great extent.Polyacrylate dispersion has the flexible richness of film forming It is flexible, the features such as coating is fast light, ageing-resistant, wet-rub resistance can be excellent, it is the leather-like spinning coating of for being widely used at present Material.But, the presence of some polar groups in conventional polypropylene acid esters emulsion, and product storing, transports, using process In affected by environmental condition, often occur go mouldy, the phenomenon such as bacteria breed, raw material is not only wasted when serious, and The important propagating source of disease can be become, human health is endangered.At the same time, coating material defines one in leather/fabric face Layer fine and close thin film, the perspiration that Severe blockage human body is distributed diffuse to the passage in the external world, cause the health of leather goods/textile Performance suffers extreme influence, and snugness of fit declines.In recent years, with the continuous improvement of human living standard, research and development are anti- Leather/weaving that bacterium property is prominent, sanitation performance is excellent is extremely urgent with coating material.
It is that target exploitation nano-ZnO and nanometer ZO/Ag are compound to improve the antibiotic property of polyacrylate coatings, sanitation performance The antibiotic property of particle, prevents coating breed bacteria, goes mouldy;It is huge using nanometer ZO and nano-ZnO/Ag compound particles Specific surface area, improves the sanitation performance of coating.
Nano material itself has the features such as size is little, and surface energy is high, is thus susceptible to reunion, bad dispersibility.In addition, receiving In the preparation process of nano composite material, nano material is poor with the affinity of the relatively low polymeric matrix of surface energy, and the two mutually mixes It is difficult to compatible during conjunction, space easily occurs in interface, there is phenomenon of phase separation.In order that nano material is evenly dispersed in polymer matrix It is in body, essential to its modifying surface.
The content of the invention
The object of the invention is exactly for the defect for making up prior art, there is provided a kind of antistatic antibiotic leather coating and its system Preparation Method.
The present invention is achieved by the following technical solutions:
A kind of antistatic antibiotic leather coating, it is made up of the raw material of following weight parts:
Beta-hydroxy alkylamide 0.1-0.3, polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, stannous chloride 1.6-2, three Ethanolamine 0.1-0.13, methyl methacrylate 190-200, sodium lauryl sulphate 3-4, hexamethylenamine 0.1-0.2, persulfuric acid Formalin 6-7 of ammonium 0.2-0.3,20-25%, zinc acetate 16-20, silver nitrate 4-7, dodecyldimethylammonium hydroxide inner salt 0.7- 1st, phthalic anhydride 0.8-1, chlorine dimethyl phthalate 0.1-0.2, copper 8-quinolinolate 0.3-1, Sucrose acetoisobutyrate 0.2-0.3, polycarboxylic acids sodium 1-2.
A kind of preparation method of described antistatic antibiotic leather coating, comprises the following steps:
(1)Above-mentioned zinc acetate, hexamethylenamine are mixed, is added in the deionized water of compound weight 60-100 times, stirring is equal It is even, it is liquid a;
(2)Above-mentioned dodecyldimethylammonium hydroxide inner salt, beta-hydroxy alkylamide are mixed, compound weight 10-17 times is added to In deionized water, stir, obtain antistatic solution;
(3)Above-mentioned polyvinylpyrrolidone, copper 8-quinolinolate are mixed, compound weight 20-30 times, 70-75% is added to Ethanol solution in, stir, mix with above-mentioned liquid a, ultrasonic 20-30 minutes, be sent in ptfe autoclave, Microwave hydrothermal 20-30 minutes at 160-170 DEG C, room temperature is cooled to, filters, precipitate with deionized water, ethanol are washed into 3-4 successively It is secondary, it is placed in baking oven, is dried, obtains modified zinc oxide;
(4)Above-mentioned modified zinc oxide, stannous chloride are mixed, is added in the dehydrated alcohol of compound weight 100-120 times, surpassed Sound 3-5 minutes, above-mentioned silver nitrate, triethanolamine are added, is stirred, the formalin of the above-mentioned 20-25% of Deca, completion of dropping After be centrifuged off supernatant, precipitate with deionized water, ethanol are washed 3-4 time successively, are placed in baking oven, at 90-100 DEG C do Dry 10-17 minutes, obtain Ag doping modified zinc oxide;
(5)Above-mentioned polyacrylamide is added in the deionized water of its weight 80-100 times, is stirred, add acetic acid or ammonia Water, regulation pH are 6-7, add above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minutes, obtain modified dispersion liquid;
(6)Above-mentioned Ammonium persulfate. is added in the deionized water of its weight 17-20 times, is stirred;
(7)Above-mentioned modified dispersion liquid, antistatic solution are mixed, are stirred, add polycarboxylic acids sodium, sodium lauryl sulphate, The insulated and stirred 3-4 minute at 50-60 DEG C, chlorine dimethyl phthalate, the 60-70% of above-mentioned methyl methacrylate weight are added, risen High-temperature is 76-80 DEG C, insulated and stirred 10-14 minute, and the remaining methyl methacrylate of Deca and Ammonium persulfate. are water-soluble respectively Liquid, insulation reaction 120-130 minute after completion of dropping, discharging add remaining each raw material, stir to room temperature, obtain the coating.
