阅读说明：本技术 热塑性聚氨酯材料、热塑性聚氨酯膜及包含其的隐形车衣 (Thermoplastic polyurethane material, thermoplastic polyurethane film and invisible car cover comprising thermoplastic polyurethane film ) 是由 王亮 王海龙 李冠毅 周玉波 金亚东 于 2021-09-30 设计创作，主要内容包括：本发明提供了一种热塑性聚氨酯材料、热塑性聚氨酯膜及包含其的隐形车衣,涉及高分子薄膜技术领域。所述热塑性聚氨酯材料主要由多元醇,多元异氰酸酯,小分子多元醇,催化剂,扩链剂,封端剂,抗氧化剂和光稳定剂以特定的比例复配得到,由上述原料制得的热塑性聚氨酯材料是一种嵌段聚合物；其中,长链二元醇构成软段,硬段则是由多种异氰酸酯和扩链剂构成,由上述软段和硬段制得的热塑性聚氨酯材料具有很好的软硬、强度、伸长等性能,进而由上述热塑性聚氨酯材料制得的热塑性聚氨酯膜具优异的强度、硬度和良好的伸长率、回弹性等性能。(The invention provides a thermoplastic polyurethane material, a thermoplastic polyurethane film and a stealth car cover comprising the thermoplastic polyurethane film, and relates to the technical field of high polymer films. The thermoplastic polyurethane material is mainly prepared by compounding polyol, polyisocyanate, micromolecular polyol, catalyst, chain extender, end capping agent, antioxidant and light stabilizer according to a specific proportion, and the thermoplastic polyurethane material prepared from the raw materials is a block polymer; the thermoplastic polyurethane film prepared from the thermoplastic polyurethane material has excellent strength, hardness, elongation, resilience and other properties.)

1. The thermoplastic polyurethane material is characterized by mainly comprising the following raw materials in parts by weight: 85-100 parts of polyol, 40-75 parts of polyisocyanate, 10-30 parts of micromolecular polyol, 0.1-0.5 part of catalyst, 5-7 parts of chain extender, 10-30 parts of end capping agent, 0.01-0.02 part of antioxidant and 0.01-0.02 part of light stabilizer.

2. The thermoplastic polyurethane material according to claim 1, wherein the thermoplastic polyurethane material consists essentially of, in parts by mass: 90-95 parts of polyol, 45-70 parts of polyisocyanate, 15-25 parts of micromolecular polyol, 0.1-0.3 part of catalyst, 5-7 parts of chain extender, 15-25 parts of end capping agent, 0.01-0.02 part of antioxidant and 0.01-0.02 part of light stabilizer;

preferably, the thermoplastic polyurethane material mainly comprises the following raw materials in parts by weight: 90 parts of polyol, 55 parts of polyisocyanate, 20 parts of small molecular polyol, 0.3 part of catalyst, 6 parts of chain extender, 20 parts of end-capping agent, 0.01 part of antioxidant and 0.01 part of light stabilizer.

3. The thermoplastic polyurethane material according to claim 1 or 2, wherein the polyol comprises at least one of polyoxypropylene polyol, polymer polyol, polytetrahydrofuran and copolyether glycols thereof, polyoxyethylene polyol, polytrimethylene ether glycol, aromatic polyether polyol, adipic acid-based polyester glycol, aromatic polyester polyol, high molecular weight polyester polyol, dimer polyester glycol, polymer polyester polyol, polycaprolactone diol, polycaprolactone triol, polycarbonate diol.

4. The thermoplastic polyurethane material according to claim 1 or 2, wherein the polyisocyanate comprises at least one of toluene diisocyanate, dimethylmethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethyl-m-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, and dimethyldiphenylmethane diisocyanate.

5. The thermoplastic polyurethane material according to claim 1 or 2, wherein the small molecule polyol comprises at least one of ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 2-propanediol, neopentyl glycol, methylpropanediol, 1, 6-hexanediol, 1, 3-propanediol, dipropylene glycol, butylethylpropanediol, diethylpentanediol, 3-methyl-1, 5-pentanediol, 1, 3-butanediol, trimethylpentanediol, ethylhexanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, and spiroglycol.

