CN101914343B - Method for preparing organic siloxane modified aqueous polyurethane coating - Google Patents
Method for preparing organic siloxane modified aqueous polyurethane coating Download PDFInfo
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- CN101914343B CN101914343B CN2010102662145A CN201010266214A CN101914343B CN 101914343 B CN101914343 B CN 101914343B CN 2010102662145 A CN2010102662145 A CN 2010102662145A CN 201010266214 A CN201010266214 A CN 201010266214A CN 101914343 B CN101914343 B CN 101914343B
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Abstract
The invention discloses a method for preparing an organic siloxane modified aqueous polyurethane coating. The method is characterized by comprising the following steps of: gradually polymerizing diisocyanate, oligo-diol, micromolecular polyol and micromolecular diol containing carboxyl to synthesize hydrophilic polyurethane with the carboxyl on a side chain; adding triethylamine to make the carboxyl on the side chain form a quaternary ammonium salt; adding epoxy siloxane for modification to obtain a siloxane modified prepolymer; dispersing the siloxane modified prepolymer in water to prepare siloxane modified polyurethane dispersion liquid; and extending chains of the dispersion liquid with polyamine to prepare the organic siloxane modified aqueous polyurethane latex coating. The latex has solid content of over 30 percent, a pH value of 6.0 to 7.0 and a semitransparent appearance with blue light. The epoxy siloxane used by the method is a general product in the market, involves in a cross-linking reaction and effectively improves the water resistance and adhesion of the coating.
Description
One, technical field
The present invention relates to a kind of preparation method of polyurethane coating, exactly is a kind of preparation method of organic siloxane modified aqueous polyurethane coating.
Two, background technology
Aqueous polyurethane coating is meant do not have or do not have organic solvent basically, the polyurethane coating that water is prepared as dispersion system.Because its high feature of environmental protection, high-decoration, high-wearing feature, high anti-stick, splitting resistance, and the construction temperature scope of relative broad, development at home and abroad is widely used rapidly.But have certain hydrophilicity after the aqueous polyurethane film forming, so water resistance is generally not high; The aqueous polyurethane film mainly relies on reactive force such as hydrogen bond and Van der Waals force and base material to combine, and therefore, sticking power is generally unsatisfactory, and especially behind high humidity environment or water logging bubble, hydrogen bond and Van der Waals force can be damaged, and sticking power can further be affected.An effective means that improves aqueous polyurethane coating sticking power is exactly in aqueous polyurethane, to introduce siloxanes to carry out modification; With this at film surface enrichment organosilicon; Produce hydrophobic interaction to improve its water resistance, utilize the sticking power of the coupled action strengthening membrane of siloxanes simultaneously base material.At present, the method with silicone-modified aqueous polyurethane coating has had certain trial.
Synthesis mechanism and the applied research for preparing the aqueous polyurethane hide finishes with epoxysilicone reported in " Chinese leather " (1999,28 (5), 3～5) and " Chinese leather " (2000,29 (9), 30～32,36).The epoxysilicone that but above report uses is produced for it voluntarily, lacks the ubiquity of using.In addition, be that epoxysilicone is joined in the aqueous polyurethane product as additive in the report, be made into compound system and be used further to leather finish.Composite operation has wherein increased operation steps, expends and produces man-hour.Epoxysilicone is not participated in the polyreaction step by step in the aqueous polyurethane building-up process in addition, and crosslinked action is very limited.
" bonding " (2000 (5); 24～27) reported that organic functions silane portion of U.S. Compton ltd has developed linking agent and the adhesion promotor of a series of epoxysilicones as carboxylated waterborne polymerics such as ACRYLIC EMULSION, butadiene-styrene latex and polyurethane dispersions voluntarily, can make tackiness agent and sealer have outstanding adhesion, mechanical property and chemical resistance.But the epoxysilicone that this report is used is also produced for it voluntarily.This report is epoxysilicone to be joined in the waterborne polymeric product be made into compound system equally in addition, just comes into operation then.Above complex process also can cause complicated operation, produce and expend the crosslinked limited problem of raising, epoxysilicone and aqueous polyurethane man-hour.
Three, summary of the invention
The present invention aims to provide a kind of organic siloxane modified preparation aqueous polyurethane coating, and technical problem to be solved is to improve the water tolerance and the sticking power of this aqueous polyurethane coating.
