CN111187564A - Heat-conducting coating capable of heating polyurethane automobile decoration film and manufacturing method thereof - Google Patents
Heat-conducting coating capable of heating polyurethane automobile decoration film and manufacturing method thereof Download PDFInfo
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Abstract
A heat-conducting coating capable of heating a polyurethane automobile decorative film and a manufacturing method thereof comprise the following raw materials in percentage by mass: 30 parts of carbon nanotube solution, 60 parts of carbon fiber chopped fiber, 10-100 parts of polybutylene terephthalate glycol, 10-200 parts of IPDI or TDI, 50-60 parts of isophorone diamine, 10-15 parts of diisobutylamine, 1600 parts of methyl ethyl ketone 1500-1600 parts, 3 parts of pigment, 15 parts of titanium dioxide and 1.5-3 parts of coupling agent. The coating has the protection and heating deicing effects, is used for protecting and heating deicing of automobiles in winter, so that automobile paint and electronic components in automobile bodies are protected, and the coating has the scratch-proof and attractive effects.
Description
Technical Field
The invention relates to the technical field of preparation of environment-friendly heating functional waterborne polyurethane coatings, in particular to a heat-conducting coating capable of heating a polyurethane automobile decorative film and a manufacturing method thereof.
Background
As a brand new coating, the polyurethane coating has beautiful appearance, good decorative performance and very good physical and mechanical properties after being coated. The composite material has the characteristics of corrosion resistance, impact resistance, low temperature resistance, high hardness, high elasticity, chemical reagent resistance and the like, and has very wide application in the related fields of automobile manufacturing and processing, ship engineering, aerospace, industrial and civil engineering and the like.
The research and development and application work of polyurethane coatings are developed in China from the 50 th of the 20 th century. With the continuous promotion and improvement of the living standard of mass substances in the society, the development speed of a series of industries related to automobile processing, furniture manufacturing and processing, petrochemical industry, mechanical industry, bridges and ships and the like is continuously promoted, and the polyurethane coating begins to enter a brand new stage of rapid development by virtue of the outstanding performance advantages. Statistical data show that the usage of polyurethane coatings in various industry fields shows a very rapid development trend since the 2004 of 1980, the total usage of the polyurethane coatings realizes breakthrough development from 0.17 ten thousand to 20 ten thousand tons, the yield of the polyurethane coatings is only second to that of alkyd resin paint, acrylic resin paint and phenolic resin paint, and the polyurethane coatings become the fourth largest variety in the coating field, and the development trend continues till now, and the yield and the application range still keep a very rapid development trend.
With the application of polyurethane coating in large quantity, the coating structure system has a large amount of organic solvent, which causes serious pollution to the environment, in 1942, Shlack successfully prepares cationic waterborne polyurethane for the first time, and in the 20 th century, 70 th generation waterborne polyurethane starts industrial production, and the annual output of waterborne polyurethane resin is about 6 ten thousand tons all over the world.
In recent years, waterborne polyurethane coatings occupy a large number of markets, but from the present, waterborne polyurethanes used at home and abroad have relatively large defects in process. After the waterborne polyurethane coating is formed into a film, the water resistance is insufficient, and a large amount of carbon dioxide bubbles generated by reaction with water in the film forming stage possibly remain in the film, so that the performance of the waterborne polyurethane coating is influenced. Most importantly, the mechanical property is insufficient after film forming, the film hardness and impact resistance are insufficient, and high cost is added, so that the film is difficult to apply to decorative films of automobiles and the like. Meanwhile, the existing heatable polyurethane coating at home and abroad has a great technical bottleneck, and is not ideal in the aspects of heating performance stability, polyurethane mechanical property and structural stability.
Disclosure of Invention
The invention aims to provide a heat-conducting coating capable of heating a polyurethane automobile decorative film and a manufacturing method thereof, which have protection and heating deicing effects, are used for protecting and heating deicing of automobiles in winter, so that automobile paint and electronic components in automobile bodies are protected, have scratch-resistant and attractive effects, and are particularly suitable for automobiles in northern China and automobiles in cold regions. The coating is coated on a substrate, the protective film is formed in a sticking mode, the heating and deicing functions can be realized after the coating is connected with an automobile battery, the heating is uniform, the safety and the stability are realized, the defects that the traditional heating material directly added is nonuniform in heating, high in crystallinity and not soft enough in film hardness and cannot be prepared into an automobile film material are overcome, the protective and deicing functions of vehicles in cold regions are facilitated, the service life of the automobiles is prolonged, and the problems in the background technology can be solved.