6. The thermoplastic polyurethane material according to claim 1 or 2, wherein the catalyst comprises at least one of triethylenediamine, bis (dimethylaminoethyl) ether, dimethylcycloethylamine, pentamethyldialkylenetriamine, tetramethylethylenediamine, dimethylethanolamine, 1, 4-dimethylpiperazine, N-methylmorpholine, dibutyltin dilaurate, dibutyltin diacetate, tetrabutyl titanate, bismuth isooctanoate, lead isooctanoate, zinc isooctanoate;

preferably, the chain extender comprises at least one of 1, 4-butanediol, ethylene glycol, dipropylene glycol, 1, 6-hexanediol, hydroquinone dihydroxyethyl ether, glycerol, trimethylolpropane, pentaerythritol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, 3, 5-diethyltoluenediamine, diethanolamine, triethanolamine, ethanolamine;

preferably, the blocking agent comprises at least one of sodium pyrosulfite, sodium bisulfite, ammonium bisulfite, parachlorophenol, para-nitrophenol, di-n-butylamine, isopropanol, ammonia water, tri-n-butylamine, ethylene glycol, n-butanol, and glycerol;

preferably, the light stabilizer comprises one of ultraviolet absorbers UV-1, UV-320, UV-326, UV-327, UV-571, UV-234, UV-1229, UV-531, UV-1164, light stabilizer 292, light stabilizer 622, light stabilizer 770, light stabilizer 783 and light stabilizer 5050;

preferably, the antioxidant comprises at least one of antioxidant 245, antioxidant 1010, antioxidant 1076, antioxidant 3114, antioxidant 1330, antioxidant 1098, antioxidant 1135 and antioxidant 1024.

7. A method for preparing a thermoplastic polyurethane material according to any one of claims 1 to 6, wherein the method comprises the following steps:

mixing the raw materials and carrying out addition polymerization reaction to obtain the thermoplastic polyurethane material.

8. A thermoplastic polyurethane film, which is obtained by coating the thermoplastic polyurethane material according to any one of claims 1 to 6, followed by drying and curing.

9. The invisible car cover is characterized by comprising a protective layer, a self-repairing layer, a base material layer, a pressure-sensitive adhesive layer and a release layer from top to bottom in sequence;

wherein the substrate layer consists essentially of the thermoplastic polyurethane film of claim 8.

10. The invisible car cover according to claim 9, wherein the thickness of the protective layer is 30-100 μm;

the thickness of the self-repairing layer is 5-30 mu m;

the thickness of the substrate layer is 50-250 micrometers;

the thickness of the pressure-sensitive adhesive layer is 15-45 μm;

the thickness of the release layer is 30-100 mu m.

Technical Field

The invention relates to the technical field of high polymer films, in particular to a thermoplastic polyurethane material, a thermoplastic polyurethane film and a stealth car cover containing the thermoplastic polyurethane film.

Background

With the development of economic society, the quantity of automobiles owned is increasing day by day, and the concern on automobile maintenance is also increasing continuously. Except factors such as physical scratching, collision, scratches and the like, and chemical corrosion and oxidation such as acid rain, oil stain, haze, ultraviolet rays and the like directly bring damages to automobile paint. This will not only affect the driving mood of the owner but also the warranty of the vehicle. The protection of general spray paint is very limited compared with original factory car paint, and the price of special spray paint is very high.

The presence of a finish protective film provides a relatively viable solution to vehicle paint protection. The paint surface protective film is also called as a car cover film or a invisible car cover, and the like, and is a generic name of a transparent protective adhesive film which is stuck outside the car paint surface to protect the car paint and improve the appearance, and has attracted much attention in recent years.

At present, the materials used by the invisible car cover are mostly PVC, PU and TPH. The PVC car clothing film is generally thick, edge wrapping is not easy during construction, yellowing is easy to occur, adhesive residue is easy to occur, toughness is poor, scratches cannot be repaired, and the car clothing film is about to be eliminated in the market. The improved TPH type garment film has good flexibility by adding the plasticizer in the traditional material, but is still brittle in the using process due to the relationship of the material, and the protective capability is weak; meanwhile, the TPH material is low in cost, the selected glue layer is easy to fall off, offset printing or glue loss can be generated on the paint surface, and the service life is about two to three years. In recent years, the common car clothing film is made of PU material, is soft, and has strong toughness, wear resistance, weather resistance and good stretchability. After the paint is attached, the paint surface of the automobile can be isolated from air, acid rain and oxidation are prevented, scratch is resisted, and the paint surface of the automobile is protected for a long time. However, PU materials have poor resistance to alkaline corrosion, gradually become yellow, and scratches cannot be repaired.

