CN105256578A - Waterborne three-proofing leather finishing agent and using method thereof - Google Patents
Waterborne three-proofing leather finishing agent and using method thereof Download PDFInfo
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- CN105256578A CN105256578A CN201510759677.8A CN201510759677A CN105256578A CN 105256578 A CN105256578 A CN 105256578A CN 201510759677 A CN201510759677 A CN 201510759677A CN 105256578 A CN105256578 A CN 105256578A
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Abstract
The invention provides a waterborne three-proofing leather finishing agent and a using method thereof. The finishing agent is prepared from a waterborne fluorine-containing or silicon-containing acrylic brush-shaped polymer with low surface energy, or a fluorine-containing or silicon-containing linear polymer containing hydroxyl reactivity groups, or a waterborne acrylic polymer or a waterborne polyurethane polymer, a waterborne cross-linking agent and a coalescing agent. A water dispersing system of the waterborne three-proofing leather finishing agent is environmentally friendly and safe, sources of the raw materials are wide, a preparing method for three-proofing leather is simple and easy to implement, and the prepared three-proofing leather has excellent waterproof, oil-proof and antifouling performance and smooth hand feeling; in addition, the gloss style of the three-proofing leather can be regulated and controlled by means of system compositions, and the three-proofing leather finishing agent, the related matching technology and three-proofing leather products have remarkable application prospects and considerable economic benefits.
Description
Technical field
The present invention relates to leather finish field, refer in particular to a kind of water dispersible anti-leather finishing agent of water-based three with waterproof, antifouling, anti-graffiti function, also relate to the using method of the anti-leather finishing agent of water-based three.
Background technology
Super-hydrophobic super oleophobic material is study hotspot in recent years, has Tuteja (Science, 2007 of the Massachusetts Institute of Technology in the world, 318,1618), Aizenberg (NATCOMMUN, 2013 of Harvard University, 4,2167), Vollmer (Science, 2012 of macromolecule research institute of MPG, 335,67; NATCOMMUN, 2013,4,2512), Parkin (Science, 2015,347 of London university, 1132), the Liu Guojun of Queen's University of Canada, the woods of Australian Deakin University is virgin, the Law in Robert Webster Xerox of U.S. research center, the Hozumi of the advanced industrial science technical research institute of Japanese national, domestic Chinese Academy of Sciences chemistry a few group such as Jiang Lei achieve the synthetic work of super-hydrophobic super oleophobic material in laboratory.At present, super-hydrophobic super oleophobic material has certain Research foundation, but does not derive Related product or industrialization technology yet.Hinder this class novel materials to transform in numerous areas application study and correlation technique and mainly contain three problems, one is that coating surface often has meticulous micro nano structure, is easy to wearing and tearing and loses super-hydrophobic super oleophobic performance; Two is due to system hydrophobic oleophobic, general use expensive have again certain toxicity containing fluorous solvent as decentralized medium; Three is that super-hydrophobic oleophobic feature makes there is more weak tack between this type coating material and substrate.
Summary of the invention
The present invention proposes the anti-leather finishing agent of a kind of water-based three and using method thereof, solves the defect being easy to wear and tear, toxic, tack is more weak that finishing agent in prior art exists.
Technical scheme of the present invention is achieved in that the anti-leather finishing agent of a kind of water-based three comprises following raw material: the fluorine-containing or siliceous linear polymer of the aqueous fluorine-containing of low-surface-energy or acrylate containing silicone class scopiform polymer, hydroxyl reactive group, water soluble acrylic acid esters polymer or aqueous polyurethane base polymer, water cross-linking agent and coalescents.
Preferably, the aqueous fluorine-containing of described low-surface-energy or acrylate containing silicone class scopiform polymer are the polymer obtained by solution free radical polymerization or emulsion polymerisation by vinyl monomer, described vinyl monomer comprises low-surface-energy monomer A and comonomer B, described low-surface-energy monomer A is vinyl fluorochemical monomer or vinyl silicon-containing monomer, described vinyl fluorochemical monomer comprises perfluoroalkyl (butyl, hexyl, octyl group or decyl) acrylate, methyl perfluoro alkyl (butyl, hexyl, octyl group or decyl) acrylate, trifluoroethyl methacrylate, acrylic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, one or more in methacrylic acid ten trifluoro monooctyl ester, described vinyl silicon-containing monomer comprises the different methoxy silane of vinyl three, the different Ethoxysilane of vinyl three, vinyl silane triisopropoxide, Deng one or more in vinyl silicon-containing monomer, described comonomer B comprise in acrylic acid, methacrylic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, octadecyl acrylate, octadecyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methylacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, isobornyl acrylate, styrene one or more.
