CN102409553B - Method for preparing solvent-free vehicle interior leather based on in-situ polymerization - Google Patents
Method for preparing solvent-free vehicle interior leather based on in-situ polymerization Download PDFInfo
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Abstract
The invention claims a method for preparing a solvent-free vehicle interior leather based on an in-situ polymerization. The method comprises the steps of: heating and melting polyether with moderate relative molecular mass or polyester polyol at lower temperature; then, adding and uniformly mixing measured liquid diisocyanate, liquid small molecular dihydric alcohol or diamine chain extender, fluorine-containing additive, catalyst, foaming agent, toner and the like; and then coating the mixed liquid on a pre-processed leather basic cloth; putting the coated cloth in a baking oven and curing, wherein the above components performs in-situ polymerization in the process of curing so as to form a leather surface; finally, after forming obtaining the solvent-free vehicle interior leather which has high physical performance, high strength, wear resistant, scraping resistant and oil resistant.
Description
Technical field
The present invention relates to a kind ofly based on the situ aggregation method preparation method of solvent-laden interior leather for automobiles not, belong to synthetic leather manufacturing technology field.
Background technology
China is world synthetic leather production and consumption big country.2010, whole nation family more than 2600 of total synthetic leather enterprise, 316 of scale above enterprises, 1575 of synthetic leather production lines, output 5,300,000,000 square meters, 1,043 hundred million yuan of the industry gross output values have accounted for 73% of Gross World Product.To 316 enterprise production statistics more than scale, China's synthetic leather overall productivity was 218.9 ten thousand tons in 2010, closed 3,900,000,000 square meters, exceeded almost one times than China GDP growth rate, showed the strong growth of China's synthetic leather industry according to State Statistics Bureau.
Chinese people fabricate-leather, synthetic leather industry start from the end of the seventies, ground technology such as a complete set of Introduced from Japan and Taiwan at that time, although the development through nearly 30 years, a lot of technology such as DMF recovery technology, Recycle Technology of Waste Water, Machine Manufacturing Technology etc. have been reached advanced world standards, but the manufacturing technique of artificial leather, synthetic leather and material still follow traditional technique and material (solvent-borne type material), in material the volatilization of machine solvent be environmental pollution mainly dye head.Usually the organic exhaust gas that produces in the dry process process has DMF, toluene, acetic acid esters, cyclohexanone and butanone etc.; Waste organic solvent gas in the wet processing process is mainly DMF; Exhaust emission on artificial leather production line is mainly DOP waste gas, toluene, acetic acid esters and butanone etc.According to measuring and calculating, every 1 PU leather production line, annual discharging DMF10.2 ton, 50.8 tons of annual discharging toluene, 50.80 tons of annual discharging butanone, the DOP discharge capacity of every composite modified PVC production line is 1.32 ton/years, 24.5 ton/years of toluene, butanone, acetate esters solvent.Therefore, artificial leather, synthetic leather industry are faced with for a long time that the environmental improvement cost is high, the severe challenge of serious waste of resources, environmental pollution, how to develop solvent-free synthetic leather manufacturing technology, are the keys of maintaining the sustainable development of synthetic leather industry.
In addition, along with the enforcement of countries in the world environmental regulation, the developed countries such as European Union, the U.S. have proposed requirements at the higher level to the ecological property of leather.The theory of ecological synthetic leather comprises following four aspects: the one, do not bring pollution to environment in manufacturing process, and the 2nd, be processed in the leather goods process harmless; The 3rd, harmless in use procedure, environment is not produced pollution; The 4th, biodegradable, and catabolite can not cause new pollution to environment.
Correspondingly, European Union member countries have formulated strict Ecology Leather/synthetic leather standard, particularly to interior leather for automobiles, its haze value and volatile organic content (VOC) have been made strict demand.
Haze value: be an important technology index of automobile cushion leather, the import of European Union is at present ordered within a certain time and is≤1mg/Kg (leather)
VOC content: almost be fit to all leather verieties, it is VOC≤1mg/Kg (leather) that the import of European Union is at present ordered within a certain time.
China is automobile making and big export country, and China's auto output rose to the 1st in world rankings in 2009, and annual accumulative total is produced 1379.10 ten thousand, automobile (increasing on year-on-year basis 48.3%); 1364.48 ten thousand of selling automobiles increase by 46.2% on a year-on-year basis.Therefore, how to develop solvent-free interior leather for automobiles manufacturing technology, most important to improving China's automobile industry competitive position in the international market.