In view of the defects of the car cover film made of the above materials, a thermoplastic polyurethane-based invisible car cover with excellent strength and hardness and good elongation, rebound resilience and other properties is researched and developed to solve the problems of yellowing and aging commonly existing in the current car cover film, so that the protection capability of the car paint is greatly improved, and the car cover film is necessary and urgent.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The first purpose of the invention is to provide a thermoplastic polyurethane material, wherein the thermoplastic polyurethane material is a block polymer, wherein a long-chain diol forms a soft segment, a hard segment comprises a plurality of isocyanates and chain extenders, and the thermoplastic polyurethane material prepared from the soft segment and the hard segment has good hardness, strength, elongation and other properties.

The second purpose of the invention is to provide a preparation method of the thermoplastic polyurethane material.

The third purpose of the invention is to provide a thermoplastic polyurethane film, which is mainly prepared by coating the thermoplastic polyurethane material, drying and curing.

The fourth purpose of the invention is to provide a invisible car cover, wherein the base material layer of the invisible car cover mainly comprises the thermoplastic polyurethane film. The invisible car cover has excellent strength, hardness, elongation, rebound resilience and other performances determined by the characteristics of the raw materials of the base material layer.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

the invention provides a thermoplastic polyurethane material which mainly comprises the following raw materials in parts by weight: 85-100 parts of polyol, 40-75 parts of polyisocyanate, 10-30 parts of micromolecular polyol, 0.1-0.5 part of catalyst, 5-7 parts of chain extender, 10-30 parts of end capping agent, 0.01-0.02 part of antioxidant and 0.01-0.02 part of light stabilizer.

Further, the thermoplastic polyurethane material mainly comprises the following raw materials in parts by weight: 90-95 parts of polyol, 45-70 parts of polyisocyanate, 15-25 parts of micromolecular polyol, 0.1-0.3 part of catalyst, 5-7 parts of chain extender, 15-25 parts of end capping agent, 0.01-0.02 part of antioxidant and 0.01-0.02 part of light stabilizer;

preferably, the thermoplastic polyurethane material mainly comprises the following raw materials in parts by weight: 90 parts of polyol, 55 parts of polyisocyanate, 20 parts of small molecular polyol, 0.3 part of catalyst, 6 parts of chain extender, 20 parts of end-capping agent, 0.01 part of antioxidant and 0.01 part of light stabilizer.

Further, the polyol includes at least one of polyoxypropylene polyol, polymer polyol, polytetrahydrofuran and copolyether glycol thereof, polyoxyethylene polyol, polytrimethylene ether glycol, aromatic polyether polyol, adipic acid-based polyester glycol, aromatic polyester polyol, high molecular weight polyester polyol, dimer polyester glycol, polymer polyester polyol, polycaprolactone diol, polycaprolactone triol, and polycarbonate diol.

Further, the polyisocyanate includes at least one of toluene diisocyanate, dimethylmethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, and dimethyldiphenylmethane diisocyanate.

Further, the small-molecule polyol comprises at least one of ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 2-propanediol, neopentyl glycol, methyl propanediol, 1, 6-hexanediol, 1, 3-propanediol, dipropylene glycol, butyl ethyl propanediol, diethyl pentanediol, 3-methyl-1, 5-pentanediol, 1, 3-butanediol, trimethyl pentanediol, ethyl hexanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, and spiroglycol.

Further, the catalyst comprises at least one of triethylene diamine, bis (dimethylaminoethyl) ether, dimethyl cyclic ethylamine, pentamethyl dialkylene triamine, tetramethyl ethylene diamine, dimethyl ethanol amine, 1, 4-dimethyl piperazine, N-methyl morpholine, dibutyltin dilaurate, dibutyltin diacetate, tetrabutyl titanate, bismuth isooctoate, lead isooctanoate and zinc isooctanoate;

preferably, the chain extender comprises at least one of 1, 4-butanediol, ethylene glycol, dipropylene glycol, 1, 6-hexanediol, hydroquinone dihydroxyethyl ether, glycerol, trimethylolpropane, pentaerythritol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, 3, 5-diethyltoluenediamine, diethanolamine, triethanolamine, ethanolamine;

preferably, the blocking agent comprises at least one of sodium pyrosulfite, sodium bisulfite, ammonium bisulfite, parachlorophenol, para-nitrophenol, di-n-butylamine, isopropanol, ammonia water, tri-n-butylamine, ethylene glycol and glycerol;

preferably, the light stabilizer comprises one of ultraviolet absorbers UV-1, UV-320, UV-326, UV-327, UV-571, UV-234, UV-1229, UV-531, UV-1164, light stabilizer 292, light stabilizer 622, light stabilizer 770, light stabilizer 783 and light stabilizer 5050;

preferably, the antioxidant comprises at least one of antioxidant 245, antioxidant 1010, antioxidant 1076, antioxidant 3114, antioxidant 1330, antioxidant 1098, antioxidant 1135 and antioxidant 1024.