A kind of described antistatic antibiotic leather coating, the using method of the coating is:Using the front coating by the present invention Supersound process 20-30 minute, be sprayed at leather surface under the pressure of 0.2MPa with spray gun, normal temperature drying, 76-80 DEG C, Press under conditions of 80bar, spray the coating of the present invention, normal temperature drying afterwards again, you can.
It is an advantage of the invention that:Zinc oxide particles are evenly dispersed into the present invention ethanol solution of stannous chloride first In, Sn2+ will promptly be adsorbed onto zinc oxide surface;Then, the ethanol solution of Ag (TEA) 2+ is added in above-mentioned reactant liquor, Sn2+ can occur ion-exchange reactionss with Ag (TEA) 2+ for adding so that Ag+ absorption forms silver-colored kind in zinc oxide surface;Reaction In the later stage, gradually Deca formalin persistently stir in solution, make Ag be reduced into Ag granules;
ZnO/Ag compound particles resistance to water of the present invention itself preferably, can effectively prevent water in being introduced into polyacrylate Molecule infiltration is in thin film, and then the water absorption rate of reduction laminated film, improves its resistance to water;
ZnO/Ag compound particles of the present invention have good anti-microbial property, and under illumination condition, ZnO surfaces produce substantial amounts of Electronics and hole, the electronics that nanometer Ag capture is generated, obtain Ag-, and then, Ag- is reacted with the oxygen molecule of ZnO surface adsorption, raw Into superoxide ion;Superoxide ion is further reacted with water, generates perhydroxyl radical and hydrogen peroxide;The H2O of hole and ZnO surface adsorption or HO- ionic reactions, form the activity hydroxy with strong oxidizing property, and activity hydroxy mutually merges generation hydrogen peroxide.Activity hydroxy Oxidability is most strong, many Organic substances of can degrading in water body oxidant;Additionally, oxidant superoxide ion, hydrogen peroxide, mistake Hydroxyl etc. can destroy biological cell by the effect of the biomacromolecules such as oxidation reaction and protein, enzyme, lipid and nucleic acid Structure, so as to kill antibacterial.In course of reaction, silver ion plays catalytic active center, and itself does not consume.Nanometer Ag As granularity is minimum, specific surface area big, surface energy is higher, is easily adsorbed by various antibacterials, so just constrains the work of antibacterial It is dynamic, the disorderly imbalance of living environment of antibacterial is made, is suppressed which to breathe, is ultimately resulted in antibacterial and " contact is dead " occurs.
After there is the coating of the present invention good antibiotic property, excellent water vapor permeability and resistance to water, gained emulsion to cover with paint, lacquer, colour wash, etc. Leather antibacterial is good, sanitation performance is excellent.Present invention adds dodecyldimethylammonium hydroxide inner salt etc., effectively raises into The antistatic property of product coating.
Specific embodiment
A kind of antistatic antibiotic leather coating, it is made up of the raw material of following weight parts:
β hydroxyalkyl amides 0.1, polyvinylpyrrolidone 1.7, polyacrylamide 0.8, stannous chloride 1.6, triethanolamine 0.1, first Base acrylic acid methyl ester. 190, sodium lauryl sulphate 3, hexamethylenamine 0.1, the formalin 6, zinc acetate of Ammonium persulfate. 0.2,20% 16th, silver nitrate 4, dodecyldimethylammonium hydroxide inner salt 0.7, phthalic anhydride 0.8, chlorine dimethyl phthalate 0.1,8 hydroxyquinoline Copper 0.3, Sucrose acetoisobutyrate 0.2, polycarboxylic acids sodium 1.
