CN103290701A - Clean production process for polyurethane synthetic leather base with ultramicro leather powder as filling material - Google Patents
Clean production process for polyurethane synthetic leather base with ultramicro leather powder as filling material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 6
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- QRCHOJSRGDNGHR-UHFFFAOYSA-N n'-octadecylbutanediamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCC(N)=O QRCHOJSRGDNGHR-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a clean production process for a polyurethane synthetic leather base with ultramicro leather powder as a filling material. The process comprises the following steps: introducing air and water-based finishing slurry blended with ultramicro leather powder into a mixer according to a certain proportion and allowing a high-quality micro-foaming finishing agent to be formed under high-speed dispersion action of a stirring head; and coating the micro-foaming finishing agent and then drying and curing the micro-foaming finishing agent so as to prepare the synthetic leather base. The method provided by the invention has the advantages of simple preparation, easy control and the like, eliminates pollution of dimethyl formamide (DMF) produced in a wet production method for synthetic leather and reduces pollution of the industry of synthetic leather; and introduction of the natural ultramicro leather powder enables moisture and air permeability of polyurethane synthetic leather to be improved.
Description
Technical field
The present invention relates to the production technology of synthetic leather, specifically be a kind of be the process for cleanly preparing of the Synthetic Leather base (bottom) of filler with ultra micro leather powder.
Background technology
Synthetic leather is institutional framework and the serviceability of simulation natural leather, and can be used as the composite of the substitute of natural leather.Be widely used in and make footwear, boots, case and bag and ball etc.
To 500 many enterprises output statistics more than the synthetic leather industry size, reach 241 ten thousand ton in 2011 according to State Statistics Bureau, close 4,300,000,000 square metres, wherein Synthetic Leather is 2,800,000,000 square metres, realize more than 1,000 hundred million yuan of total industrial output values, increase by 9.57% on a year-on-year basis, production rank the first in the world.China has become in the world synthetic leather and has produced first big country, consumption big country and foreign trade big country.
At present, the PU synthetic leather mainly adopts solvent type production technology, and technological process is: non-weaving cloth → solvent borne polyurethane wet method gel coating (bottom) → washing → drying → solvent borne polyurethane dry method is moved membrane coat (surface layer) → finishing.Wet process technique is to use dimethyl formamide (DMF) solution of resin that nonwoven fabric or felt are handled, and re-uses water displacement dimethyl formamide (DMF) and forms loose structure.
The wet processing production process can produce dimethyl formamide (DMF) waste water.From survey data, the rate of recovery 90% of DMF has that 10% dimethyl formamide (DMF) is decomposed, the environment that enters such as residual.The wet processing production process can produce DMF waste water, gentle line waste water and sanitary wastewater, also has the waste residues such as industrial leftover bits and pieces that produce in the residual and production process of the still that produces in the recovery system.Dimethyl formamide (DMF) can be invaded body through respiratory tract, skin and alimentary canal, causes toxic reaction.During the PU synthetic leather is produced, all adopt the PU resin of organic solvent as basic unit and the surface layer of producing the leather product, such PU resin all makes by polymerization as primary solvent with toluene, dimethylbenzene, acetone, butanone (MEK), ethyl acetate and dimethyl formamide (DMF) etc.These solvents, toxic and side effect is big, not only causes environmental pollution, and the harm health is and inflammable and explosive, very easily accident such as initiation fire.
Synthetic leather is the industry that certain pollution is arranged, and all can produce environmental contaminants in production process, corollary apparatus and the product depth processing procedure of product, and a large amount of pollutants is discharged among the environment, and environmental problem highlights day by day.If can realize in synthetic leather is produced that pollutant reduces, will vacate huge environmental carrying capacity on the one hand, the sector is done more; On the other hand, will reduce cost significantly, increase economic benefit of enterprises, strengthen the market competitiveness of enterprise, and make the sector do byer force.Therefore, in the fast development of synthetic leather industry, how to realize the reduction of synthetic leather industry pollutant, not only concerning existence, the development of synthetic leather industry, also substantial connection regional economy sustainable development, is a reality and urgent subject.
