CN108912807B - Method for improving wear resistance of waterborne polyurethane coating - Google Patents
Method for improving wear resistance of waterborne polyurethane coating Download PDFInfo
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- CN108912807B CN108912807B CN201810940234.2A CN201810940234A CN108912807B CN 108912807 B CN108912807 B CN 108912807B CN 201810940234 A CN201810940234 A CN 201810940234A CN 108912807 B CN108912807 B CN 108912807B
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- polyurethane coating
- galactomannan
- aqueous polyurethane
- coating
- wear resistance
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- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229920000926 Galactomannan Polymers 0.000 claims abstract description 33
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 claims abstract description 31
- 239000003973 paint Substances 0.000 claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 238000005299 abrasion Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 25
- 239000011248 coating agent Substances 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005034 decoration Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000006228 supernatant Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VGQXTTSVLMQFHM-UHFFFAOYSA-N peroxyacetyl nitrate Chemical compound CC(=O)OO[N+]([O-])=O VGQXTTSVLMQFHM-UHFFFAOYSA-N 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a method for improving the wear resistance of an aqueous polyurethane coating. 1% of the water-based paint is added, and the molecular weight range is 0.4 multiplied by 104～1.5×104The low molecular weight galactomannan of Da improves the wear resistance of the coating by 5.58-49.11%. The method for improving the wear resistance of the aqueous polyurethane coating has the advantages of simple process, easy control of conditions and good paint film performance, and can be widely applied to the fields of decoration, furniture, construction, machinery, chemical industry and the like.
Description
Technical Field
The invention belongs to the technical field of environment-friendly coatings, and particularly relates to a method for improving the wear resistance of a waterborne polyurethane coating.
Background
The paint is a chemical mixture capable of being covered on the surface of an object firmly and used for protection, decoration, marking and other special purposes. The coating materials can be classified into organic solvent type coating materials, water-based coating materials, and the like according to the difference of solvents in the coating materials. Wherein, the dispersion medium of the solvent-based paint is an organic solvent, which plays a role in dissolving resin and diluting the paint. In the film-forming curing process of the solvent-based coating, after the organic solvent is volatilized, a film-forming substance is dried and formed into a film, so that a hard protective film is formed, and the effects of protecting and beautifying wood products and other substrates are achieved. The solvent-based paint mainly comprises volatile organic compounds such as benzene series, organic ketone, amine, alcohol, ether, ester, acid and the like, and the volatile organic compounds can generate a plurality of photochemical reactions under the action of sunlight to form secondary pollutants with higher toxicity, such as ozone, aldehydes, peroxyacetyl nitrate and the like. The special mixture composed of these nitrogen oxides, hydrocarbon compounds and their intermediate products of photochemical reaction is photochemical smog, and the generation of ozone is the sign of photochemical smog. Therefore, research and development of low pollution and environmental protection become a new direction for the development of the coating industry.
The water-based paint contains no or few volatile substances and air pollutants, has little harm to the environment and human health, and has become a research hotspot of green environment-friendly paints in the fields of furniture, buildings and the like. However, compared with the traditional solvent-based coating, the water-based coating has lower hardness and poorer wear resistance, and is not suitable for the fields of machinery, chemical engineering and the like with strong coating wear resistance. Therefore, the improvement of the wear resistance of the water-based paint is an important measure for improving the application field of the water-based paint in the paint industry.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention aims to provide a method for improving the wear resistance of an aqueous polyurethane coating, which uniformly disperses low-molecular-weight galactomannan with a certain molecular weight range in the aqueous coating and improves the wear resistance and the glossiness of the aqueous coating under the condition of not changing the hardness of the coating. The method has the advantages of simple process, easily controlled conditions and good paint film performance, and can be widely applied to the fields of decoration, furniture, construction, machinery, chemical industry and the like.
The technical scheme is as follows: in order to achieve the above object, the technical solution of the present invention is as follows:
a method for improving the wear resistance of aqueous polyurethane paint is characterized in that a galactomannan component is added into the aqueous polyurethane paint.
The addition amount of the galactomannan in g/mL is 1-3%.