The invention provides a preparation method of the thermoplastic polyurethane material, which comprises the following steps:

mixing the raw materials, and then carrying out addition polymerization reaction to obtain the thermoplastic polyurethane material.

The thermoplastic polyurethane film is mainly prepared by coating the thermoplastic polyurethane material, drying and curing.

The invention provides an invisible car cover which sequentially comprises a protective layer, a self-repairing layer, a base material layer, a pressure-sensitive adhesive layer and a release layer from top to bottom;

wherein, the substrate layer mainly comprises the thermoplastic polyurethane film.

Further, the thickness of the protective layer is 30-100 μm;

the thickness of the self-repairing layer is 5-30 mu m;

the thickness of the substrate layer is 50-250 micrometers;

the thickness of the pressure-sensitive adhesive layer is 15-45 μm;

the thickness of the release layer is 30-100 mu m.

Compared with the prior art, the invention has the beneficial effects that:

the thermoplastic polyurethane material provided by the invention is mainly prepared by compounding polyol, polyisocyanate, micromolecular polyol, a catalyst, a chain extender, a blocking agent, an antioxidant and a light stabilizer according to a specific proportion, wherein the polyol forms a soft segment, the polyisocyanate and the micromolecular polyol form a hard segment, the catalyst is used for catalyzing an amination reaction between the terminal alcohol and the terminal isocyanate group in the early stage and a chain extension reaction between the terminal isocyanate and the chain extender in the chain extension stage, and the weather resistance of the final polyurethane material is improved by adding the antioxidant and the light stabilizer. The thermoplastic polyurethane material prepared from the raw materials is polymerized from long-chain-segment raw materials and short-chain-segment raw materials and is a block polymer. Wherein, the long-chain dihydric alcohol forms the soft section, the hard section is formed by many isocyanic ester and chain extender, the thermoplastic polyurethane material made of above-mentioned soft section and hard section has very good soft or hard, intensity, elongation, etc.

The preparation method of the thermoplastic polyurethane material provided by the invention comprises the steps of mixing the raw materials and carrying out addition polymerization reaction to obtain the thermoplastic polyurethane material. The preparation method has the advantages of simple processing technology and easy operation.

The thermoplastic polyurethane film provided by the invention is mainly prepared by coating the thermoplastic polyurethane material and drying and curing, and the thermoplastic polyurethane film prepared from the thermoplastic polyurethane material has excellent strength and hardness and good performances such as elongation and rebound resilience.

The invisible car cover comprises a protective layer, a self-repairing layer, a base material layer, a pressure-sensitive adhesive layer and a release layer; wherein, the substrate layer mainly comprises the thermoplastic polyurethane film. The invisible car cover has excellent strength, hardness, elongation, rebound resilience and other performances determined by the characteristics of the raw materials of the base material layer.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.

According to one aspect of the invention, the thermoplastic polyurethane material mainly comprises the following raw materials in parts by weight: 85-100 parts of polyol, 40-75 parts of polyisocyanate, 10-30 parts of micromolecular polyol, 0.1-0.5 part of catalyst, 5-7 parts of chain extender, 10-30 parts of end capping agent, 0.01-0.02 part of antioxidant and 0.01-0.02 part of light stabilizer.

The thermoplastic polyurethane material provided by the invention is mainly prepared by compounding polyol, polyisocyanate, micromolecular polyol, a catalyst, a chain extender, a blocking agent, an antioxidant and a light stabilizer according to a specific proportion, wherein the polyol forms a soft segment, the polyisocyanate and the micromolecular polyol form a hard segment, the catalyst is used for catalyzing an amination reaction between the terminal alcohol and the terminal isocyanate group in the early stage and a chain extension reaction between the terminal isocyanate and the chain extender in the chain extension stage, and the weather resistance of the final polyurethane material is improved by adding the antioxidant and the light stabilizer. The thermoplastic polyurethane material prepared from the raw materials is polymerized from long-chain-segment raw materials and short-chain-segment raw materials and is a block polymer. Wherein, the long-chain dihydric alcohol forms the soft section, the hard section is formed by many isocyanic ester and chain extender, the thermoplastic polyurethane material made of above-mentioned soft section and hard section has very good soft or hard, intensity, elongation, etc.