In the process hides process, operations such as shaving, deburring can produce a large amount of leather solid waste.Data shows that the annual leather processing procedure of China produces 1,500,000 tons leather solid waste.If these solid waste can't effectively be handled, then both taken the place, polluted environment again, also be simultaneously the significant wastage to resource.The leather solid waste is carried out pulverization process through centrifugal mill and is obtained ultra micro leather powder.The ultra micro leather powder that obtains with ultramicro grinding leather solid waste is main raw material, utilizes maleic anhydride, maleic acid anhydride-propenoic acid graft modification, has obtained the ultra micro leather powder (prior art) of stable performance.
Summary of the invention
The objective of the invention is to adopt natural ultra micro leather powder is filler, a kind of process for cleanly preparing based on the Synthetic Leather base is provided, eliminate the pollution of dimethyl formamide (DMF) in the synthetic leather wet process technique, reduce the pollution of synthetic leather industry, improve vapor pervious and the gas permeability of synthetic leather.
Technical scheme of the present invention is: a kind of is the process for cleanly preparing of the Synthetic Leather base of filler with ultra micro leather powder, it is characterized in that,
(1) preparation is mixed with the water-based covering with paint slurry of ultra micro leather powder;
(2) the little foaming finishing agent of preparation: described water-based is covered with paint, lacquer, colour wash, etc. slurry be processed as little foaming finishing agent;
(3) be coated with base: apply little foaming finishing agent layer and dry slaking, make the synthetic leather base.
Composition and content that described water-based is covered with paint, lacquer, colour wash, etc. slurry are: waterborne film-forming agent 45-65%, aqueous foaming agent 1-3%, aqueous foam stabilizing agent 1-3%, ultra micro leather powder 10-18%, water-based filler 8-15%, mill base 5-20%, crosslinking agent 1-5%, surplus is auxiliary agents such as levelling agent, delustering agent, softener, casein liquid, antitack agent.
Described auxiliary agent comprises more than one in levelling agent, delustering agent, softener, casein liquid and the antitack agent.
Described waterborne film-forming agent comprises more than one in polyaminoester emulsion, emulsion acrylic resin, butadiene resin emulsion and the casein liquid.
Described aqueous foaming agent is more than one in anionic surfactant, cationic surface active agent and the nonionic surface active agent.
Described ultra micro leather powder is maleic anhydride modified ultra micro leather powder or/and maleic acid anhydride-propenoic acid modification ultra micro leather powder, and the particle diameter of this ultra micro leather powder is 30-80 μ m, more than one in the modification ultra micro leather powder.
Described aqueous foam stabilizing agent comprises more than one in polyvinyl alcohol, carboxyethyl cellulose, hydroxypropyl cellulose, soluble starch and the gelatin.
Described mill base, delustering agent, softener, casein liquid, antitack agent, crosslinking agent, levelling agent are water miscible.
Described crosslinking agent is: more than one in aziridines, isocyanates, the crosslinked worker's agent of amine.
Described little foaming finishing agent preparation method is: water-based covering with paint slurry and the air that will be mixed with ultra micro leather powder were imported mixing chamber in 1: 1～1: 5 by setting volume ratio, formed high-quality little foaming finishing agent under the high speed dispersion effect of stirring-head.