The molecular weight range of the galactomannan is 0.4 × 104～1.5×104Da。
The molecular weight range of the galactomannan is 1.5 × 104Da。
The method for improving the wear resistance of the aqueous polyurethane coating comprises the steps of adding the galactomannan component before the aqueous polyurethane coating is used, and uniformly mixing.
According to the method for improving the wear resistance of the aqueous polyurethane coating, every 100mL of the aqueous polyurethane coating contains 71.4mL of polyurethane polyhydroxy prepolymer dispersion liquid and 28.6mL of polyisocyanate curing agent.
Galactomannan (GM) is a nonlinear heteropolysaccharide which takes mannose as a basic structural unit and forms a main chain through beta-1, 4-glycosidic bonds, and galactose is connected to the main chain through alpha-1, 6-glycosidic bonds, and has the characteristics of acid and alkali resistance, good thermal stability, high molecular weight, high viscosity, high hydroxyl content, strong water solubility and the like. According to the application, the galactomannan is uniformly dispersed in the coating, rich hydroxyl in the polysaccharide can be in hydrogen bond combination with alcoholic hydroxyl of polyhydric alcohol in the water-based coating, and the galactomannan and the coating are crosslinked to form a compound, so that the water-based coating is endowed with some special properties.
Has the advantages that: compared with the prior art, the galactomannan with a certain molecular weight range is added into the waterborne polyurethane coating, so that the wear resistance of the waterborne coating can be effectively improved under the condition of not changing the hardness of the coating. The method has the advantages of simple process, easily controlled conditions and good paint film performance, and can be widely applied to the fields of decoration, furniture, construction, machinery, chemical industry and the like.
Detailed Description
The invention is further illustrated by the following examples. The examples are intended to illustrate, but not to limit, the invention. Those of ordinary skill in the art will understand that these examples are not intended to limit the present invention in any way, and that appropriate modifications can be made without departing from the spirit and scope of the present invention.
In the following examples, galactomannan molecular weights (Mw) were determined by HPLC. Chromatograph: HPLC high performance liquid chromatograph; a chromatographic column: three columns, namely a Waters Ultrahydrogel TM 2000 (7.8X 300mm), a Waters Ultrahydrogel TM 250 (7.8X 300mm) and a Waters Ultrahydrogel TM 120 (7.8X 300mm), are connected in series in sequence; mobile phase: ionized water with the flow rate of 0.6 mL/min; column temperature: 65 ℃; detecting by a difference detector; standard samples: polyethylene glycol (molecular weight 360-120000 Da).
Example 1
Preparation method of low molecular weight galactomannan
(1) Galactomannan extract preparation. Mechanically pulverizing air-dried sesbania endosperm sheet, adding distilled water at a solid-liquid ratio of 1: 50, extracting at 50 deg.C for 24 hr, centrifuging at 10000 rpm for 10min to obtain supernatant, adding anhydrous ethanol into the supernatant to obtain precipitate, and vacuum drying the precipitate to obtain galactomannan powder.
(2) The endo-mannanase selectively hydrolyzes galactomannans. Weighing 20.0g of the galactomannan extract obtained in the step (1) into a 2L enzyme reaction tank, adding distilled water, endo-mannase and 1mol/L citric acid buffer solution to enable the volume of reaction liquid to be 1000mL, fully and uniformly mixing, reacting for 24h under the conditions of substrate concentration of 10%, enzyme addition of 20U/g galactomannan, pH value of 4.8 and 50 ℃, after the enzymatic hydrolysis reaction is finished, placing an enzymatic hydrolysate at 100 ℃ for 10min to inactivate the endo-mannase, centrifuging for 10min under the condition of 10000 r/min, and obtaining supernatant which is the enzymatic hydrolysate containing the incomplete degradation product of the galactomannan.