In order to achieve the purpose, the invention provides the following technical scheme: a heat-conducting coating capable of heating a polyurethane automobile decoration film comprises the following raw materials in parts by mass:
30 parts of carbon nanotube solution, 60 parts of carbon fiber chopped fiber, 10-100 parts of polybutylene terephthalate glycol, 10-200 parts of IPDI or TDI, 50-60 parts of isophorone diamine, 10-15 parts of diisobutylamine, 1600 parts of methyl ethyl ketone 1500-1600 parts, 3 parts of pigment, 15 parts of titanium dioxide and 1.5-3 parts of coupling agent.
Further, the length of the carbon fiber chopped fiber is 2-5 mm.
Further, the coupling agent is a silane coupling agent or an aluminum zirconium coupling agent.
Further, the purity of the polybutylene terephthalate glycol is 99.5% or more.
Further, the pigment is preferably an oily color paste but not limited to an oily color paste.
Further, the titanium dioxide is nanoscale titanium dioxide.
Further, the solid content of the polyurethane coating ranges from 30% to 45%.
The invention also provides a manufacturing method of the heat-conducting coating capable of heating the polyurethane automobile decorative film, which comprises the following steps:
s1: modification of carbon nanotubes and fibers: adding 1.5-3% of coupling agent into 30 parts of carbon nanotube solution, stirring for 2 hours at 85-95 ℃, refluxing dispersion liquid through a condenser pipe, soaking 60 parts of carbon fiber chopped fibers in 3-5% of coupling agent solution, heating at 60-80 ℃, heating for 4-5 hours, condensing and refluxing the solution through the condenser pipe, and then filtering and placing the carbon fiber chopped fibers;
s2: preparation of prepolymer solution: reacting 10-100 parts of polybutylene terephthalate glycol with 10-200 parts of IPDI or TDI in methyl ethyl ketone at the reaction temperature of 120-140 ℃ for 3h to prepare a prepolymer solution with the solid content of 80-85%;
s3: introduction of a modifying group: 1000 parts of prepolymer solution in S2, 50-60 parts of isophorone diamine (IPDA) and 10-15 parts of diisobutylamine react for 1h in 1500-1600 parts of methyl ethyl ketone at 40-60 ℃ to obtain modified solution;
s4: preparation of polyurethane: adding 70-80 parts of 75% IPDI into the solution in S3, heating and stirring at 80 ℃ for 3h, adding 10 parts of a mixed solution of methyl ethyl ketone and isopropanol, and continuing stirring for 30 minutes to obtain a 30% concentration resin solution, wherein the viscosity of the solution at 25 ℃ is 1000-1200mPa & S;
s5: preparation of polyurethane coating: 100 parts of the solution in S4 is taken, 5 parts of carbon nanotubes, 15 parts of carbon fibers, 3 parts of pigment and 15 parts of titanium dioxide in S1 are added, and stirring is carried out under a high-speed stirrer, wherein the stirring speed is 1000 revolutions per minute, and the stirring time is 30 minutes.
Compared with the prior art, the invention has the characteristics of scratch resistance, attractive appearance, good deicing effect and the like. The solid content of the coating reaches more than 60%, the crystallinity and the softness are properly controlled, the key requirements of automobile electronic equipment, electronic products, important electronic packaging and the like in cold regions can be effectively protected, and the coating has wide application prospects in the fields of military industry and civil use.
Detailed Description
The following examples will explain the present invention in detail, but the present invention is not limited thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples, the conductivity was tested according to ISO 11713-2000; impact resistance test of paint film; GB/T1731-1993 paint film flexibility assay; GB/T1763-1979 paint film resistance to chemical reagents.
A heat-conducting coating capable of heating a polyurethane automobile decoration film comprises the following raw materials in parts by mass:
30 parts of carbon nanotube solution, 60 parts of carbon fiber chopped fiber, 10-100 parts of polybutylene terephthalate glycol, 10-200 parts of IPDI or TDI, 50-60 parts of isophorone diamine, 10-15 parts of diisobutylamine, 1600 parts of methyl ethyl ketone 1500-1600 parts, 3 parts of pigment, 15 parts of titanium dioxide and 1.5-3 parts of coupling agent.