The preparation method of organic siloxane modified aqueous polyurethane coating of the present invention; At first carry out step-reaction polymerization by vulcabond and low poly-dihydric alcohol, small molecules polyvalent alcohol and carboxylic small molecules divalent alcohol; Adding triethylamine then makes side chain carboxyl group form quaternary ammonium salt; Add the epoxysilicone modification again, obtain silicone-modified performed polymer.At last silicone-modified performed polymer is dispersed in the water, makes the siloxane modified polyurethane dispersion liquid; This siloxane modified polyurethane dispersion liquid is used the polyamine chain extension, makes the organic siloxane modified aqueous polyurethane emulsion coatings thus.
Specifically this preparation method comprises the preparation and the polyamine chain extending reaction of silicone-modified performed polymer and dispersion liquid thereof; Difference with the prior art be described silicone-modified performed polymer preparation at first by vulcabond and low poly-dihydric alcohol, small molecules polyvalent alcohol and butanone under catalyzer dibutyl tin laurate existence condition in 65-90 ℃ of stirring reaction 1.5-2.5 hour, the mol ratio of vulcabond, low poly-dihydric alcohol, small molecules polyvalent alcohol is 3-5: 1: 0.7-1.0; The butanone consumption is the 10-30% of low poly-dihydric alcohol quality; The consumption of dibutyl tin laurate is the 0.1-0.3% of vulcabond, low poly-dihydric alcohol and small molecules polyvalent alcohol total mass; The first step is reacted main polymerization and is generated polyurethane backbone; Carry out the reaction of second step then; On main chain, introduce carboxylic side chain; Specifically be in the first step reaction solution, to add carboxylic small molecules divalent alcohol in 65-90 ℃ of stirring reaction 2.5-6 hour, the mol ratio of carboxylic small molecules divalent alcohol and vulcabond is 1: 4-6; Carboxyl on the three-step reaction formula side chain and triethylamine generate quaternary ammonium salt, specifically are in the second step reaction solution, to add triethylamine in 20-45 ℃ of stirring reaction 10-40 minute, and the mol ratio of triethylamine and carboxyl is 0.9-1.1: 1; Four-step reaction is and the silicone-modified performed polymer of the cross-linking modified generation of epoxysilicone, specifically is in three-step reaction liquid, to add epoxysilicone in 20-45 ℃ of stirring reaction 10-30 minute, and the mol ratio of epoxysilicone and carboxyl is 1: 5-10.Described carboxyl mole number is exactly the mole number of carboxylic small molecules divalent alcohol.
The preparation of described performed polymer dispersion liquid is exactly that four-step reaction liquid is under agitation at the uniform velocity added in 5-20 ℃ the deionized water until being uniformly dispersed the volume ratio 1 of reaction solution and deionized water: 1.5-4.
Described polyamine chain extending reaction is that the polyamine solution with mass percentage concentration 5-15% was added drop-wise in the performed polymer dispersion liquid reaction 1-2 hour under 5-20 ℃ of stirring; Be warming up to then and obtained this waterborne polyurethane emulsion coating in 30-45 ℃ of stirring reaction 20-40 minute, the mol ratio of polyamine and low poly-dihydric alcohol is 0.8-1.0: 1.
Described vulcabond is selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) or tolylene diisocyanate (TDI).
Described low poly-dihydric alcohol is selected from W 166 PPG-210 or PPG-220 or PTMG PTMG-1000 or PTMG-2000.
Described small molecules polyvalent alcohol is selected from 1,4-butyleneglycol, 1,2-Ucar 35 or TriMethylolPropane(TMP) (TMP).
Described carboxylic small molecules divalent alcohol is selected from dimethylol propionic acid (DMPA) or dimethylolpropionic acid (DMBA).
Described epoxysilicone is selected from γ-Racemic glycidol oxygen propyl trimethoxy silicane (KH560), γ-glycidyl ether oxygen base propyl group Union carbide A-162 or γ-glycidyl ether oxygen base propyl group methyldiethoxysilane.
Described polyamine is selected from quadrol, diethylenetriamine, triethylene tetramine or TEPA.
This waterborne polyurethane emulsion coating solid content＞30%, pH=6.0～7.0, the translucent blueing light of outward appearance belongs to microemulsion.