In a preferred embodiment of the present invention, the thermoplastic polyurethane material mainly comprises the following raw materials in parts by weight: 90-95 parts of polyol, 45-70 parts of polyisocyanate, 15-25 parts of micromolecular polyol, 0.1-0.3 part of catalyst, 5-7 parts of chain extender, 15-25 parts of end capping agent, 0.01-0.02 part of antioxidant and 0.01-0.02 part of light stabilizer;

preferably, the thermoplastic polyurethane material mainly comprises the following raw materials in parts by weight: 90 parts of polyol, 55 parts of polyisocyanate, 20 parts of small molecular polyol, 0.3 part of catalyst, 6 parts of chain extender, 20 parts of end-capping agent, 0.01 part of antioxidant and 0.01 part of light stabilizer.

In the invention, the technical effect of the thermoplastic polyurethane material is further optimized by further adjusting and optimizing the dosage ratio of the raw materials of each component.

In a preferred embodiment of the present invention, the polyol includes at least one of polyoxypropylene polyol, polymer polyol, polytetrahydrofuran and copolyether glycol thereof, polyoxyethylene polyol, polytrimethylene ether glycol, aromatic polyether polyol, adipic acid-based polyester glycol, aromatic polyester polyol, high molecular weight polyester polyol, dimer polyester glycol, polymer polyester polyol, polycaprolactone diol, polycaprolactone triol, polycarbonate diol.

As a preferred embodiment, the above polyols are saturated aliphatic and alicyclic polyols such as dimer polyester diol, polycaprolactone diol, polycarbonate diol, and the like.

In a preferred embodiment of the present invention, the polyisocyanate includes Toluene Diisocyanate (TDI), dimethylmethylene diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (NDI), 1, 4-cyclohexane diisocyanate (CHDI), at least one of Xylylene Diisocyanate (XDI), cyclohexanedimethylene diisocyanate (HXDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), tetramethylm-xylylene diisocyanate (TMXDI), norbornane diisocyanate (NBDI), dimethylbiphenyl diisocyanate (TODI), methylcyclohexyl diisocyanate (HTDI), and dimethyldiphenylmethane diisocyanate (DMMDI).

As a preferred embodiment, the above-mentioned polyisocyanate is a saturated aliphatic and alicyclic polyisocyanate such as isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, or the like.

In a preferred embodiment of the present invention, the small molecule polyol includes at least one of Ethylene Glycol (EG), 1, 4-Butanediol (BDO), diethylene glycol (DEG), 1, 2-Propanediol (PG), neopentyl glycol (NPG), Methyl Propanediol (MPD), 1, 6-Hexanediol (HDO), 1, 3-Propanediol (PDO), dipropylene glycol (DPG), Butyl Ethyl Propanediol (BEPD), diethyl pentanediol (DEPD), 3-methyl-1, 5-pentanediol (MPD), 1, 3-Butanediol (BG), trimethyl pentanediol (TMPD), Ethyl Hexanediol (EHD), 1, 4-dimethylolcyclohexane (CHDM), Cyclohexanediol (CHDO), and Spiroglycol (SPG).

As a preferred embodiment, the small molecule polyol is a saturated small molecule polyol such as 1, 3-butanediol, cyclohexanediol, 1, 3-propanediol, and the like.

In a preferred embodiment of the present invention, the catalyst comprises at least one of Triethylenediamine (TEDA), bis (dimethylaminoethyl) ether (BDMAEE), Dimethylcyclethylamine (DMCHA), Pentamethyldialkylenetriamine (PMDETA), Tetramethylethylenediamine (TMEDA), Dimethylethanolamine (DMEA), 1, 4-Dimethylpiperazine (DMP), N-methylmorpholine (NMM), dibutyltin Dilaurate (DBTL), dibutyltin Diacetate (DBTAC), tetrabutyl titanate (TBT), bismuth isooctanoate, lead isooctanoate, zinc isooctanoate;

in a preferred embodiment, the catalyst is an organometallic catalyst such as dibutyltin dilaurate, dibutyltin diacetate, bismuth isooctanoate, or the like.

Preferably, the chain extender includes at least one of 1, 4-Butanediol (BDO), Ethylene Glycol (EG), dipropylene glycol (DPG), 1, 6-Hexanediol (HDO), hydroquinone dihydroxyethyl ether (HQEE), glycerol, trimethylolpropane, pentaerythritol, 3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), 3, 5-diethyltoluenediamine (DETDA), diethanolamine, triethanolamine, ethanolamine;

as a preferred embodiment, the chain extender is an alcohol chain extender such as 1, 4-butanediol, 1, 6-hexanediol, dipropylene glycol, etc.