The described a kind of concrete technology that is coated with base is: by the double-pole doctor knife coater with little foaming finishing agent blade coating film forming, enter the dry slaking of drying tunnel then, by double-pole doctor knife coater blade coating film forming, enter the dry slaking of drying tunnel, the micro porous coating that forms surfacing at non-weaving cloth or knitted cloth is the Synthetic Leather base; Adopt the aqueous polyurethane slurry that roll coating process will contain aqueous polyurethane, thickener and levelling agent to be coated on above the polyurathamc bottom then, carry out drying by drying tunnel, form smooth smooth aqueous polyurethane superficial layer;
Another kind of concrete technology is: be coated with base little foaming finishing agent is coated on the release liners of motion with reversing rolling method or roller lining knife coating, advance dry solidification with baking oven; Be coated with again after the cooling and be covered with the bonding coat bed material, laminated on base cloth and solidified subsequently; After super-dry, cooling, peel off; Leather and release liners difference rolling; Last recycling flush coater carries out surface treatment, finally obtains the finished product synthetic leather.
The present invention is directed to the pollution problem that has DMF in the synthetic leather wet process technique, technology, the elimination synthetic leather primary pollution source that (DMF) cuts down is polluted in key breakthrough synthetic leather wet production source, realizes the synthetic leather cleaner production, development synthetic leather recycling economy; Ultra micro leather powder is applied to can increase substantially vapor pervious performance, the moisture absorption water vapour permeability of product in the Synthetic Leather processing, improves surperficial feel, give the performance of product section natural leather.Preparation technology is simple, production environment is friendly.
The specific embodiment
Contain physical foaming method in a kind of process for cleanly preparing based on Synthetic Leather base (bottom) of the present invention, required material comprises film forming agent, blowing agent, foam stabiliser mill base, ultra micro leather powder, filler etc.
The film forming agent polymer all can be done expanded material, and resin anion (R.A.), non-cationic resin, resin cation etc. are preferably resin anion (R.A.) and non-ionic resin, and the resin anion (R.A.) foam volume is better than non-ionic resin usually.As for kind such as acrylic resin, butadiene resin or the polyurethane resin etc. of polymer, or their mixture.
Blowing agent comprises anionic surfactant, cationic surfactant and non-ionic surface active agent.Anionic surfactant comprises alkyl carboxylate, alkyl sulfate salt, alkyl phosphate salt, alkylsulfonate etc.; Cationic surfactant comprises amine salt such as fatty amine salt, ethanolamine salt, polyethylene polyamines salt; Quaternary; Heterocyclic such as imidazoline, moroxydine class, triazine derivative; Ionic surfactant pack is drawn together polyoxyethylene-type, polyalcohol type, alkylolamides type etc.The preferential lauryl sodium sulfate of blowing agent (NaLS), neopelex (ABS), alkyl glycoside (APG), nonyl alcohol polyoxyethylene ether (AEO-9), paregal O, TX-10 etc.
Foam stabiliser comprises tackify type foam stabilisers such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), ammonium stearate, lauryl alcohol, N-octadecyl succinamide sulfonate.
Ultra micro leather powder is included as unmodified ultra micro leather powder, chlorobenzoyl chloride graft modification ultra micro leather powder, modified by maleic acid anhydride graft ultra micro leather powder, acrylic graft-modified ultra micro leather powder, polyurethane grafted modification ultra micro leather powder.
Except resin and blowing promotor, also can add other additive to improve the physical and mechanical properties of stackability, embossing and coating.These additives comprise: aqueous color paste, delustering agent, softener, casein liquid, antitack agent, crosslinking agent, levelling agent etc.
A kind of process for cleanly preparing process based on the Synthetic Leather base of the present invention is as follows:
At room temperature, the water-based of mixing is covered with paint, lacquer, colour wash, etc. slurry and air input mixer by a certain percentage, under the high speed dispersion effect of stirring-head, control about rotating speed 2000r/m in.The film forming agent resin that add to need bubbles at blender, aqueous color paste, blowing agent, foam stabiliser, delustering agent, softener, casein liquid, antitack agent, crosslinking agent, levelling agent etc., stir fast together, Foamex is emitted bubble, make volumetric expansion to original 1.5 times, can make the air that forms stable foam reach best distribution with fine particle.
The present invention is further described below in conjunction with two different implementing process.