For the coating effect of the chemical structure that characterizes staple in the waterborne polyurethane emulsion coating, coating and performance etc.; With coating hydrostomia film forming on polyfluortetraethylene plate; After the seasoning, handle 4hr at 80 ℃, obtaining thickness is the water white transparency urethane high-polymer membrane of 0.3-0.4mm.This film is used for the mensuration of IR Characterization, mechanical property and the mensuration of water resistance; Identical emulsion is filmed with the mode of brushing on sheet glass, dry naturally, handle 4hr for 80 ℃, obtain, be used to the to film detection of dried adhesion property and water-fast adhesion property of this plate by the test plate of water white transparency urethane high-polymer membrane covering.
The water tolerance of film and the test result of physical strength are shown film immerses the water-intake rate 5-8% of 24h in the water, in room temperature water, soak and do not whiten in 30 days; Dry film tensile strength 17.8-22.9MPa, elongation at break can reach 434-510%; Tensile strength under the film room temperature behind the immersion 24h still can remain on 12.9-21.1MPa, and elongation at break can remain on 338-480%.
The adhesion property test result that glass surface is filmed shows that dry film can reach 1 grade at the sticking power of glass surface, and aliphatics aqueous polyurethane coating sticking power after 7 days in glass surface is filmed immersion water still can maintain the 1-2 level; And aromatic waterborne polyurethane coating 7 days postadhesion power in glass surface is filmed immersion water can maintain the 2-3 level.
Organic siloxane modified aqueous polyurethane emulsion coatings of the present invention is, epoxysilicone modification quaternized through step-reaction polymerization, triethylamine, in water, disperses, obtains with the polyamine chain extension at last.The present invention prepares at coating and adds epoxysilicone in the intermediate steps, so epoxysilicone can be full cross-linked in coating.In addition, coating products of the present invention can directly use, and need not other complex process.With " Chinese leather " (1999,28 (5), 3～5) and " Chinese leather " (2000; 29 (9), 30～32,36) the aqueous polyurethane leather finish articles for use in the report; And " bonding " (2000 (5); 24～27) method of modifying in the report is compared, and the present invention has adopted epoxysilicone product common on the market, and production process is smaller to the dependence of raw material sources; Epoxysilicone crosslinked more abundant in coating improved the water tolerance and the sticking power of filming effectively; Coating products need not complex process before using, and can reduce operation, and the user uses difficulty to reduce, and cost reduces, thereby has market outlook preferably.
Four, description of drawings
Fig. 1 is the infared spectrum that aqueous polyurethane emulsion is filmed.
Infrared result shows, at 3340cm
-1There is the stretching vibration peak of NH at the place, at 1740cm
-1There is the C=O stretching vibration peak of CO-NH at the place, at 1547cm
-1There is the NH formation vibration peak of CO-NH at the place, the eigen vibration peak that these three peaks are carbamates in the urethane, and explaining has polyurethane(s) to generate really in institute's synthetic waterborne polyurethane emulsion coating; 1100cm
-1There are the flexural vibration peak of Si-O-Si, 1250cm in the place
-1The place is-CH
2Among-the Si-CH
2-the flexural vibration peak, confirmed that silicone ingredients is combined in the molecular structure of waterborne polyurethane emulsion coating through Si-O-Si key and Si-C key really.
Five, embodiment
Below pass through the preparation method of embodiment further explain epoxysilicone modified aqueous polyurethane emulsion of the present invention.
In the 250mL there-necked flask, add isophorone diisocyanate (IPDI) 18g, polypropylene oxide glycol (PPG220) 20g, PTMG (PTMG-2000) 20g, 1; 4-butyleneglycol 1.5g, 10mL butanone and 0.1g dibutyl tin laurate stirred under 200 rev/mins of speed, in about 2 hours of 80～85 ℃ of reactions; Add 2.46g dimethylol propionic acid (DMPA); Under 200 rev/mins of speed, stir, maintain the temperature at 80～85 ℃ and reacted again 3.5～4 hours, be cooled to 30～40 ℃; Add the 1.86g triethylamine, at 200 rev/mins of about 20min of speed stirring reaction.Add 0.55g γ-Racemic glycidol oxygen propyl trimethoxy silicane (KH560) subsequently; Under 200 rev/mins of speed, stir; Keep 30～40 ℃ of reaction 20min; Joining in 10～15 ℃ the 105g deionized water at the uniform velocity in 8 minutes, deionized water stirs with 1000r/min speed in the adition process.Continue stir about 15min, in the mixed solution that obtains, be added dropwise to water-reducible about 1.2g diethylenetriamine with 10g then, temperature remains on 10～15 ℃ in the dropping process, and the time is controlled to be 5～8 minutes, and stirring velocity is about 1000r/min.Drip and finish the continued stirring, be warmed up to 35～40 ℃ after 1.5 hours and continue about 30 minutes of reaction.