A kind of preparation method of described antistatic antibiotic leather coating, comprises the following steps:
(1)Above-mentioned zinc acetate, hexamethylenamine are mixed, is added in the deionized water of 60 times of compound weight, is stirred, be Liquid a;
(2)By above-mentioned dodecyldimethylammonium hydroxide inner salt, β hydroxyalkyl amides mix, be added to 10 times of compound weight go from In sub- water, stir, obtain antistatic solution;
(3)Above-mentioned polyvinylpyrrolidone, 8 copper quinolinates are mixed, 20 times of compound weight, 70% ethanol is added to In solution, stir, mix with above-mentioned liquid a, ultrasound 20 minutes is sent in ptfe autoclave, micro- at 160 DEG C Ripple hydro-thermal 20 minutes, is cooled to room temperature, filters, precipitate with deionized water, ethanol is washed 3 times successively, is placed in baking oven, does It is dry, obtain modified zinc oxide;
(4)Above-mentioned modified zinc oxide, stannous chloride are mixed, is added in the dehydrated alcohol of 100 times of compound weight, ultrasound 3 Minute, above-mentioned silver nitrate, triethanolamine being added, is stirred, the formalin of Deca above-mentioned 20%, centrifugation after completion of dropping are removed Supernatant is removed, precipitate with deionized water, ethanol is washed 3 times successively, is placed in baking oven, be dried 10 minutes at 90 DEG C, obtain silver-colored Doping vario-property Zinc Oxide;
(5)Above-mentioned polyacrylamide is added in the deionized water of 80 times of its weight, is stirred, add acetic acid or ammonia, It is 6 to adjust pH, adds above-mentioned Ag doping modified zinc oxide, ultrasound 20 minutes to obtain modified dispersion liquid;
(6)Above-mentioned Ammonium persulfate. is added in the deionized water of 17 times of its weight, is stirred;
(7)Above-mentioned modified dispersion liquid, antistatic solution are mixed, are stirred, add polycarboxylic acids sodium, sodium lauryl sulphate, Insulated and stirred 3 minutes at 50 DEG C, add chlorine dimethyl phthalate, the 60% of above-mentioned methyl methacrylate weight, rise high-temperature be 76 DEG C, insulated and stirred 10 minutes, the remaining methyl methacrylate of Deca and ammonium persulfate aqueous solution, protect after completion of dropping respectively Temperature reaction 120 minutes, discharging add remaining each raw material, stir to room temperature, obtain the coating.
A kind of described antistatic antibiotic leather coating, the using method of the coating is:Using the front coating by the present invention Supersound process 20 minutes, is sprayed at leather surface, normal temperature drying, in 76 DEG C, the bar of 80bar under the pressure of 0.2MPa with spray gun Press under part, spray the coating of the present invention, normal temperature drying afterwards again, you can.
Performance test:
Leather after liquid is covered with paint, lacquer, colour wash, etc. is 96.33% to the bacteriostasis rate of Candida albicans, is 80.0% to the bacteriostasis rate of mycete.

Claims (3)

1. a kind of antistatic antibiotic leather coating, it is characterised in that it is made up of the raw material of following weight parts:
Beta-hydroxy alkylamide 0.1-0.3, polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, stannous chloride 1.6-2, three Ethanolamine 0.1-0.13, methyl methacrylate 190-200, sodium lauryl sulphate 3-4, hexamethylenamine 0.1-0.2, persulfuric acid Formalin 6-7 of ammonium 0.2-0.3,20-25%, zinc acetate 16-20, silver nitrate 4-7, dodecyldimethylammonium hydroxide inner salt 0.7- 1st, phthalic anhydride 0.8-1, chlorine dimethyl phthalate 0.1-0.2, copper 8-quinolinolate 0.3-1, Sucrose acetoisobutyrate 0.2-0.3, polycarboxylic acids sodium 1-2.