The method that embodiment 1, the direct coating of employing are produced Synthetic Leather:
Technological process is:
1, the preparation of ultra micro leather powder: with scissors leather castoff is cut into earlier and is no more than 1cm
2The bulk of size, and then use centrifugal mill that leather castoff is carried out pulverization process.Utilize centrifugal mill high speed rotation of blade bump leather, and make between leather and the leather, produce high-speed impact between leather and the barrel and reach the purpose of pulverizing.Can obtain the ultra micro leather powder of 30～80 μ m through the pulverizing of centrifugal mill, to the powder graft modification of ultra micro leather or do not carry out graft modification, modification ultra micro leather powder adopts modified by maleic acid anhydride graft, belongs to prior art.
2, the little foaming finishing agent of preparation: 50 parts of polyurethane resins, 15 parts of aqueous color pastes, 15 parts in ultra micro leather powder, 2 parts of blowing agents, 2 parts of foam stabilisers, 3 parts of crosslinking agents, 1 part of levelling agent, 5 parts of delustering agents, 19 parts of softeners, 2 parts of antitack agents (being weight portion).The above water-based of mixing is covered with paint, lacquer, colour wash, etc. slurry and air by a certain percentage, volume ratio input in 1: 1～1: 5 mixing chamber, the high-quality foaming finishing agent of formation under the high speed dispersion effect of stirring-head.
3, priming operation: non-weaving cloth or knitted cloth are sent into the through type coating roller, in non-weaving cloth or the little foaming finishing agent of knitted cloth blade coating film forming, form bottom with the double-pole doctor knife coater.The speed of a motor vehicle that directly is coated with production line of through type coating roller is 8m/min.
4, bottom baking and curing: send into the dry slaking of drying tunnel, the drying tunnel temperature of slaking is 120 ℃.Then, adopt the through type rotary ironing machine to press non-weaving cloth or the knitted cloth that obtains having micro porous coating down at 150 ℃.
Embodiment 2, the indirect coating of employing are produced the Synthetic Leather technological process:
1, the preparation of ultra micro leather powder: with scissors it is cut into earlier and is no more than 1cm
2The bulk of size, and then use centrifugal mill that leather castoff is carried out pulverization process.Utilize centrifugal mill high speed rotation of blade bump leather, and make between leather and the leather, produce high-speed impact between leather and the barrel and reach the purpose of pulverizing.Can obtain the ultra micro leather powder of 30～80 μ m through the pulverizing of centrifugal mill, to the powder graft modification of ultra micro leather or do not carry out graft modification, modification ultra micro leather powder adopts maleic anhydride one acrylic graft-modified.
2, the little foaming finishing agent of preparation: 55 parts of polyurethane resins, 10 parts of aqueous color pastes, 20 parts in ultra micro leather powder, 2 parts of blowing agents, 2 parts of foam stabilisers, 3 parts of crosslinking agents, 1 part of levelling agent, 5 parts of delustering agents, 19 parts of softeners, 2 parts of antitack agents.The water-based of mixing is covered with paint, lacquer, colour wash, etc. slurry and air is imported mixing chamber by a certain percentage, forms high-quality foaming finishing agent under the high speed dispersion effect of stirring-head.
3, be coated with surface layer, surface layer oven dry: release liners is sent into the through type coating roller, by double-pole doctor knife coater blade coating foaming finishing agent film forming, enter the dry slaking of drying tunnel, form surface layer.The drying tunnel temperature of slaking is 120 ℃, and the speed of a motor vehicle that directly is coated with production line of through type coating roller is 8m/min.
4. non-weaving cloth or knitted cloth are sent into the through type coating roller, two shower nozzle feeding systems by compressed ir spray gun atomizing, spray to non-weaving cloth or above the knitted cloth, applied amounts is 120g/m with adhesive (the Impranil DLU of Bayer company)
2, entering the drying tunnel drying then, the drying tunnel temperature of slaking is 120 ℃, the speed of a motor vehicle that directly is coated with production line of through type coating roller is 8m/min.