Summary of the invention
the objective of the invention is to provide for the deficiencies in the prior art based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation, be characterized in polyethers that relative molecular mass is moderate or polyester polyol heating and melting at low temperatures, then the vulcabond that adds metering, little molecule dihydroxylic alcohols or diamine chain extenders, catalyst, blowing agents etc. mix, then with on the even coating of mixed liquor and pretreated leather base cloth, send into slaking in baking oven, in-situ polymerization (in-situ) reaction occurs and forms the leather surface layer in said components in maturing process, can obtain not contain any organic solvent after foaming, high object height, intensity is high, wear-resisting, the interior leather for automobiles of scratch resistance.
Purpose of the present invention realizes by following technical measures, and wherein said raw material umber is parts by weight except specifying.
A kind of enforcement based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation comprises the following steps:
(1) base cloth preliminary treatment:
Base cloth after the preliminary treatment such as traditional splicing, traction, stretching and bristle, then is sprayed one deck water-base cation polyurethane, and quantity for spray 20-40g/m2 adopts press polish Kun to carry out press polish and processes after slaking, standby;
(2) preparation of polyurethane slurry (weight portion)
In 100 parts of sealing Scattered Kettles that add with heating, temperature control and dispersal device of the polyethers of relative molecular mass 2000-4000 or polyester polyol, at 45 ℃ of left and right heating and meltings, then add liquid vulcabond 20-40 part of metering, liquid little molecule dihydroxylic alcohols or diamine chain extenders 5-10 part, fluorine-containing auxiliary agent 3-5 part, catalyst 0.2-0.5 part, blowing agent 3-5 part, toner 10-20 part, dissolving, mix, standby;
(3) coating
Adopt straight coating method, polyurethane slurry is coated with scrapes on pretreated base cloth, coating layer thickness is controlled 0.2-0.3mm, then puts into the baking oven slaking, and oven temperature interval and curing time are set to respectively 90 ℃～110 ℃, 90-120s; 120 ℃～130 ℃, 60-90s gets semi-finished product;
(4) foaming
Above-mentioned semi-finished product are put into the baking oven foaming, and temperature range is divided into three sections, 180 ℃～185 ℃ of leading portions, and 190 ℃～195 ℃, stage casing, 200 ℃～210 ℃ of back segments, foamed time is 120～150s.
(5) surface treatment
Semi-finished product after foaming are looked the needs of color and luster, brightness, adopt three editions surface treating machine machines to carry out color and luster, brightness adjustment, the material that uses is aqueous surface-treating agent, the starching amount is controlled at 20-40g/m2, curing temperature and time are respectively 140-150 ℃, 60-90s, the leather base after surface treatment gets product after conventional embossing, gage.
Prepared interior leather for automobiles does not contain any organic solvent, has wear-resisting, scratch resistance, oil resistant is dirty, has the property of washing.
What a kind of water-base cation polyurethane of using based on the foaming synthetic leather manufacture method preliminary treatment of aqueous polyurethane of base cloth was elastic modelling quantity lower than in the aliphatic of 10MPa and/or aromatic urethane is at least a.
The polyether Glycols of relative molecular mass 2000-4000 is that polypropylene glycol, polyethylene glycol, polytetrahydrofuran diol and/or polyester diol are at least a in PCDL, polycaprolactone dihydroxylic alcohols, polyester adipate dihydroxylic alcohols.
The liquid vulcabond is TDI (toluene di-isocyanate(TDI)), liquid MDI (liquid diphenylmethane methane diisocyanate), H
12At least a in MDI (hydrogenation MDI), IPDI (isoflurane chalcone diisocyanate) and/or HDI (hexamethylene diisocyanate).
Liquid little molecule dihydroxylic alcohols or diamine chain extenders are at least a in ethylene glycol, BDO, ethylenediamine and/or diethylenetriamine.
Fluorine-containing auxiliary agent is fluorine-containing surfactant, C
8-12At least a in fluorine alcohol and/or fluorine-containing siloxanes.
Catalyst is at least a in dibutyl tin laurate and/or stannous octoate.