Example 1
A method for manufacturing a heat-conducting coating capable of heating a polyurethane automobile decoration film comprises the following steps:
s1: modification of carbon nanotubes and fibers: adding 30 parts of carbon nanotube solution into 1.5 parts of coupling agent, stirring for 2 hours at 85 ℃, refluxing the dispersion liquid through a condenser pipe, soaking 60 parts of carbon fiber chopped fibers in 3 parts of coupling agent solution, heating at 60 ℃ for 5 hours, condensing and refluxing the solution through the condenser pipe, and filtering and placing the carbon fiber chopped fibers;
s2: preparation of prepolymer solution: reacting 10 parts of polybutylene terephthalate glycol with 100 parts of IPDI in methyl ethyl ketone at the reaction temperature of 120 ℃ for 3 hours to prepare a prepolymer solution with the solid content of 85%;
s3: introduction of a modifying group: reacting 1000 parts of prepolymer solution in S2 with 50 parts of isophorone diamine (IPDA) and 10 parts of diisobutylamine in 1500 parts of methyl ethyl ketone at 40 ℃ for 1h to obtain modified solution;
s4: preparation of polyurethane: adding 70 parts of 75% IPDI (NCO content 12%) into the solution in S3, heating and stirring at 80 ℃ for 3 hours, adding 10 parts of a mixed solution of methyl ethyl ketone and isopropanol, and continuing stirring for 30 minutes to obtain a 30% concentration resin solution, wherein the viscosity of the solution at 25 ℃ is 1000mPa & S;
s5: preparation of polyurethane coating: 100 parts of the solution in S4 is taken, 5 parts of carbon nanotubes, 15 parts of carbon fibers, 3 parts of pigment and 15 parts of titanium dioxide in S1 are added, and stirring is carried out under a high-speed stirrer, wherein the stirring speed is 1000 revolutions per minute, and the stirring time is 30 minutes.
Example 2
A method for manufacturing a heat-conducting coating capable of heating a polyurethane automobile decoration film comprises the following steps:
s1: modification of carbon nanotubes and fibers: 30 parts of a carbon nanotube solution was added to 3% of a coupling agent, stirred at 85 ℃ for 2 hours, and the dispersion was refluxed through a condenser tube. Soaking 60 parts of carbon fiber chopped fibers in 5 parts of coupling agent solution, heating at 60 ℃ for 4 hours, condensing and refluxing the solution through a condensing tube, and then filtering and placing the carbon fiber chopped fibers;
s2: preparation of prepolymer solution: reacting 50 parts of polybutylene terephthalate glycol with 100 parts of IPDI in methyl ethyl ketone at the reaction temperature of 120 ℃ for 3 hours to prepare a prepolymer solution with the solid content of 80-85%;
s3: introduction of a modifying group: reacting 1000 parts of prepolymer solution in S2 with 50 parts of isophorone diamine (IPDA) and 10 parts of diisobutylamine in 1500 parts of methyl ethyl ketone at 40 ℃ for 1h to obtain modified solution;
s4: preparation of polyurethane: adding 70 parts of 75% IPDI (NCO content 12%) into the solution in S3, heating and stirring at 80 ℃ for 3 hours, adding 10 parts of a mixed solution of methyl ethyl ketone and isopropanol, and continuing stirring for 30 minutes to obtain a 30% concentration resin solution, wherein the viscosity of the solution at 25 ℃ is 1200mPa & S;
s5: preparation of polyurethane coating: 100 parts of the solution in S4 is taken, 5 parts of carbon nanotubes, 15 parts of carbon fibers, 3 parts of pigment and 15 parts of titanium dioxide in S1 are added, and stirring is carried out under a high-speed stirrer, wherein the stirring speed is 1000 revolutions per minute, and the stirring time is 40 minutes.