5. laminatedly subsequently solidify fully on base cloth and in addition, peel off after super-dry, cooling, leather and release liners be rolling respectively.
6. then, adopt the through type rotary ironing machine to press non-weaving cloth or the knitted cloth that obtains having micro porous coating down at 150 ℃.
7. last, to have micro porous coating non-weaving cloth or knitted cloth and send into the through type coating roller, the logical coating roller that adopts is coated on film forming on the micro porous coating with waterborne polyurethane resin, enter the dry slaking of drying tunnel, the drying tunnel temperature of slaking is 80 ℃, finally carry out finishing, it is sent into the drying tunnel drying, obtain finished product after the drying.
Claims (10)
1. one kind is the process for cleanly preparing of the Synthetic Leather base of filler with ultra micro leather powder, it is characterized in that,
(1) preparation is mixed with the water-based covering with paint slurry of ultra micro leather powder;
(2) the little foaming finishing agent of preparation: described water-based is covered with paint, lacquer, colour wash, etc. slurry be processed as little foaming finishing agent;
(3) be coated with base: apply little foaming finishing agent layer and dry slaking, make the synthetic leather base,
Composition and content that described water-based is covered with paint, lacquer, colour wash, etc. slurry are: waterborne film-forming agent 45-65%, aqueous foaming agent 1-3%, aqueous foam stabilizing agent 1-3%, ultra micro leather powder 10-18%, water-based filler 8-15%, mill base 5-20%, crosslinking agent 1-5%, surplus is auxiliary agents such as levelling agent, delustering agent, softener, casein liquid, antitack agent.
2. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that described auxiliary agent comprises more than one in levelling agent, delustering agent, softener, casein liquid and the antitack agent.
3. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that described waterborne film-forming agent comprises more than one in polyaminoester emulsion, emulsion acrylic resin, butadiene resin emulsion and the casein liquid.
4. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that described aqueous foaming agent is more than one in anionic surfactant, cationic surface active agent and the nonionic surface active agent.
5. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that, described ultra micro leather powder is that maleic anhydride modified ultra micro leather powder is or/and maleic acid anhydride-propenoic acid modification ultra micro leather powder, the particle diameter of this ultra micro leather powder is 30-80 μ m, more than one in the modification ultra micro leather powder.
6. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that described aqueous foam stabilizing agent comprises more than one in polyvinyl alcohol, carboxyethyl cellulose, hydroxypropyl cellulose, soluble starch and the gelatin.
7. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that described mill base, delustering agent, softener, casein liquid, antitack agent, crosslinking agent, levelling agent are water miscible.
8. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that described crosslinking agent is: more than one in aziridines, isocyanates, the crosslinked worker's agent of amine.
9. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that, described little foaming finishing agent preparation method is: water-based covering with paint slurry and the air that will be mixed with ultra micro leather powder were imported mixing chamber in 1: 1～1: 5 by setting volume ratio, formed high-quality little foaming finishing agent under the high speed dispersion effect of stirring-head.