What aqueous surface-treating agent was elastic modelling quantity in the aliphatic of 50～70MPa and/or aromatic urethane add lustre to gloss oil and/or delustring gloss oil is at least a.
Blowing agent, toner are equal to common process.
The present invention has following remarkable advantage:
1, technology set one-tenth provided by the invention, moulding, slaking are in one, and operation is brief, save energy consumption, have increased substantially production efficiency;
2, adopt in-situ polymerization technology to produce on the spot leather coating, eliminate the environmental pollution that organic solvent causes from the source, save a large amount of organic solvent resources, significantly improve labourer's employment environment, be conducive to the sustainable development of industry.
3, prepared automotive trim does not contain any organic solvent, has satisfied European Union's ecological synthetic leather requirement, also have simultaneously wear-resisting, scratch resistance, oil resistant dirty, have the property of washing, improved synthetic leather product hierarchy and competitiveness in the international market.
The specific embodiment
Below by embodiment, the present invention is specifically described.Be necessary to be pointed out that at this present embodiment only is used for the present invention is further illustrated, can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
In addition, also what deserves to be explained is, below each embodiment umber used be weight portion.
Embodiment 1
(1) base cloth preliminary treatment:
Base cloth after the preliminary treatment such as traditional splicing, traction, stretching and bristle, then is sprayed one deck elastic modelling quantity 10MPa water-base cation polyurethane, quantity for spray 20g/m
2, adopt press polish Kun to carry out press polish after 80-100 ℃ of slaking and process, standby;
(2) preparation of polyurethane slurry (weight portion)
Relative molecular mass 2000 polypropylene glycol 50kg, poly adipate succinic acid ester dihydroxylic alcohols 50kg add in sealing Scattered Kettle with heating, temperature control and dispersal device, 45 ℃ of lower heat fused, then add 20.0 parts of toluene di-isocyanate(TDI)s, diethylenetriamine 5.0kg, fluorine-containing octanol 5.0kg, catalyst dibutyl tin laurate 0.2kg, blowing agent 3.0kg, toner 10.0kg, dissolving, mix, standby;
(3) coating
Adopt straight coating method, polyurethane slurry is coated with scrapes on pretreated base cloth, coating layer thickness is controlled 0.2mm, then puts into the baking oven slaking, and oven temperature interval and curing time are set to respectively 100 ℃, 90s; 130 ℃, 60s gets semi-finished product;
(4) foaming
Above-mentioned semi-finished product are put into the baking oven foaming, and temperature range is divided into three sections, 180 ℃～185 ℃ of leading portions, and 190 ℃～195 ℃, stage casing, 200 ℃～210 ℃ of back segments, foamed time is 120s.
(5) surface treatment
Use elastic modelling quantity 50MPa water-based extinction type aliphatic polyurethane surface conditioning agent to carry out lustrous surface and regulate processing, the starching amount is controlled at 20g/m
2, curing temperature and time are respectively 140-150 ℃, 60s, and the leather base after surface treatment gets product after conventional embossing.
Embodiment 2
(1) base cloth preliminary treatment:
Base cloth after the preliminary treatment such as traditional splicing, traction, stretching and bristle, then is sprayed one deck elastic modelling quantity 8MPa water-base cation polyurethane, and quantity for spray 25g/m2 adopts press polish Kun to carry out press polish and processes after 100 ℃ of slakings, standby;
(2) preparation of polyurethane slurry (weight portion)
Relative molecular mass 2000 polypropylene glycols, each 50kg of polyethylene glycol adipate dihydroxylic alcohols add in sealing Scattered Kettle with heating, temperature control and dispersal device, 45 ± 1 ℃ of heat fused, then add 33.0 parts of liquid MDI (liquid diphenylmethane methane diisocyanate), butanediol 2.0kg diethylenetriamine 6.0kg, fluorine-containing lauryl alcohol 5.0kg, the inferior tin 0.2kg of octoate catalyst, blowing agent 3.0kg, toner 15.0kg, dissolving, mix, standby;
(3) coating
Adopt straight coating method, polyurethane slurry is coated with scrapes on pretreated base cloth, coating layer thickness is controlled 0.25mm, then puts into the baking oven slaking, and oven temperature interval and curing time are set to respectively 90 ℃, 120s; 120 ℃, 90s gets semi-finished product;
(4) foaming
Above-mentioned semi-finished product are put into the baking oven foaming, and temperature range is divided into three sections, 180 ℃～185 ℃ of leading portions, and 190 ℃～195 ℃, stage casing, 200 ℃～210 ℃ of back segments, foamed time is 120s.