The waterborne polyurethane emulsion coating solid content that obtains is approximately 36%, pH=6.0～7.0, the translucent blueing light of outward appearance.
The water tolerance of film and the test result of physical strength are shown the water-intake rate that film immerses 24h in the water is merely 5.8%, in room temperature water, soak and do not whiten in 30 days; The dry film tensile strength can reach 22.9MPa, and elongation at break can reach 510%; Tensile strength under the film room temperature behind the immersion 24h still can remain on 21.1MPa, and elongation at break can remain on 480%;
The adhesion property test result that glass surface is filmed shows that dry film can reach 1 grade at the sticking power of glass surface, and the sticking power in the immersion water after 7 days still can maintain 1～2 grade.
Comprehensive above result shows; Epoxysilicone KH560 can play good modifying function to aqueous polyurethane emulsion; Aqueous polyurethane emulsion film forming after the modification has mechanical property, water resistance preferably; In addition glass is also had very excellent adhesion property, this adhesion property is also insensitive to the interference of moisture content.
Embodiment 2
Adopt the process identical with embodiment 1; Use γ-glycidyl ether oxygen base propyl group Union carbide A-162 0.65g instead and replace γ-Racemic glycidol oxygen propyl trimethoxy silicane (KH560) 0.55g, prepared aqueous polyurethane product is with embodiment 1 same method film forming and preparation test plate.Immerse under its film room temperature that the 24h water-intake rate is 6.2% in the water, steep in water and not whiten in 30 days; The dry film tensile strength is 21.8MPa, and elongation at break is 498%; Tensile strength under the film room temperature behind the immersion 24h still can remain on 20.1MPa, and elongation at break can remain on 450%; Dry film can reach 1 grade at the sticking power of glass surface, and the sticking power in the immersion water after 7 days still can maintain 1～2 grade.
Embodiment 3
Adopt the process identical, replace diethylenetriamine 1.2g with triethylene tetramine 1.2g in the stage of polyamine chain extension with embodiment 1, prepared waterborne polyurethane emulsion coating use with the method film forming of embodiment 1 with prepare test plate.Immerse under its film room temperature that the 24h water-intake rate is 5.9% in the water, steep in water and not whiten in 30 days; The dry film tensile strength is 23.1MPa, and elongation at break is 522%; Tensile strength under the film room temperature behind the immersion 24h still can remain on 20.8MPa, and elongation at break can remain on 470%; Dry film can reach 1 grade at the sticking power of glass surface, and the sticking power in the immersion water after 7 days still can maintain 1～2 grade.
Embodiment 4
Adopt the process identical with embodiment 1; The step-reaction polymerization stage with TriMethylolPropane(TMP) (TMP) 0.9g, 1; 4-butyleneglycol 0.6g replaces 1,4-butyleneglycol 1.5g, prepared waterborne polyurethane emulsion coating with the identical method film forming of embodiment 1 with prepare test plate.Immerse under its film room temperature that the 24h water-intake rate is 4.9% in the water, steep in water and not whiten in 30 days; The dry film tensile strength is 25.7MPa, and elongation at break is 466%; Tensile strength under the film room temperature behind the immersion 24h still remains on 23.1MPa, and elongation at break remains on 415%; Dry film reaches 1 grade at the sticking power of glass surface, and the sticking power in the immersion water after 7 days still maintains 1～2 grade.