10. according to claim 1 is the Synthetic Leather base process for cleanly preparing of filler with ultra micro leather powder, it is characterized in that, the described a kind of concrete technology that is coated with base is: by the double-pole doctor knife coater with little foaming finishing agent blade coating film forming, enter the dry slaking of drying tunnel then, by double-pole doctor knife coater blade coating film forming, enter the dry slaking of drying tunnel, the micro porous coating that forms surfacing at non-weaving cloth or knitted cloth is the Synthetic Leather base; Adopt the aqueous polyurethane slurry that roll coating process will contain aqueous polyurethane, thickener and levelling agent to be coated on above the polyurathamc bottom then, carry out drying by drying tunnel, form smooth smooth aqueous polyurethane superficial layer;
Another kind of concrete technology is: be coated with base little foaming finishing agent is coated on the release liners of motion with reversing rolling method or roller lining knife coating, advance dry solidification with baking oven; Be coated with again after the cooling and be covered with the bonding coat bed material, laminated on base cloth and solidified subsequently; After super-dry, cooling, peel off; Leather and release liners difference rolling; Last recycling flush coater carries out surface treatment, finally obtains the finished product synthetic leather.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104404779A (en) * | 2014-11-26 | 2015-03-11 | 安徽宝博合成革有限公司 | Mirror-surface leather with crystal transferred and attached |
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| CN105986485A (en) * | 2016-01-26 | 2016-10-05 | 芜湖环瑞汽车内饰件有限公司 | Natural leather powder added high-breathability automotive interior decoration leather and preparation method thereof |
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| CN106120369A (en) * | 2016-07-29 | 2016-11-16 | 嘉兴金州聚合材料有限公司 | A kind of four-side elastic synthetic leather |
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| CN113622201A (en) * | 2021-08-23 | 2021-11-09 | 胡玉婷 | Polyurethane synthetic leather with high moisture absorption and air permeability and preparation method thereof |
| CN114150512A (en) * | 2021-12-20 | 2022-03-08 | 丽水合力新材料有限公司 | Smooth PU waterborne synthetic leather of environmental protection |
| CN114423833A (en) * | 2019-07-09 | 2022-04-29 | 赢创运营有限公司 | Polyol ether based foam additives for polyurethane dispersions with high filler content |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102080332A (en) * | 2010-12-27 | 2011-06-01 | 陕西科技大学 | Preparation method of waterborne polyurethane synthetic leather base |
| CN102276850A (en) * | 2011-04-27 | 2011-12-14 | 中国皮革和制鞋工业研究院 | Surface modified hide powder and preparation method thereof |
| CN102409552A (en) * | 2011-09-02 | 2012-04-11 | 福建宝利特集团有限公司 | Preparation method of environment-friendly foaming artificial leather |
| CN102504688A (en) * | 2011-11-23 | 2012-06-20 | 烟台万华聚氨酯股份有限公司 | Water-borne polyurethane foam layer for synthetic leather and preparation method for water-borne polyurethane foam layer |
| CN102758359A (en) * | 2012-07-06 | 2012-10-31 | 河南永合塑胶有限公司 | Polyurethane synthetic leather cleaning production process based on direct coating method |
| CN102758360A (en) * | 2012-07-06 | 2012-10-31 | 河南永合塑胶有限公司 | Polyurethane synthetic leather cleaning production process based on release paper transfer coating method |
-
2013
- 2013-04-15 CN CN2013101286001A patent/CN103290701A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102080332A (en) * | 2010-12-27 | 2011-06-01 | 陕西科技大学 | Preparation method of waterborne polyurethane synthetic leather base |
| CN102276850A (en) * | 2011-04-27 | 2011-12-14 | 中国皮革和制鞋工业研究院 | Surface modified hide powder and preparation method thereof |
| CN102409552A (en) * | 2011-09-02 | 2012-04-11 | 福建宝利特集团有限公司 | Preparation method of environment-friendly foaming artificial leather |
| CN102504688A (en) * | 2011-11-23 | 2012-06-20 | 烟台万华聚氨酯股份有限公司 | Water-borne polyurethane foam layer for synthetic leather and preparation method for water-borne polyurethane foam layer |
| CN102758359A (en) * | 2012-07-06 | 2012-10-31 | 河南永合塑胶有限公司 | Polyurethane synthetic leather cleaning production process based on direct coating method |
| CN102758360A (en) * | 2012-07-06 | 2012-10-31 | 河南永合塑胶有限公司 | Polyurethane synthetic leather cleaning production process based on release paper transfer coating method |
Non-Patent Citations (2)
| Title |
|---|
| 程正平 等: ""超微皮革粉体的表面改性和应用研究"", 《中国皮革》 * |
| 马兆国 等: ""皮革废弃物的超微粉碎及其应用"", 《中国皮革》 * |
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