(5) surface treatment
Use the surface treatment of elastic modelling quantity 60MPa water-based extinction type aromatic urethane to carry out lustrous surface and regulate processing, the starching amount is controlled at 30g/m2, and curing temperature and time are respectively 150 ℃, 60s, and the leather base after surface treatment gets product after conventional embossing.
Embodiment 3
(1) base cloth preliminary treatment:
Base cloth after the preliminary treatment such as traditional splicing, traction, stretching and bristle, then is sprayed one deck elastic modelling quantity 5MPa water-base cation polyurethane, and quantity for spray 30g/m2 adopts press polish Kun to carry out press polish and processes after 100 ℃ of slakings, standby;
(2) preparation of polyurethane slurry (weight portion)
The poly-polycaprolactone dihydroxylic alcohols 60kg of relative molecular mass 3000 polytetrahydrofuran diol 40kg, relative molecular mass 4000 adds in sealing Scattered Kettle with heating, temperature control and dispersal device, 45 ± 1 ℃ of heat fused, then add 29.5 parts of H12MDI (hydrogenation MDI), diethylenetriamine 10.0kg, flucride siloxane alcohol 5.0kg, catalyst dibutyl tin laurate 0.5kg, blowing agent 3.5kg, toner 20.0kg dissolving, mix, standby;
(3) coating
Adopt straight coating method, polyurethane slurry is coated with scrapes on pretreated base cloth, coating layer thickness is controlled 0.25mm, then puts into the baking oven slaking, and oven temperature interval and curing time are set to respectively 110 ℃, 100s; 130 ℃, 90s gets semi-finished product;
(4) foaming
Above-mentioned semi-finished product are put into the baking oven foaming, and temperature range is divided into three sections, 180 ℃～185 ℃ of leading portions, and 190 ℃～195 ℃, stage casing, 205 ℃～210 ℃ of back segments, foamed time is 120s.
(5) surface treatment
Use elastic modelling quantity 60MPa water-based half light type type polyurethane surface conditioning agent to carry out lustrous surface and regulate processing, the starching amount is controlled at 30g/m2, and curing temperature and time are respectively 150 ℃, 60s, and the leather base after surface treatment gets product after conventional embossing.
Embodiment 4
(1) base cloth preliminary treatment:
Base cloth after the preliminary treatment such as traditional splicing, traction, stretching and bristle, then is sprayed one deck elastic modelling quantity 10MPa water-base cation polyurethane, and quantity for spray 40g/m2 adopts press polish Kun to carry out press polish and processes after 100 ℃ of slakings, standby;
(2) preparation of polyurethane slurry (weight portion)
Relative molecular mass 4000 PCDL 100kg add in sealing Scattered Kettle with heating, temperature control and dispersal device, 45 ± 1 ℃ of heat fused, then add IPDI (isoflurane chalcone diisocyanate) 32kg, HDI (hexamethylene diisocyanate) 8kg, ethylene glycol 7.0kg, ethylenediamine 2.0kg fluorine-containing surfactant 4.5kg, the inferior tin 0.45kg of octoate catalyst, blowing agent 5.0kg, toner 20.0kg dissolving, mix, standby;
(3) coating
Adopt straight coating method, polyurethane slurry is coated with scrapes on pretreated base cloth, coating layer thickness is controlled 0.3mm, then puts into the baking oven slaking, and oven temperature interval and curing time are set to respectively 110 ℃, 120s; 130 ℃, 90s gets semi-finished product;
(4) foaming
Above-mentioned semi-finished product are put into the baking oven foaming, and temperature range is divided into three sections, 180 ℃～185 ℃ of leading portions, and 190 ℃～195 ℃, stage casing, 205 ℃～210 ℃ of back segments, foamed time is 140s.
(5) surface treatment
Use elastic modelling quantity 70MPa water-based light type aliphatic polyurethane surface conditioning agent to carry out lustrous surface and regulate processing, the starching amount is controlled at 25g/m2, and curing temperature and time are respectively 130 ℃, 60s, and the leather base after surface treatment gets product after conventional embossing.