Preferably, the fluorine-containing or siliceous linear polymer of described hydroxyl reactive group comprises one or more in the fluorochemical polyether of fluorinated hydroxy polyethers, hydroxyl polysiloxane and water-solubility modifying or polysiloxanes.
Preferably, described water cross-linking agent is through hydroxy polyethers (molecular weight 100-2000), the finally water dispersible isocyanate ester compound that the hydrophilic compounds such as methyl diethanolamine, dihydromethyl propionic acid, dimethylolpropionic acid are modified or the isocyanate ester compound adopting methyl ethyl ketoxime end-capping reagent to close, described isocyanate ester compound comprises toluene di-isocyanate(TDI) (TDI), ditolylmethane vulcabond (MDI), naphthalene diisocyanate (NDI), PPDI (PPDI), dimethyl diphenyl vulcabond (TODI), polymethylene multi-phenenyl isocyanate (PAPI), 1, 6-hexamethylene diisocyanate (HDI), trimethyl-1, 6-hexamethylene diisocyanate (m-TMXDI), isoflurane chalcone diisocyanate (IPDI), 1, 4-cyclohexane diisocyanate (CHDI), dicyclohexyl vulcabond (H
12mDI) one or more, in Methylcyclohexyl diisocyanate (HTDI), cyclohexanedimethyleterephthalate vulcabond (HXDI), norbornene alkyl diisocyanate (NB-DI), HDI tripolymer.
Preferably, described water soluble acrylic acid esters polymer comprises the polymer obtained by polymerisation in solution or emulsion polymerisation by described comonomer B, described aqueous polyurethane base polymer is the water dispersible aqueous polyurethane base polymer that soft section of compound and hydrophilic compounds are obtained by reacting, described soft section of compound comprise in described isocyanate ester compound, polyether Glycols or polyalcohol, polyester polyol one or more, hydrophilic compounds comprise in methyl diethanolamine, dihydromethyl propionic acid, dimethylolpropionic acid one or more.
Preferably, described coalescents comprises one or more and the cosolvent in dibutyltin dilaurate, triethylenediamine, two (dimethylaminoethyl) ether and hydroxyl and isocyano has been reacted to the compound of catalytic action; Described cosolvent comprise in MEK, acetone, ethyl acetate, butyl acetate, toluene, dimethyl formamide, glycol ethers, oxolane, dioxane and halogenated hydrocarbons one or more.
Preferably, the aqueous fluorine-containing of described low-surface-energy or acrylate containing silicone class scopiform polymer account for the 1-50wt% of the anti-leather finishing agent of described water-based three, fluorine-containing or the siliceous linear polymer of described hydroxyl reactive group accounts for the 0-20wt% of the anti-leather finishing agent of described water-based three, described water cross-linking agent accounts for the 0-80% of the anti-leather finishing agent of described water-based three, described water soluble acrylic acid esters polymer or aqueous polyurethane base polymer account for the 0-60wt% of the anti-leather finishing agent of described water-based three, and described coalescents accounts for the 0-50wt% of the anti-leather finishing agent of described water-based three.
The using method of the anti-leather finishing agent of a kind of water-based three, it is characterized in that: by spraying or dip-coating or blade coating, top layer coating is carried out to semifinished leather products by after anti-for described water-based three leather finishing agent dilute with water, then to leather coating carry out 130 DEG C ~ 170 DEG C be time 1min ~ 10min oven dry be cross-linked film forming.
Beneficial effect of the present invention is: water-based three anti-leather finishing agent aqueous dispersion Environmental Safety, raw material sources are extensive, the preparation method of three anti-leathers is simple, three anti-leathers of preparation have excellent waterproof, grease proofing and antifouling property have smooth feel, the gloss style of other three anti-leathers is by the regulation and control of system composition, and three anti-leather finishing agents and relevant supporting technology and three anti-leather products have significant application prospect and considerable economic benefit.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the coating conditions of aqueous anti-doodling leather finishing agent on glass, and can find out that coating is completely transparent, permanent pen can not leave pen touch in coating.