Preferably, the end-capping agent comprises at least one of sodium pyrosulfite, sodium bisulfite, ammonium bisulfite, parachlorophenol, para-nitrophenol, di-n-butylamine, isopropanol, ammonia water, tri-n-butylamine, n-butanol, ethylene glycol, propanol, and glycerol;

in a preferred embodiment, the end-capping agent is a monofunctional alcohol end-capping agent such as isopropyl alcohol, n-butyl alcohol, propyl alcohol, or the like.

Preferably, the light stabilizer comprises one of ultraviolet absorbers UV-1, UV-320, UV-326, UV-327, UV-571, UV-234, UV-1229, UV-531, UV-1164, light stabilizer 292, light stabilizer 622, light stabilizer 770, light stabilizer 783 and light stabilizer 5050;

preferably, the antioxidant comprises at least one of antioxidant 245, antioxidant 1010, antioxidant 1076, antioxidant 3114, antioxidant 1330, antioxidant 1098, antioxidant 1135 and antioxidant 1024.

According to one aspect of the present invention, a method for preparing the above thermoplastic polyurethane material comprises the steps of:

mixing the raw materials and carrying out addition polymerization reaction to obtain the thermoplastic polyurethane material.

The preparation method of the thermoplastic polyurethane material provided by the invention comprises the steps of mixing the raw materials and carrying out addition polymerization reaction to obtain the thermoplastic polyurethane material. The preparation method has the advantages of simple processing technology and easy operation.

According to one aspect of the present invention, a thermoplastic polyurethane film is obtained by coating the above thermoplastic polyurethane material, drying and curing.

The thermoplastic polyurethane film provided by the invention is mainly prepared by coating the thermoplastic polyurethane material and drying and curing, and the thermoplastic polyurethane film prepared from the thermoplastic polyurethane material has excellent strength and hardness and good performances such as elongation and rebound resilience.

According to one aspect of the invention, the invisible car cover comprises a protective layer, a self-repairing layer, a base material layer, a pressure-sensitive adhesive layer and a release layer from top to bottom in sequence;

wherein, the substrate layer mainly comprises the thermoplastic polyurethane film.

The invisible car cover provided by the invention sequentially comprises a protective layer, a self-repairing layer, a base material layer, a pressure-sensitive adhesive layer and a release layer from top to bottom; wherein, the substrate layer mainly comprises the thermoplastic polyurethane film. The invisible car cover has excellent strength, hardness, elongation, rebound resilience and other performances determined by the characteristics of the raw materials of the base material layer.

In a preferred embodiment of the present invention, the thickness of the protective layer is 30 to 100 μm;

the thickness of the self-repairing layer is 5-30 mu m;

the thickness of the substrate layer is 50-250 micrometers;

the thickness of the pressure-sensitive adhesive layer is 15-45 μm;

the thickness of the release layer is 30-100 mu m.

In the above preferred embodiment, the protective layer is a PET protective layer, which functions to maintain a certain rigid shape; the self-repairing layer has the functions of resisting surface scratch self-repairing, resisting acid-base corrosion and resisting dirt; the substrate layer has the functions of impact resistance, heat resistance, cold resistance, aging resistance and ultraviolet ray resistance; the pressure-sensitive adhesive layer has the function of bonding the film and the paint surface, and the high viscosity can cause offset printing and white edges to easily occur in construction. Too low viscosity can cause the problems of edge warping, falling, bubbles even corner falling after being torn off and the like; the release layer is a PET release film and has the function of tightly fitting the invisible car cover and the back adhesive.

The technical solution of the present invention will be further described with reference to examples and comparative examples.

Example 1

A thermoplastic polyurethane material, the preparation method of the thermoplastic polyurethane material comprises the following steps:

accurately weighing 90 parts of G3450J (Asahi Kasei Chemicals Co., Ltd.) into a round-bottom reaction flask, raising the temperature to 85 ℃ until G3450J melts, adding 55 parts of trimethyl-1, 6-hexamethylene diisocyanate (Sanjing Kasei Chemicals Co., Ltd.) and 20 parts of 1, 4-cyclohexanedimethanol with stirring, adjusting the stirring speed to 300rps, and adding 0.3 part of dibutyltin diacetate after 30 min. The extent of reaction progress was determined by NCO titration and when the actual NCO content was monitored to be around the theoretical NCO content, 6 parts of 1, 4-butanediol were added. The reaction was continued for another 6h and was stopped by adding 20 parts of n-butanol. Then, 0.01 part of UV-1164 and 0.01 part of antioxidant 1330 are added, and stirring is continued for 340 min.

In this embodiment, G3450J is a polyester polyol, trimethyl-1, 6-hexamethylene diisocyanate is aliphatic isocyanate, 1, 4-cyclohexanedimethanol is alicyclic small-molecular diol, dibutyltin diacetate is an organic metal catalyst, 1, 4-butanediol is an alcohol chain extender, and n-butanol is a monofunctional alcohol-based end-capping agent.