Embodiment 5
In the 250mL there-necked flask, add tolylene diisocyanate (TDI) 14.2g, polypropylene oxide glycol (PPG220) 20g, PTMG (PTMG-2000) 20g, 1,4-butyleneglycol 1.5g, 10mL butanone and 0.1g dibutyl tin laurate were in about 1.5 hours of 70～75 ℃ of reactions; Under 150 rev/mins of speed, stir; Add 2.46g dimethylol propionic acid (DMPA), under 200 rev/mins of speed, stir, maintain the temperature at 70～75 ℃ and reacted again 4 hours; Be cooled to 20～30 ℃; Add the 1.86g triethylamine, under 200 rev/mins of speed, stir stir about 15min.Add 0.55gKH560 then, at the uniform velocity join in 5 minutes in 5～10 ℃ the 105g deionized water, keeping rotating speed is 1200 rev/mins of stir about 15min, adds with the water-reducible about 1.2g diethylenetriamine of 10g; After 1200 rev/mins speed stirrings 1.5 hours, keep rotating speed to stir 30 minutes at 30～35 ℃.It is about 33% to obtain solid content, pH=6.5～7.0, the waterborne polyurethane emulsion coating of the translucent blueing light of outward appearance.
The water tolerance of film and the test result of physical strength are shown the water-intake rate that film forming immerses 24h in the water is 7.2%, in room temperature water, soak and do not whiten in 30 days; The dry film tensile strength can reach 18.2MPa, and elongation at break reaches 440%; Tensile strength under the film room temperature behind the immersion 24h still can remain on 13.8MPa, and elongation at break can remain on 387%;
The adhesion property test result that glass surface is filmed shows that dry film can reach 1 grade at the sticking power of glass surface, and the sticking power in the immersion water after 7 days still can maintain 2～3 grades.
Embodiment 6
Adopt the process identical, use γ-glycidyl ether oxygen base propyl group Union carbide A-162 0.65g instead and replace γ-Racemic glycidol oxygen propyl trimethoxy silicane (KH560) 0.55g with embodiment 6.Prepared aqueous polyurethane product is used the method film forming and preparation test plate with embodiment 1.Immerse under its film room temperature that the 24h water-intake rate is 7.5% in the water, steep in water and not whiten in 30 days; The dry film tensile strength is 18.9MPa, and elongation at break is 457%; Tensile strength under the film room temperature behind the immersion 24h still can remain on 14.0MPa, and elongation at break can remain on 352%; Dry film can reach 1 grade at the sticking power of glass surface, and the sticking power in the immersion water after 7 days still can maintain 2～3 grades.
Embodiment 7
Adopt the process identical with embodiment 6, the stage of chain extension is with triethylene tetramine 1.2g replacement diethylenetriamine 1.2g after dispersion.Prepared aqueous polyurethane product is used the method film forming and preparation test plate with embodiment 1.Immerse under its film room temperature that the 24h water-intake rate is 7.9% in the water, steep in water and not whiten in 30 days; The dry film tensile strength is 17.8MPa, and elongation at break is 434%; Tensile strength under the film room temperature behind the immersion 24h still can remain on 12.9MPa, and elongation at break can remain on 338%; Dry film can reach 1 grade at the sticking power of glass surface, and the sticking power in the immersion water after 7 days still can maintain 2～3 grades.
Claims (1)
1. the preparation method of an organic siloxane modified aqueous polyurethane coating; The preparation and the polyamine chain extending reaction that comprise silicone-modified performed polymer and dispersion liquid thereof; It is characterized in that: the preparation of described silicone-modified performed polymer at first by vulcabond and low poly-dihydric alcohol, small molecules polyvalent alcohol and butanone under catalyzer dibutyl tin laurate existence condition in 65-90 ℃ of stirring reaction 1.5-2.5 hour; The mol ratio of vulcabond, low poly-dihydric alcohol, small molecules polyvalent alcohol is 3-5: 1: 0.7-1.0; The butanone consumption is the 10-30% of low poly-dihydric alcohol quality, and catalyst levels is the 0.1-0.3% of vulcabond, low poly-dihydric alcohol and small molecules polyvalent alcohol total mass; In reaction solution, add carboxylic small molecules divalent alcohol then in 65-90 ℃ of stirring reaction 2.5-6h, the mol ratio of carboxyl and vulcabond is 1: 