Embodiment 5
(1) base cloth preliminary treatment:
Base cloth after the preliminary treatment such as traditional splicing, traction, stretching and bristle, then is sprayed one deck elastic modelling quantity 7MPa water-base cation polyurethane, and quantity for spray 30g/m2 adopts press polish Kun to carry out press polish and processes after 90-100 ℃ of slaking, standby;
(2) preparation of polyurethane slurry (weight portion)
Relative molecular mass 2000 polyethylene glycol glycol 30kg, relative molecular mass 3000 PCDL 70kg add in sealing Scattered Kettle with heating, temperature control and dispersal device, 45 ± 1 ℃ of heat fused, then add TDI (toluene di-isocyanate(TDI)) 14.2kg, H12MDI (hydrogenation MDI) 16.0kgkg, ethylenediamine 3.0kg, butanediol 2.0kg fluorine-containing surfactant 2.0kg, the inferior tin 0.2kg of octoate catalyst, dibutyl tin laurate 0.2kg, blowing agent 5.0kg, toner 16.0kg dissolving, mix, standby;
(3) coating
Adopt straight coating method, polyurethane slurry is coated with scrapes on pretreated base cloth, coating layer thickness is controlled 0.3mm, then puts into the baking oven slaking, and oven temperature interval and curing time are set to respectively 110 ℃, 110s; 130 ℃, 80s gets semi-finished product;
(4) foaming
Above-mentioned semi-finished product are put into the baking oven foaming, and temperature range is divided into three sections, 180 ℃～185 ℃ of leading portions, and 190 ℃～195 ℃, stage casing, 205 ℃～210 ℃ of back segments, foamed time is 140s.
(5) surface treatment
Use elastic modelling quantity 70MPa water-based light type aliphatic polyurethane surface conditioning agent to carry out lustrous surface and regulate processing, the starching amount is controlled at 25g/m2, and curing temperature and time are respectively 130 ℃, 60s, and the leather base after surface treatment gets product after conventional embossing.
Claims (10)
1. one kind prepares not solvent-laden interior leather for automobiles method based on situ aggregation method, it is characterized in that the enforcement of the method comprises the following steps:
(1) base cloth preliminary treatment:
Base cloth after traditional splicing, traction, stretching and bristle preliminary treatment, then is sprayed one deck water-base cation polyurethane, quantity for spray 20-40g/m
2, the dry rear press polish Kun that adopts carries out the press polish processing, and is standby;
(2) preparation of polyurethane slurry (weight portion)
In 100 parts of sealing Scattered Kettles that add with heating, temperature control and dispersal device of the polyethers of relative molecular mass 2000-4000 or polyester polyol, at 45 ℃ of left and right heating and meltings, then add vulcabond 20-40 part of metering liquid shape, liquid little molecule dihydroxylic alcohols or diamine chain extenders 5-10 part, fluorine-containing auxiliary agent 2-5 part, catalyst 0.2-0.5 part, blowing agent 3-5 part, toner 10-20 part, dissolving, mix, standby;
(3) coating
Adopt straight coating method, polyurethane slurry is coated with scrapes on pretreated base cloth, coating layer thickness is controlled 0.2-0.3mm, then puts into the baking oven slaking, and oven temperature interval and curing time are set to respectively 90 ℃～110 ℃, 90-130s; 120 ℃～130 ℃, 60-90s gets semi-finished product;
(4) foaming
Above-mentioned semi-finished product are put into the baking oven foaming, and temperature range is divided into three sections, 180 ℃～185 ℃ of leading portions, and 190 ℃～195 ℃, stage casing, 200 ℃～210 ℃ of back segments, foamed time is 120～150s;
(5) surface treatment
Semi-finished product after foaming are looked the needs of color and luster, brightness, adopt three editions surface treating machines to carry out color and luster, brightness adjustment, the material that uses is aqueous surface-treating agent, the starching amount is controlled at 20-40g/m2, baking temperature and time are respectively 140-150 ℃, 60-90s, the leather base after surface treatment gets product after conventional embossing, gage.
2. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, it is characterized in that its coating of prepared interior leather for automobiles is to adopt the preparation of original position (in-situ) polymerization, do not contain any organic solvent, that coating has is wear-resisting, scratch resistance, oil resistant are dirty, has the property of washing.
3. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, what it is characterized in that water-base cation polyurethane that the base cloth preliminary treatment is used is elastic modelling quantity lower than in the aliphatic of 10MPa and/or aromatic urethane is at least a.
4. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, the polyether Glycols that it is characterized in that relative molecular mass 2000-4000 is that polypropylene glycol, polyethylene glycol, polytetrahydrofuran diol and/or polyester diol are at least a in PCDL, polycaprolactone dihydroxylic alcohols, polyester adipate dihydroxylic alcohols.
5. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, it is characterized in that the liquid vulcabond is at least a in TDI (toluene di-isocyanate(TDI)), liquid MDI (liquid '-diphenylmethane diisocyanate), H12MDI (hydrogenation MDI), IPDI (isoflurane chalcone diisocyanate) and/or HDI (hexamethylene diisocyanate).
6. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, it is characterized in that liquid little molecule dihydroxylic alcohols or diamine chain extenders are at least a in ethylene glycol, BDO, ethylenediamine and/or diethylenetriamine.
7. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, it is characterized in that fluorine-containing auxiliary agent is fluorine-containing surfactant, C
8-12At least a in fluorine alcohol and/or fluorine-containing siloxanes.
8. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, it is characterized in that catalyst is at least a in dibutyl tin laurate and/or stannous octoate.
9. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, what it is characterized in that aqueous surface-treating agent is elastic modelling quantity in the aliphatic of 50～70MPa and/or aromatic urethane add lustre to type, half light type and/or extinction type is at least a.
10. a kind of based on the not solvent-laden interior leather for automobiles method of situ aggregation method preparation as claimed in claim 1, it is characterized in that blowing agent, the same common process of toner.
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| JP6207304B2 (en) * | 2012-09-27 | 2017-10-04 | セーレン株式会社 | Synthetic leather and method for producing the same |
| CN102964563B (en) * | 2012-11-27 | 2014-08-20 | 上海汇得化工有限公司 | One-component, high-solid-content and low-crystallinity polyurethane resin and preparation method thereof |
| CN103289043B (en) * | 2013-05-24 | 2015-08-05 | 福建大元化工有限公司 | A kind of urethane resin |
| CN103483546A (en) * | 2013-09-26 | 2014-01-01 | 南京年吉冷冻食品有限公司 | Preparation method for water-repellent oil-repellent fluorinated polyurethane rigid foamed plastic |
| CN107602802A (en) * | 2017-09-20 | 2018-01-19 | 合肥安利聚氨酯新材料有限公司 | A kind of sofa artificial leather middle foaming layer solvent-free polyurethane resin and preparation method thereof |
| CN109457500B (en) * | 2018-12-06 | 2021-09-07 | 福建中裕新材料技术有限公司 | High-physical-property solid solvent-free leather |
| CN109825084A (en) * | 2018-12-29 | 2019-05-31 | 江苏创景科技有限公司 | A kind of foaming bi-component organic silicon potting adhesive and preparation method thereof |
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| CN1302250A (en) * | 1998-05-22 | 2001-07-04 | 麦格纳内部系统公司 | Decorative automobile interior trim articles with integral in-mold coated polyurethane aromatic elastomer covering and process for making the same |
| CN101591420A (en) * | 2008-05-27 | 2009-12-02 | 上海合达聚合物科技有限公司 | A kind of plastic-blasting polyurethane composition, its preparation method and application thereof |
| CN101941321A (en) * | 2010-08-03 | 2011-01-12 | 丽水市优耐克水性树脂科技有限公司 | Method for manufacturing synthetic leather and synthetic leather |
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| DE10039249A1 (en) * | 2000-08-11 | 2002-02-28 | Bayer Ag | Coated, flexible fabrics |
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|---|---|---|---|---|
| CN1302250A (en) * | 1998-05-22 | 2001-07-04 | 麦格纳内部系统公司 | Decorative automobile interior trim articles with integral in-mold coated polyurethane aromatic elastomer covering and process for making the same |
| CN101591420A (en) * | 2008-05-27 | 2009-12-02 | 上海合达聚合物科技有限公司 | A kind of plastic-blasting polyurethane composition, its preparation method and application thereof |
| CN101941321A (en) * | 2010-08-03 | 2011-01-12 | 丽水市优耐克水性树脂科技有限公司 | Method for manufacturing synthetic leather and synthetic leather |
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