Example 2

A thermoplastic polyurethane material, the preparation method of the thermoplastic polyurethane material comprises the following steps:

accurately weighing 90 parts of T4691 (Asahi Kasei Chemicals Co., Ltd.) in a round-bottom reaction flask, raising the temperature to 85 ℃ until G3450J melts, adding 55 parts of trimethyl-1, 6-hexamethylene diisocyanate (Mitsui Kasei chemical Co., Ltd.) and 20 parts of 1, 4-cyclohexanedimethanol with stirring, adjusting the stirring speed to 300rps, and adding 0.3 part of dibutyltin diacetate after 30 min. The extent of reaction progress was determined by NCO titration and when the actual NCO content was monitored to be around the theoretical NCO content, 6 parts of 1, 4-butanediol were added. The reaction was continued for another 6h and was stopped by adding 20 parts of n-butanol. Then, 0.01 part of UV-1164 and 0.01 part of antioxidant 1330 are added, and stirring is continued for 40 min.

In this embodiment, T4691 is a polyester polyol, trimethyl-1, 6-hexamethylene diisocyanate is aliphatic isocyanate, 1, 4-cyclohexanedimethanol is alicyclic small-molecular diol, dibutyltin diacetate is an organic metal catalyst, 1, 4-butanediol is an alcohol chain extender, and n-butanol is a monofunctional alcohol-based capping agent.

Example 3

A thermoplastic polyurethane material, the preparation method of the thermoplastic polyurethane material comprises the following steps:

accurately weighing 90 parts of CD210HL (Asahi Kasei Chemicals Co., Ltd.) into a round-bottom reaction flask, raising the temperature to 85 ℃ until G3450J melts, adding 55 parts of trimethyl-1, 6-hexamethylene diisocyanate (Sanjing Kasei Co., Ltd.) and 20 parts of 1, 4-cyclohexanedimethanol with stirring, adjusting the stirring speed to 300rps, and adding 0.3 part of dibutyltin diacetate after 30 min. The extent of reaction progress was determined by NCO titration and when the actual NCO content was monitored to be around the theoretical NCO content, 6 parts of 1, 4-butanediol were added. The reaction was continued for another 6h and terminated by the addition of 10-30 parts of n-butanol. Then, 0.01 part of UV-1164 and 0.01 part of antioxidant 1330 are added, and stirring is continued for 40 min.

In this embodiment, CD210HL is a polyester polyol, trimethyl-1, 6-hexamethylene diisocyanate is aliphatic isocyanate, 1, 4-cyclohexanedimethanol is alicyclic small-molecular diol, dibutyltin diacetate is an organometallic catalyst, 1, 4-butanediol is an alcohol chain extender, and n-butanol is a monofunctional alcohol-based end-capping agent.

Example 4

A thermoplastic polyurethane material, the preparation method of the thermoplastic polyurethane material comprises the following steps:

accurately weighing 90 parts of CD210 (Asahi Kasei Chemicals Co., Ltd.) into a round-bottom reaction flask, raising the temperature to 85 ℃ until G3450J melts, adding 55 parts of trimethyl-1, 6-hexamethylene diisocyanate (Mitsui Kasei chemical Co., Ltd.) and 20 parts of 1, 4-cyclohexanedimethanol with stirring, adjusting the stirring speed to 300rps, and adding 0.3 part of dibutyltin diacetate after 30 min. The extent of reaction progress was determined by NCO titration and when the actual NCO content was monitored to be around the theoretical NCO content, 6 parts of 1, 4-butanediol were added. The reaction was continued for another 6h and was stopped by adding 20 parts of n-butanol. Then, 0.01 part of UV-1164 and 0.01 part of antioxidant 1330 are added, and stirring is continued for 40 min.

In this embodiment, CD210 is a polyester polyol, trimethyl-1, 6-hexamethylene diisocyanate is aliphatic isocyanate, 1, 4-cyclohexanedimethanol is alicyclic small-molecule diol, dibutyltin diacetate is an organic metal catalyst, 1, 4-butanediol is an alcohol chain extender, and n-butanol is a monofunctional alcohol-based capping agent.