(3) Low molecular weight galactomannan fractions of various molecular weight ranges were prepared. And (3) taking 1000mL of galactomannan enzymolysis supernatant in the step (2), adding absolute ethyl alcohol under the stirring condition to ensure that the concentration of the ethyl alcohol in the system is 40% (v/v), and centrifuging for 10min under the condition of 10000 r/min to obtain supernatant and precipitate. The precipitate was washed 3 times with 30mL of 40% (v/v) aqueous ethanol, centrifuged (10000 rpm, 10min), freeze-dried to give a solid sample P1, and its molecular weight was measured. The supernatant was used for further fractionation in the next stage.
(4) And (4) taking the supernatant obtained after the solid-liquid separation in the step (3), adding absolute ethyl alcohol under the stirring condition to ensure that the concentration of the ethyl alcohol in the system is 50% (v/v), and centrifuging for 10min under the condition of 10000 r/min to obtain the supernatant and the precipitate. The precipitate was washed 3 times with 30mL of 50% (v/v) aqueous ethanol, centrifuged (10000 rpm, 10min), freeze-dried to give a solid sample P2, and its molecular weight was measured. The supernatant was used for further fractionation in the next stage.
(5) And (4) taking the supernatant obtained after the solid-liquid separation in the step (4), adding absolute ethyl alcohol under the stirring condition to ensure that the concentration of the ethyl alcohol in the system is 65% (v/v), and centrifuging for 10min under the condition of 10000 r/min to obtain the supernatant and the precipitate. The precipitate was washed 3 times with 30mL of a 65% (v/v) aqueous ethanol solution, centrifuged (10000 rpm, 10min), freeze-dried to give a solid sample P3, and its molecular weight was measured.
The results showed that the obtained low molecular weight galactomannans P1, P2 and P3 of different molecular weights had molecular weights of 1.5X 104Da、0.8×104Da and 0.4X 104Da。
Example 2
The preparation of the high-wear-resistance waterborne polyurethane coating comprises the following steps
(1) A commercially available polyurethane polyhydroxy prepolymer dispersion liquid (solid content is 40%, w/v) and a polyisocyanate curing agent (solid content is 80%, w/v) were weighed out, 71.4mL of polyurethane polyhydroxy prepolymer dispersion liquid and 28.6mL of polyisocyanate curing agent were weighed out according to a ratio of 10: 4 (v: v) of prepolymer dispersion liquid to curing agent, and dispersed for 10min at 25 ℃ by a homogenizer to obtain an aqueous polyurethane coating.
(2) And (2) adding 1g, 2g and 3g of galactomannan (P1, P2 and P3) with different molecular weights as a modifier into 100mL of the aqueous polyurethane coating obtained in the step (1) according to the addition amount of the low molecular weight galactomannan of 1%, 2% and 3%, and dispersing for 10min at 25 ℃ by using a homogenizer to obtain the modified aqueous polyurethane coating.
Example 3
The aqueous polyurethane coating and the modified polyurethane coating prepared in example 2 were applied to the surface of a wood substrate by pressure spraying. The wood substrate used was a multilayer plywood with a size of 10X 10cm and a coating thickness of 60 μm. After the coating on the surface of the wood substrate is solidified into a film, the substrate is placed in a 50 ℃ forced air drying oven to be dried for 120min to evaporate redundant moisture in the coating, and after the substrate is placed in a ventilation mode at room temperature for 7d, the adhesion, the glossiness, the abrasion loss and the pencil hardness are detected.
The performance results of the aqueous polyurethane coating and the modified aqueous polyurethane coating are shown in table 1.