2. a kind of preparation method of antistatic antibiotic leather coating as claimed in claim 1, it is characterised in that including following step Suddenly:
(1)Above-mentioned zinc acetate, hexamethylenamine are mixed, is added in the deionized water of compound weight 60-100 times, stirring is equal It is even, it is liquid a;
(2)Above-mentioned dodecyldimethylammonium hydroxide inner salt, beta-hydroxy alkylamide are mixed, compound weight 10-17 times is added to In deionized water, stir, obtain antistatic solution;
(3)Above-mentioned polyvinylpyrrolidone, copper 8-quinolinolate are mixed, compound weight 20-30 times, 70-75% is added to Ethanol solution in, stir, mix with above-mentioned liquid a, ultrasonic 20-30 minutes, be sent in ptfe autoclave, Microwave hydrothermal 20-30 minutes at 160-170 DEG C, room temperature is cooled to, filters, precipitate with deionized water, ethanol are washed into 3-4 successively It is secondary, it is placed in baking oven, is dried, obtains modified zinc oxide;
(4)Above-mentioned modified zinc oxide, stannous chloride are mixed, is added in the dehydrated alcohol of compound weight 100-120 times, surpassed Sound 3-5 minutes, above-mentioned silver nitrate, triethanolamine are added, is stirred, the formalin of the above-mentioned 20-25% of Deca, completion of dropping After be centrifuged off supernatant, precipitate with deionized water, ethanol are washed 3-4 time successively, are placed in baking oven, at 90-100 DEG C do Dry 10-17 minutes, obtain Ag doping modified zinc oxide;
(5)Above-mentioned polyacrylamide is added in the deionized water of its weight 80-100 times, is stirred, add acetic acid or ammonia Water, regulation pH are 6-7, add above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minutes, obtain modified dispersion liquid;
(6)Above-mentioned Ammonium persulfate. is added in the deionized water of its weight 17-20 times, is stirred;
(7)Above-mentioned modified dispersion liquid, antistatic solution are mixed, are stirred, add polycarboxylic acids sodium, sodium lauryl sulphate, The insulated and stirred 3-4 minute at 50-60 DEG C, chlorine dimethyl phthalate, the 60-70% of above-mentioned methyl methacrylate weight are added, risen High-temperature is 76-80 DEG C, insulated and stirred 10-14 minute, and the remaining methyl methacrylate of Deca and Ammonium persulfate. are water-soluble respectively Liquid, insulation reaction 120-130 minute after completion of dropping, discharging add remaining each raw material, stir to room temperature, obtain the coating.
3. a kind of antistatic antibiotic leather coating according to claim 1,2, it is characterised in that the using method of the coating For:Using the front coating supersound process 20-30 minute by the present invention, leather table is sprayed under the pressure of 0.2MPa with spray gun Face, normal temperature drying, under conditions of 76-80 DEG C, 80bar press, spray again afterwards the present invention coating, normal temperature drying, i.e., Can.
CN201610975146.7A 2016-11-07 2016-11-07 Anti-static anti-microbial leather coating and preparation method thereof Withdrawn CN106566351A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023131855A1 (en) * 2022-01-05 2023-07-13 SCG Chemicals Public Company Limited Antimicrobial composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105925099A (en) * 2016-05-11 2016-09-07 滁州职业技术学院 Anti-flaming antisepsis leather coating and preparation method thereof
CN105936788A (en) * 2016-05-11 2016-09-14 滁州职业技术学院 Self-cleaning antibiosis leather coating and preparation method thereof
CN106010213A (en) * 2016-07-13 2016-10-12 蚌埠市正园电子科技有限公司 Anti-static water-based polyester coating and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105925099A (en) * 2016-05-11 2016-09-07 滁州职业技术学院 Anti-flaming antisepsis leather coating and preparation method thereof
CN105936788A (en) * 2016-05-11 2016-09-14 滁州职业技术学院 Self-cleaning antibiosis leather coating and preparation method thereof
CN106010213A (en) * 2016-07-13 2016-10-12 蚌埠市正园电子科技有限公司 Anti-static water-based polyester coating and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023131855A1 (en) * 2022-01-05 2023-07-13 SCG Chemicals Public Company Limited Antimicrobial composition

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