Fig. 2 is the coated leather of aqueous anti-doodling leather finishing agent, and can find out, ball pen or permanent pen leather is after application write, and vestige can be wiped completely with common paper handkerchief.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The present invention adopts Industrial raw material, deep design, transformation and perfect have been carried out to super-hydrophobic oleophobic polymeric system, successfully prepare the water dispersible polymer coating materials with waterproof, grease proofing, anti-graffiti function, and according to leather finish industry technique and performance requirement, have developed the anti-leather finishing agent of water-based three.Water-based three of the present invention anti-leather finishing agent aqueous dispersion Environmental Safety, raw material sources are extensive, the preparation method of three anti-leathers is simple, three anti-leathers of preparation have excellent waterproof, grease proofing and antifouling property have smooth feel, the gloss style of other three anti-leathers is by the regulation and control of system composition, and three anti-leather finishing agents and relevant supporting technology and three anti-leather products have significant application prospect and considerable economic benefit.
Embodiment 1: the anti-leather finishing agent A of water-based three
100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 50g fluorinated hydroxy polyethers, 50g water soluble acrylic acid esters polymer, 50g aqueous polyurethane base polymer, 100g water-based HDI tripolymer, 10g dibutyltin dilaurate, 50g acetone are mixed, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent A of water-based three.
Embodiment 2: the anti-leather finishing agent B of water-based three
100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 40g fluorinated hydroxy polyethers, 60g water soluble acrylic acid esters polymer, 40g aqueous polyurethane base polymer, 100g water-based HDI tripolymer, 5g dibutyltin dilaurate, 50g butyl acetate are mixed, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent B of water-based three.
Embodiment 3: the anti-leather finishing agent C of water-based three
100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 40g fluorinated hydroxy polyethers, 20g water soluble acrylic acid esters polymer, 100g water-based HDI tripolymer, 5g triethylenediamine, 50g butyl acetate are mixed, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent C of water-based three.
Embodiment 4: the anti-leather finishing agent D of water-based three
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 40g hydroxyl polysiloxanes, 20g water soluble acrylic acid esters polymer, 20g aqueous polyurethane base polymer, 50g water-based HDI tripolymer, 5g triethylenediamine, 50g butyl acetate mix, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent D of water-based three.
Embodiment 5: the anti-leather finishing agent E of water-based three
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 60g hydroxyl polysiloxanes, 20g water soluble acrylic acid esters polymer, 20g aqueous polyurethane base polymer, 100g water-based HDI tripolymer, 5g triethylenediamine, 50g butyl acetate mix, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent D of water-based three.
Embodiment 6: the anti-leather finishing agent F of water-based three
By 100g aqueous silicon-acrylate class scopiform polymer, 60g hydroxyl polysiloxanes, 20g water soluble acrylic acid esters polymer, 20g aqueous polyurethane base polymer, 100g water-based HDI tripolymer, 5g dibutyltin dilaurate, 50g butyl acetate mix, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent F of water-based three.
Embodiment 7: the anti-leather finishing agent G of water-based three
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 60g hydroxyl polysiloxanes, 20g aqueous polyurethane base polymer, 100g water-based HDI tripolymer, 5g dibutyltin dilaurate, 50g butyl acetate mix, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent F of water-based three.
Embodiment 8: the anti-leather finishing agent H of water-based three
By 100g aqueous silicon-acrylate class scopiform polymer, 60g fluorinated hydroxy polyethers, 20g aqueous polyurethane base polymer, 100g water-based HDI tripolymer, 5g dibutyltin dilaurate, 50g butyl acetate mix, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent H of water-based three.
Embodiment 9: the anti-leather finishing agent I of water-based three
By 100g aqueous silicon-acrylate class scopiform polymer, 60g fluorinated hydroxy polyethers, 20g aqueous polyurethane base polymer, 100g water-based HDI tripolymer, 5g triethylenediamine, 50g butyl acetate mix, adding water and being dispersed to solid content is 35%, obtains the anti-leather finishing agent I of water-based three.
Test one: coating transparent is tested
Adopt blade coating mode to be coated on slide anti-for water-based three leather finishing agent, adopt the transmitance of ultraviolet method testing coating, result display transmitance is up to 98.9%.Perusal coating is completely transparent.
Test two: leather anti-ball pen scribble performance after covering with paint, lacquer, colour wash, etc.
Adopt blade coating mode, leather is carried out to the top layer coating of the anti-leather finishing agent of water-based three, after surface drying, 140o dries crosslinked film forming 3min, and experimental result display ball pen leather is after application write, and vestige can be wiped completely with common paper handkerchief.