Example 3
A method for manufacturing a heat-conducting coating capable of heating a polyurethane automobile decoration film comprises the following steps:
s1: modification of carbon nanotubes and fibers: 30 parts of the carbon nanotube solution was added to 2 parts of the coupling agent, stirred at 85 ℃ for 2 hours, and the dispersion was refluxed through a condenser tube. Soaking 60 parts of carbon fiber chopped fibers in 4 parts of a coupling agent solution, heating at the temperature of 60 ℃ for 4.5 hours, condensing and refluxing the solution through a condensing tube, and then filtering and placing the carbon fiber chopped fibers;
s2: preparation of prepolymer solution: reacting 100 parts of polybutylene terephthalate glycol with 100 parts of IPDI in methyl ethyl ketone at the reaction temperature of 120 ℃ for 3 hours to prepare a prepolymer solution with the solid content of 82%;
s3: introduction of a modifying group: reacting 1000 parts of prepolymer solution in S2 with 50 parts of isophorone diamine (IPDA) and 10 parts of diisobutylamine in 1500 parts of methyl ethyl ketone at 40 ℃ for 1h to obtain modified solution;
s4: preparation of polyurethane: adding 70 parts of 75% IPDI (NCO content 12%) into the solution in S3, heating and stirring at 80 ℃ for 3 hours, adding 10 parts of a mixed solution of methyl ethyl ketone and isopropanol, and continuing stirring for 30 minutes to obtain a 30% concentration resin solution, wherein the viscosity of the solution at 25 ℃ is 1100mPa & S;
s5: preparation of polyurethane coating: 100 parts of the solution in S4 is taken, 5 parts of carbon nanotubes, 15 parts of carbon fibers, 3 parts of pigment and 15 parts of titanium dioxide in S1 are added, and stirring is carried out under a high-speed stirrer, wherein the stirring speed is 1000 revolutions per minute, and the stirring time is 30 minutes.
Example 4
A method for manufacturing a heat-conducting coating capable of heating a polyurethane automobile decoration film comprises the following steps:
s1: modification of carbon nanotubes and fibers: 30 parts of a carbon nanotube solution was added to 3% of a coupling agent, stirred at 85 ℃ for 2 hours, and the dispersion was refluxed through a condenser tube. Soaking 60 parts of carbon fiber chopped fibers in 3-5% of a coupling agent solution, heating at 60 ℃ for 5 hours, condensing and refluxing the solution through a condensing tube, and then filtering and placing the carbon fiber chopped fibers;
s2: preparation of prepolymer solution: reacting 100 parts of polybutylene terephthalate glycol with 200 parts of IPDI in methyl ethyl ketone at the reaction temperature of 120 ℃ for 3 hours to prepare a prepolymer solution with the solid content of 82%;
s3: introduction of a modifying group: reacting 1000 parts of prepolymer solution in S2 with 50 parts of isophorone diamine (IPDA) and 10 parts of diisobutylamine in 1500 parts of methyl ethyl ketone at 40 ℃ for 1h to obtain modified solution;
s4: preparation of polyurethane: adding 70 parts of 75% IPDI (NCO content 12%) into the solution in S3, heating and stirring at 80 ℃ for 3 hours, adding 10 parts of a mixed solution of methyl ethyl ketone and isopropanol, and continuing stirring for 30 minutes to obtain a 30% concentration resin solution, wherein the viscosity of the solution at 25 ℃ is 1200mPa & S;
s5: preparation of polyurethane coating: and (3) taking 100 parts of the solution in the S4, adding 5 parts of carbon nanotubes, 15 parts of carbon fibers, 3 parts of pigment and 15 parts of titanium dioxide in the S1, and stirring at a high-speed stirrer at 1200 rpm for 30 minutes.