TABLE 1 Properties of aqueous polyurethane coating and modified aqueous polyurethane coating
| Numbering | Addition amount (%) | Grade of adhesion | Hardness of pencil | Amount of wear (g) | Abrasion resistance increasing rate (%) |
| Water-based paint | 0 | 2 | 5H | 0.0167 | - |
| P1+ Water-based paint | 1 | 2 | 5H | 0.0085 | 49.11 |
| P1+ Water-based paint | 2 | 2 | 5H | 0.0091 | 45.51 |
| PI + water paint | 3 | 2 | 5H | 0.0104 | 37.72 |
| P2+ Water-based paint | 1 | 2 | 5H | 0.0103 | 38.32 |
| P2+ Water-based paint | 2 | 2 | 5H | 0.0105 | 37.13 |
| P2+ Water-based paint | 3 | 2 | 4H | 0.0117 | 29.94 |
| P3+ Water-based paint | 1 | 2 | 5H | 0.0151 | 9.58 |
| P3+ Water-based paint | 2 | 2 | 4H | 0.0155 | 7.19 |
| P3+ Water-based paint | 3 | 2 | 4H | 0.0161 | 3.59 |
The result shows that the addition of the low molecular weight galactomannan modifier with different molecular weights in the waterborne polyurethane coating does not change the adhesion capability of the coating on a wood substrate and the hardness of the coating. When the addition amount is 1%, the molecular weight is 1.5X 104Da、0.8×104Da and 0.4X 104With Da of low molecular weight galactomannan, the abrasion resistance of the water paint is improved by 49.11%, 38.32% and 9.58%, respectively, which shows that the galactomannan as a modifier of the water paint can improve the abrasion resistance.
Claims (4)
1. A method for improving the wear resistance of aqueous polyurethane paint is characterized by comprising the following steps: the aqueous polyurethane coating is added with a galactomannan component; the addition amount of the galactomannan is 1-3 g/100mL, and the molecular weight of the galactomannan is 0.8 multiplied by 104Da ~1.5×104Da。
2. The method of claim 1, wherein the galactomannan has a molecular weight in the range of 1.5 x 104Da。
3. The method for improving the abrasion resistance of the aqueous polyurethane coating according to claim 1, wherein the galactomannan component is added and mixed uniformly before the aqueous polyurethane coating is used.
4. The method for improving the abrasion resistance of an aqueous polyurethane coating according to claim 1, wherein the aqueous polyurethane coating contains 71.4mL of the polyurethane polyhydroxy prepolymer dispersion and 28.6mL of the polyisocyanate curing agent per 100mL of the aqueous polyurethane coating.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810940234.2A CN108912807B (en) | 2018-08-16 | 2018-08-16 | Method for improving wear resistance of waterborne polyurethane coating |
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| CN201810940234.2A CN108912807B (en) | 2018-08-16 | 2018-08-16 | Method for improving wear resistance of waterborne polyurethane coating |
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| CN108912807B true CN108912807B (en) | 2021-02-19 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348530A (en) * | 2008-09-17 | 2009-01-21 | 北京林业大学 | Galactomannan gum got by irradiation degradation, preparation and use thereof |
| CN104761940A (en) * | 2015-03-25 | 2015-07-08 | 田福东 | Wear-resistant waterborne polyurethane coating |
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2018
- 2018-08-16 CN CN201810940234.2A patent/CN108912807B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348530A (en) * | 2008-09-17 | 2009-01-21 | 北京林业大学 | Galactomannan gum got by irradiation degradation, preparation and use thereof |
| CN104761940A (en) * | 2015-03-25 | 2015-07-08 | 田福东 | Wear-resistant waterborne polyurethane coating |
Non-Patent Citations (1)
| Title |
|---|
| 纳米纤维素改性水性聚氨酯及其在木器涂料中的应用;潘汝潭;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180115(第1期);正文第7-8，24-26、33-35页 * |
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Application publication date: 20181130 Assignee: Suzhou Hertz Electronic Technology Co.,Ltd. Assignor: NANJING FORESTRY University Contract record no.: X2021320000035 Denomination of invention: A method to improve the wear resistance of Waterborne Polyurethane Coatings Granted publication date: 20210219 License type: Common License Record date: 20210528 |
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Application publication date: 20181130 Assignee: Suzhou Xiaohan culture media Co.,Ltd. Assignor: NANJING FORESTRY University Contract record no.: X2022320000026 Denomination of invention: Method for improving wear resistance of waterborne polyurethane coating Granted publication date: 20210219 License type: Common License Record date: 20220302 |
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Application publication date: 20181130 Assignee: Nanjing Licheng Biomedical Technology Co.,Ltd. Assignor: NANJING FORESTRY University Contract record no.: X2024320000011 Denomination of invention: A method to improve the wear resistance of waterborne polyurethane coatings Granted publication date: 20210219 License type: Common License Record date: 20240516 |