Test three: leather grease proofness marking pen scribble performance after covering with paint, lacquer, colour wash, etc.
Adopt blade coating mode, leather is carried out to the top layer coating of the anti-leather finishing agent of water-based three, after surface drying, 140o dries crosslinked film forming 3min, and experimental result display permanent pen leather is after application write, and vestige can be wiped completely with common paper handkerchief.
Test result as shown in Figure 1, 2.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. the anti-leather finishing agent of water-based three, is characterized in that comprising following raw material: the fluorine-containing or siliceous linear polymer of the aqueous fluorine-containing of low-surface-energy or acrylate containing silicone class scopiform polymer, hydroxyl reactive group, water soluble acrylic acid esters polymer or aqueous polyurethane base polymer, water cross-linking agent and coalescents.
2. the anti-leather finishing agent of water-based three as claimed in claim 1, is characterized in that: aqueous fluorine-containing or the acrylate containing silicone class scopiform polymer of described low-surface-energy are the polymer obtained by solution free radical polymerization or emulsion polymerisation by vinyl monomer, described vinyl monomer comprises low-surface-energy monomer A and comonomer B, described low-surface-energy monomer A is vinyl fluorochemical monomer or vinyl silicon-containing monomer, described vinyl fluorochemical monomer comprises perfluoroalkyl (butyl, hexyl, octyl group or decyl) acrylate, methyl perfluoro alkyl (butyl, hexyl, octyl group or decyl) acrylate, trifluoroethyl methacrylate, acrylic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, one or more in methacrylic acid ten trifluoro monooctyl ester, described vinyl silicon-containing monomer comprises the different methoxy silane of vinyl three, the different Ethoxysilane of vinyl three, vinyl silane triisopropoxide, Deng one or more in vinyl silicon-containing monomer, described comonomer B comprise in acrylic acid, methacrylic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, octadecyl acrylate, octadecyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methylacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, isobornyl acrylate, styrene one or more.
3. the anti-leather finishing agent of water-based three as claimed in claim 1, is characterized in that: the fluorine-containing or siliceous linear polymer of described hydroxyl reactive group comprise in the fluorochemical polyether of fluorinated hydroxy polyethers, hydroxyl polysiloxane and water-solubility modifying or polysiloxanes one or more.
4. the anti-leather finishing agent of water-based three as claimed in claim 2, it is characterized in that: described water cross-linking agent is through hydroxy polyethers (molecular weight 100-2000), the finally water dispersible isocyanate ester compound that the hydrophilic compounds such as methyl diethanolamine, dihydromethyl propionic acid, dimethylolpropionic acid are modified or the isocyanate ester compound adopting methyl ethyl ketoxime end-capping reagent to close, described isocyanate ester compound comprises toluene di-isocyanate(TDI) (TDI), ditolylmethane vulcabond (MDI), naphthalene diisocyanate (NDI), PPDI (PPDI), dimethyl diphenyl vulcabond (TODI), polymethylene multi-phenenyl isocyanate (PAPI), 1, 6-hexamethylene diisocyanate (HDI), trimethyl-1, 6-hexamethylene diisocyanate (m-TMXDI), isoflurane chalcone diisocyanate (IPDI), 1, 4-cyclohexane diisocyanate (CHDI), dicyclohexyl vulcabond (H
12mDI) one or more, in Methylcyclohexyl diisocyanate (HTDI), cyclohexanedimethyleterephthalate vulcabond (HXDI), norbornene alkyl diisocyanate (NB-DI), HDI tripolymer.
5. the anti-leather finishing agent of water-based three as claimed in claim 4, it is characterized in that: described water soluble acrylic acid esters polymer comprises the polymer obtained by polymerisation in solution or emulsion polymerisation by described comonomer B, described aqueous polyurethane base polymer is the water dispersible aqueous polyurethane base polymer that soft section of compound and hydrophilic compounds are obtained by reacting, described soft section of compound comprises described isocyanate ester compound, polyether Glycols or polyalcohol, one or more in polyester polyol, hydrophilic compounds comprises methyl diethanolamine, dihydromethyl propionic acid, one or more in dimethylolpropionic acid.