Example 5
A method for manufacturing a heat-conducting coating capable of heating a polyurethane automobile decoration film comprises the following steps:
s1: modification of carbon nanotubes and fibers: 30 parts of a carbon nanotube solution was added to 3% of a coupling agent, stirred at 85 ℃ for 2 hours, and the dispersion was refluxed through a condenser tube. Soaking 60 parts of carbon fiber chopped fibers in a 5% coupling agent solution, heating at 60 ℃ for 5 hours, condensing and refluxing the solution through a condensing tube, and then filtering and placing the carbon fiber chopped fibers;
s2: preparation of prepolymer solution: reacting 100 parts of polybutylene terephthalate glycol with 200 parts of IPDI in methyl ethyl ketone at the reaction temperature of 140 ℃ for 3 hours to prepare a prepolymer solution with the solid content of 80%;
s3: introduction of a modifying group: reacting 1000 parts of prepolymer solution in S2 with 50 parts of isophorone diamine (IPDA) and 10 parts of diisobutylamine in 1500 parts of methyl ethyl ketone at 40 ℃ for 1h to obtain modified solution;
s4: preparation of polyurethane: adding 70 parts of 75% IPDI (NCO content 12%) into the solution in S3, heating and stirring at 80 ℃ for 3h, adding 10 parts of a mixed solution of methyl ethyl ketone and isopropanol, and continuing stirring for 30 minutes to obtain a 30% concentration resin solution, wherein the viscosity of the solution at 25 ℃ is 1000-1200mPa & S;
s5: preparation of polyurethane coating: 100 parts of the solution in S4 was taken, and 5 parts of carbon nanotubes, 15 parts of carbon fibers, 3 parts of pigment and 15 parts of titanium dioxide in S1 were added thereto, and the mixture was stirred in a high-speed stirrer at 1100 rpm for 30 minutes.
Example 6
A method for manufacturing a heat-conducting coating capable of heating a polyurethane automobile decoration film comprises the following steps:
s1: modification of carbon nanotubes and fibers: 30 parts of the carbon nanotube solution was added with 2.5% of a coupling agent, stirred at 85 ℃ for 2 hours, and the dispersion was refluxed through a condenser tube. Soaking 60 parts of carbon fiber chopped fibers in a 5% coupling agent solution, heating at 60 ℃ for 5 hours, condensing and refluxing the solution through a condensing tube, and then filtering and placing the carbon fiber chopped fibers;
s2: preparation of prepolymer solution: reacting 100 parts of polybutylene terephthalate glycol with 200 parts of IPDI in methyl ethyl ketone at the reaction temperature of 140 ℃ for 3 hours to prepare a prepolymer solution with the solid content of 80%;
s3: preparation of prepolymer solution: reacting 50 parts of polybutylene terephthalate glycol with 100 parts of IPDI in methyl ethyl ketone at the reaction temperature of 120 ℃ for 3 hours to prepare a prepolymer solution with the solid content of 80%;
s4: preparation of polyurethane: adding 70 parts of 75% IPDI (NCO content 12%) into the solution in S3, heating and stirring at 80 ℃ for 3 hours, adding 10 parts of a mixed solution of methyl ethyl ketone and isopropanol, and continuing stirring for 30 minutes to obtain a 30% concentration resin solution, wherein the viscosity of the solution at 25 ℃ is 1200mPa & S;
s5: preparation of polyurethane coating: 100 parts of the solution in S4 was added to 5 parts of carbon nanotubes, 15 parts of carbon fibers, 3 parts of pigment and 15 parts of titanium dioxide in (1), and the mixture was stirred in a high-speed stirrer at 1000 rpm for 30 minutes.
The principle of the invention lies in the modification of the carbon nano tube and the carbon fiber material, so that the material and the waterborne polyurethane can be uniformly dispersed to form a uniform system, the carbon material is modified to increase the bonding property with the waterborne polyurethane, the molecular weight and the crystallinity of the waterborne polyurethane are ensured by changing the proportion of soft-hard segment monomers and adding other functional monomers and matching with process conditions, so that a film formed by a coating can be suitable for manufacturing an automobile film, meanwhile, the crystallinity is properly controlled, so that the film has certain scratch resistance and heat resistance stability after being pasted, and the whole film layer is not subjected to bubble generation and yellowing oxidation after being heated.
The automobile film has the advantages of scratch resistance, attractive appearance and heating deicing function, and is suitable for automobile film protection in cold regions.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The heat-conducting coating capable of heating the polyurethane automobile decorative film is characterized by comprising the following raw materials in parts by mass:
30 parts of carbon nanotube solution, 60 parts of carbon fiber chopped fiber, 10-100 parts of polybutylene terephthalate glycol, 10-200 parts of IPDI or TDI, 50-60 parts of isophorone diamine, 10-15 parts of diisobutylamine, 1600 parts of methyl ethyl ketone 1500-1600 parts, 3 parts of pigment, 15 parts of titanium dioxide and 1.5-3 parts of coupling agent.