4-6; Added the triethylamine stirring reaction 10-40 minute earlier down at 20-45 ℃ at last; The back adds the epoxysilicone stirring reaction and obtained silicone-modified performed polymer in 10-30 minute; The mol ratio of triethylamine and carboxyl is 0.9-1.1: 1, and the mol ratio of epoxysilicone and carboxyl is 1: 5-10; The preparation of described silicone-modified performed polymer dispersion liquid is that above-mentioned performed polymer is at the uniform velocity joined under 5-20 ℃ of stirring in the deionized water until being uniformly dispersed the volume ratio 1 of performed polymer and deionized water: 1.5-4; Described polyamine chain extending reaction is that the polyamine solution with mass percentage concentration 5-15% was added drop-wise in the above-mentioned dispersion liquid reaction 1-2 hour under 5-20 ℃ of stirring; Be warming up to then 30-45 ℃ of stirring reaction 20-40 minute, the mol ratio of polyamine and low poly-dihydric alcohol is 0.8-1.0: 1;
Described vulcabond is selected from isophorone diisocyanate, hexamethylene diisocyanate or tolylene diisocyanate;
Described low poly-dihydric alcohol is selected from W 166 PPG-210 or PPG-220 or PTMG PTMG-1000 or PTMG-2000;
Described small molecules polyvalent alcohol is selected from 1,4-butyleneglycol, 1,2-Ucar 35 or TriMethylolPropane(TMP);
Described carboxylic small molecules divalent alcohol is selected from dimethylol propionic acid or dimethylolpropionic acid;
Described epoxysilicone is selected from γ-Racemic glycidol oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl group Union carbide A-162 or γ-glycidyl ether oxygen base propyl group methyldiethoxysilane;
Described polyamine is selected from quadrol, diethylenetriamine, triethylene tetramine or TEPA.
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| CN102827340B (en) * | 2011-06-13 | 2014-04-02 | 中国科学院化学研究所 | Organosilicon-modified waterborne polyurethane composite material and applications thereof |
| CN102408652B (en) * | 2011-08-09 | 2013-06-12 | 合肥工业大学 | Preparation method of organosiloxane modified WPU/PVA (waterborne polyurethane/polyvinyl alcohol) film |
| CN102505499A (en) * | 2011-11-01 | 2012-06-20 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for organic silicon modified waterborne blending polyurethane wool anti-felting finishing agent |
| CN102617823B (en) * | 2012-03-29 | 2013-06-12 | 合肥工业大学 | Process for preparing hydroxyl polyhedral oligomeric silsesquioxane modified polyurethane |
| CN103450437B (en) * | 2013-08-28 | 2015-10-28 | 桐乡市濮院毛针织技术服务中心 | A kind of organic siloxane modified aqueous polyurethane prepares the method for wool softening agent |
| CN104448206B (en) * | 2014-12-25 | 2017-10-10 | 广州冠志新材料科技有限公司 | A kind of environment-friendly type strippable water-soluble polyurethane resin and its preparation method and application |
| CN104910782A (en) * | 2015-06-17 | 2015-09-16 | 牛无畏 | Organosilicon modified water-based polyurethane paint |
| CN105622878B (en) * | 2016-02-26 | 2018-04-27 | 武汉理工大学 | A kind of preparation method of aqueous waterproofing paint |
| CN105968285A (en) * | 2016-06-02 | 2016-09-28 | 深圳市深赛尔股份有限公司 | Waterborne silane polyurea resin and preparation method thereof |
| CN107974837B (en) * | 2017-12-06 | 2020-04-24 | 佛山市顺德区德美瓦克有机硅有限公司 | Polyurethane modified organic silicon copolymer containing quaternary ammonium salt and preparation method thereof |
| CN109160994B (en) * | 2018-08-02 | 2021-01-15 | 万华化学集团股份有限公司 | Polyurethane dispersion for dry coating primer, and preparation method and application thereof |
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| CN101020738A (en) * | 2007-03-21 | 2007-08-22 | 广州市合工大实力新材料研究院有限公司 | Water-base polyurethane material and its prepn process and application |
| CN101497687A (en) * | 2009-01-16 | 2009-08-05 | 海聚高分子材料科技（广州）有限公司 | Anti-scratch aqueous polyurethane disperse system with high hygrometric state adhesive force and use thereof |
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| CN101020738A (en) * | 2007-03-21 | 2007-08-22 | 广州市合工大实力新材料研究院有限公司 | Water-base polyurethane material and its prepn process and application |
| CN101497687A (en) * | 2009-01-16 | 2009-08-05 | 海聚高分子材料科技（广州）有限公司 | Anti-scratch aqueous polyurethane disperse system with high hygrometric state adhesive force and use thereof |
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