6. the anti-leather finishing agent of water-based three as claimed in claim 1, is characterized in that: described coalescents comprises one or more and the cosolvent in dibutyltin dilaurate, triethylenediamine, two (dimethylaminoethyl) ether and hydroxyl and isocyano reacted to the compound of catalytic action; Described cosolvent comprise in MEK, acetone, ethyl acetate, butyl acetate, toluene, dimethyl formamide, glycol ethers, oxolane, dioxane and halogenated hydrocarbons one or more.
7. the anti-leather finishing agent of water-based three as described in claim 1-6, it is characterized in that: the aqueous fluorine-containing of described low-surface-energy or acrylate containing silicone class scopiform polymer account for the 1-50wt% of the anti-leather finishing agent of described water-based three, fluorine-containing or the siliceous linear polymer of described hydroxyl reactive group accounts for the 0-20wt% of the anti-leather finishing agent of described water-based three, described water cross-linking agent accounts for the 0-80% of the anti-leather finishing agent of described water-based three, described water soluble acrylic acid esters polymer or aqueous polyurethane base polymer account for the 0-60wt% of the anti-leather finishing agent of described water-based three, described coalescents accounts for the 0-50wt% of the anti-leather finishing agent of described water-based three.
8. one kind as arbitrary in claim 1-7 as described in the using method of the anti-leather finishing agent of water-based three, it is characterized in that: by spraying or dip-coating or blade coating, top layer coating is carried out to semifinished leather products by after anti-for described water-based three leather finishing agent dilute with water, then to leather coating carry out 130 DEG C ~ 170 DEG C be time 1min ~ 10min oven dry be cross-linked film forming.
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| CN105837736A (en) * | 2016-06-19 | 2016-08-10 | 王金明 | Preparation method of cold-resistant leather coating agent |
| CN105970630A (en) * | 2016-07-20 | 2016-09-28 | 安徽贵谷电子商务有限公司 | Anti-staining down jacket fabric |
| CN106221473A (en) * | 2016-08-29 | 2016-12-14 | 四川达威科技股份有限公司 | A kind of composite resin and preparation method thereof |
| CN107177706A (en) * | 2017-06-07 | 2017-09-19 | 海宁瑞星皮革有限公司 | A kind of preparation method for cleaning three proofings ox head layer glove leather |
| CN108148509A (en) * | 2017-11-17 | 2018-06-12 | 孝感市锐思新材科技有限公司 | A kind of preparation method of leather polishing new material |
| CN108504269A (en) * | 2018-03-26 | 2018-09-07 | 华南理工大学 | A kind of floride-free nonpolluting coating and preparation method thereof of ultraviolet light/sun light curable |
| CN109182622A (en) * | 2018-08-09 | 2019-01-11 | 广州市迪孚卡乐进出口贸易有限公司 | A kind of corium nursing waterproof film forming agent and preparation method thereof |
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| CN111786016A (en) * | 2019-04-03 | 2020-10-16 | 深圳格林德能源集团有限公司 | Fluorine-containing polyurethane solid composite electrolyte and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107177706A (en) * | 2017-06-07 | 2017-09-19 | 海宁瑞星皮革有限公司 | A kind of preparation method for cleaning three proofings ox head layer glove leather |
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| CN108504269A (en) * | 2018-03-26 | 2018-09-07 | 华南理工大学 | A kind of floride-free nonpolluting coating and preparation method thereof of ultraviolet light/sun light curable |
| CN109182622A (en) * | 2018-08-09 | 2019-01-11 | 广州市迪孚卡乐进出口贸易有限公司 | A kind of corium nursing waterproof film forming agent and preparation method thereof |
| CN109182622B (en) * | 2018-08-09 | 2021-02-26 | 广州市迪孚卡乐进出口贸易有限公司 | Leather care waterproof film forming agent and preparation method thereof |
| CN111786016A (en) * | 2019-04-03 | 2020-10-16 | 深圳格林德能源集团有限公司 | Fluorine-containing polyurethane solid composite electrolyte and preparation method thereof |
| CN111786016B (en) * | 2019-04-03 | 2021-08-03 | 深圳格林德能源集团有限公司 | Fluorine-containing polyurethane solid composite electrolyte and preparation method thereof |
| CN111235879A (en) * | 2020-03-10 | 2020-06-05 | 湖南再红湘绣有限公司 | Preparation method of silk-woven fabric for Hunan embroidery |
| CN114134257A (en) * | 2021-11-10 | 2022-03-04 | 中牛集团有限公司 | Production method of high-grade antibacterial cow leather silica gel leather |
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