2. The heat conductive coating of the heatable polyurethane-based automotive decorative film according to claim 1, wherein the length of the carbon fiber chopped fiber is 2 to 5 mm.
3. The heat conductive coating material for a heatable polyurethane automotive decorative film according to claim 1, wherein the coupling agent is a silane coupling agent or an aluminum zirconium coupling agent.
4. The heat conductive coating material for a heatable polyurethane automotive decorative film according to claim 1, wherein the purity of the polybutylene terephthalate glycol is 99.5% or more.
5. The heat-conducting paint of the heatable polyurethane automobile decoration film as claimed in claim 1, wherein the pigment is preferably but not limited to oil color paste.
6. The heat conductive coating of heatable polyurethane automotive decorative film according to claim 1, wherein the titanium dioxide is nano-sized titanium dioxide.
7. The thermally conductive coating material for a heatable polyurethane-based automotive decorative film according to claim 1, wherein the urethane coating material has a solid content ranging from 30 to 45%.
8. The method for manufacturing the heat conductive paint of the heatable polyurethane automobile decorative film according to claim 1, which comprises the following steps:
s1: modification of carbon nanotubes and fibers: adding 1.5-3% of coupling agent into 30 parts of carbon nanotube solution, stirring for 2 hours at 85-95 ℃, refluxing dispersion liquid through a condenser pipe, soaking 60 parts of carbon fiber chopped fibers in 3-5% of coupling agent solution, heating at 60-80 ℃, heating for 4-5 hours, condensing and refluxing the solution through the condenser pipe, and then filtering and placing the carbon fiber chopped fibers;
s2: preparation of prepolymer solution: reacting 10-100 parts of polybutylene terephthalate glycol with 10-200 parts of IPDI or TDI in methyl ethyl ketone at the reaction temperature of 120-140 ℃ for 3h to prepare a prepolymer solution with the solid content of 80-85%;
s3: introduction of a modifying group: 1000 parts of prepolymer solution in S2, 50-60 parts of isophorone diamine (IPDA) and 10-15 parts of diisobutylamine react for 1h in 1500-1600 parts of methyl ethyl ketone at 40-60 ℃ to obtain modified solution;
s4: preparation of polyurethane: adding 70-80 parts of 75% IPDI into the solution in S3, heating and stirring at 80 ℃ for 3h, adding 10 parts of a mixed solution of methyl ethyl ketone and isopropanol, and continuing stirring for 30 minutes to obtain a 30% concentration resin solution, wherein the viscosity of the solution at 25 ℃ is 1000-1200mPa & S;
s5: preparation of polyurethane coating: 100 parts of the solution in S4 is taken, 5 parts of carbon nanotubes, 15 parts of carbon fibers, 3 parts of pigment and 15 parts of titanium dioxide in S1 are added, and stirring is carried out under a high-speed stirrer, wherein the stirring speed is 1000 revolutions per minute, and the stirring time is 30 minutes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891667A (en) * | 2023-06-29 | 2023-10-17 | 上海交通大学 | Regenerated carbon fiber composite electric heating anti-icing/deicing coating material and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103649243A (en) * | 2011-07-13 | 2014-03-19 | Posco公司 | Resin composition for a surface treatment, and steel sheet coated with same |
| CN105025598A (en) * | 2015-07-06 | 2015-11-04 | 广东天弼陶瓷有限公司 | Electrothermal composite ceramic brick and preparation method thereof |
| CN105452332A (en) * | 2013-07-31 | 2016-03-30 | 三菱化学株式会社 | Method for producing polycarbonate diol and polycarbonate diol, and method for producing polyurethane and polyurethane |
| CN105622891A (en) * | 2015-12-21 | 2016-06-01 | 江南大学 | Preparation method for polysiloxane emulsion modified waterborne polyurethane emulsion |
| CN105705597A (en) * | 2013-08-27 | 2016-06-22 | 关西涂料株式会社 | Water-based paint composition and painted article |
| CN105732940A (en) * | 2016-05-11 | 2016-07-06 | 江南大学 | Preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion |
| CN106488938A (en) * | 2014-07-07 | 2017-03-08 | 东曹株式会社 | UV resistant absorbent polyurethane urea resin compositionss, the formed body employing said composition and coating material |
| CN104212170B (en) * | 2014-08-11 | 2017-08-25 | 广东昌亿新材料有限公司 | A kind of wear-resisting polyphenyl thioether composite material of high heat conduction and preparation method thereof |
| CN107384166A (en) * | 2017-06-27 | 2017-11-24 | 天长市巨龙车船涂料有限公司 | A kind of frost prevention antifreeze vehicle coating |
| CN107641483A (en) * | 2017-07-17 | 2018-01-30 | 常州中英科技股份有限公司 | A kind of high heat conduction bonding sheet and preparation method thereof |
| CN109081897A (en) * | 2018-08-01 | 2018-12-25 | 万华化学集团股份有限公司 | The excellent polyurethane of wet-hot aging performance or the aqueous dispersion of polyurethane-urea and its preparation method and application |
| CN110105828A (en) * | 2019-04-28 | 2019-08-09 | 苏州格瑞丰纳米科技有限公司 | A kind of graphene slurry, preparation method and application for metal coating |
| CN110312330A (en) * | 2019-06-27 | 2019-10-08 | 江阴暖烯石墨烯科技有限公司 | A kind of safety electric film and preparation method thereof |
-
2020
- 2020-03-05 CN CN202010147502.2A patent/CN111187564A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103649243A (en) * | 2011-07-13 | 2014-03-19 | Posco公司 | Resin composition for a surface treatment, and steel sheet coated with same |
| CN105452332A (en) * | 2013-07-31 | 2016-03-30 | 三菱化学株式会社 | Method for producing polycarbonate diol and polycarbonate diol, and method for producing polyurethane and polyurethane |
| CN105705597A (en) * | 2013-08-27 | 2016-06-22 | 关西涂料株式会社 | Water-based paint composition and painted article |
| CN106488938A (en) * | 2014-07-07 | 2017-03-08 | 东曹株式会社 | UV resistant absorbent polyurethane urea resin compositionss, the formed body employing said composition and coating material |
| CN104212170B (en) * | 2014-08-11 | 2017-08-25 | 广东昌亿新材料有限公司 | A kind of wear-resisting polyphenyl thioether composite material of high heat conduction and preparation method thereof |
| CN105025598A (en) * | 2015-07-06 | 2015-11-04 | 广东天弼陶瓷有限公司 | Electrothermal composite ceramic brick and preparation method thereof |
| CN105622891A (en) * | 2015-12-21 | 2016-06-01 | 江南大学 | Preparation method for polysiloxane emulsion modified waterborne polyurethane emulsion |
| CN105732940A (en) * | 2016-05-11 | 2016-07-06 | 江南大学 | Preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion |
| CN107384166A (en) * | 2017-06-27 | 2017-11-24 | 天长市巨龙车船涂料有限公司 | A kind of frost prevention antifreeze vehicle coating |
| CN107641483A (en) * | 2017-07-17 | 2018-01-30 | 常州中英科技股份有限公司 | A kind of high heat conduction bonding sheet and preparation method thereof |
| CN109081897A (en) * | 2018-08-01 | 2018-12-25 | 万华化学集团股份有限公司 | The excellent polyurethane of wet-hot aging performance or the aqueous dispersion of polyurethane-urea and its preparation method and application |
| CN110105828A (en) * | 2019-04-28 | 2019-08-09 | 苏州格瑞丰纳米科技有限公司 | A kind of graphene slurry, preparation method and application for metal coating |
| CN110312330A (en) * | 2019-06-27 | 2019-10-08 | 江阴暖烯石墨烯科技有限公司 | A kind of safety electric film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 宁佳玲主编: "《高等无机合成》", 30 September 2007, 华东理工大学出版社 * |
| 武丹主编: "《汽车材料》", 31 January 2015, 北京理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891667A (en) * | 2023-06-29 | 2023-10-17 | 上海交通大学 | Regenerated carbon fiber composite electric heating anti-icing/deicing coating material and preparation method and application thereof |
| CN116891667B (en) * | 2023-06-29 | 2024-05-28 | 上海交通大学 | Regenerated carbon fiber composite electric heating anti-icing/deicing coating material and preparation method and application thereof |
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Application publication date: 20200522 |