Example 5

A thermoplastic polyurethane material, the preparation method of the thermoplastic polyurethane material comprises the following steps:

accurately weighed 90 parts of CD210PL asahi chemical co., ltd.) was charged into a round-bottom reaction flask, the temperature was raised to 85 ℃ until G3450J melted, followed by addition of 55 parts of trimethyl-1, 6-hexamethylene diisocyanate (mitsui chemical co., ltd.) and 20 parts of 1, 4-cyclohexanedimethanol with stirring, the stirring speed was adjusted to 300rps, and after 30min, 0.3 part of dibutyltin diacetate was added. The extent of reaction progress was determined by NCO titration and when the actual NCO content was monitored to be around the theoretical NCO content, 6 parts of 1, 4-butanediol were added. The reaction was continued for another 6h and was stopped by adding 20 parts of n-butanol. Then, 0.01 part of UV-1164 and 0.01 part of antioxidant 1330 are added, and stirring is continued for 40 min.

In this embodiment, CD210PL is a polyester polyol, trimethyl-1, 6-hexamethylene diisocyanate is aliphatic isocyanate, 1, 4-cyclohexanedimethanol is alicyclic small-molecular diol, dibutyltin diacetate is an organometallic catalyst, 1, 4-butanediol is an alcohol chain extender, and n-butanol is a monofunctional alcohol-based end-capping agent.

Examples 6 to 10

Heating the thermoplastic polyurethane materials prepared in the embodiments 1-5 to 70 ℃, and then respectively coating the thermoplastic polyurethane materials on the surface of a layer of release film, wherein the thickness of the release film is 150 micrometers; then transferring the film into an oven, and curing at a high temperature of 150 ℃ to obtain the thermoplastic polyurethane film.

Comparative example 1

A thermoplastic polyurethane material, the preparation method of the thermoplastic polyurethane material comprises the following steps:

accurately weighing 90 parts of GE210 (Shanghai high-bridge petrochemical industry), adding the GE210 into a round-bottom reaction bottle, raising the temperature to 85 ℃ until G3450J is molten, then adding 55 parts of trimethyl-1, 6-hexamethylene diisocyanate (Sanjing chemical Co., Ltd.) and 20 parts of 1, 4-cyclohexanedimethanol under stirring, adjusting the stirring speed to 300rps, and adding 0.3 part of dibutyltin diacetate after 30 min. The extent of reaction progress is determined by NCO titration, and when the actual NCO content is monitored to be around the theoretical NCO content, 5 to 7 parts of 1, 4-butanediol are added. The reaction was continued for another 6h and terminated by the addition of 10-30 parts of n-butanol. Then, 0.01 part of UV-1164 and 0.01 part of antioxidant 1330 are added, and stirring is continued for 40 min.

In the comparative example, GE210 is polyether polyol, trimethyl-1, 6-hexamethylene diisocyanate is aliphatic isocyanate, 1, 4-cyclohexanedimethanol is alicyclic micromolecular diol, dibutyltin diacetate is an organic metal catalyst, 1, 4-butanediol is an alcohol chain extender, and n-butyl alcohol is a monofunctional alcohol end-capping agent.

Comparative example 2

A thermoplastic polyurethane material, the preparation method of the thermoplastic polyurethane material comprises the following steps:

accurately weighing 90 parts of G3450J (Asahi Kasei Chemicals Co., Ltd.) into a round-bottom reaction flask, raising the temperature to 85 ℃ until G3450J melts, adding 55 parts of trimethyl-1, 6-hexamethylene diisocyanate (Sanjing Kasei Chemicals Co., Ltd.) and 20 parts of 1, 4-cyclohexanedimethanol with stirring, adjusting the stirring speed to 300rps, and adding 0.3 part of dibutyltin diacetate after 30 min. The extent of reaction progress was determined by NCO titration and when the actual NCO content was monitored to be around the theoretical NCO content, 6 parts of 1, 4-butanediol were added. The reaction was continued for another 6h and was stopped by adding 20 parts of n-butanol.

In the comparative example, G3450J is polyester polyol, trimethyl-1, 6-hexamethylene diisocyanate is aliphatic isocyanate, 1, 4-cyclohexanedimethanol is alicyclic micromolecular diol, dibutyltin diacetate is an organic metal catalyst, 1, 4-butanediol is an alcohol chain extender, and n-butyl alcohol is a monofunctional alcohol end-capping agent.

Comparative examples 3 and 4

The thermoplastic polyurethane materials prepared in comparative examples 1 and 2 were heated to 70 ℃, and then coated on the surface of a release film, respectively, to a thickness of 150 μm; then transferring the film into an oven, and curing at a high temperature of 150 ℃ to obtain the thermoplastic polyurethane film.

Experimental example 1

In order to show that the thermoplastic polyurethane prepared by the method has good properties such as hardness, strength and elongation, the thermoplastic polyurethane films prepared in examples 6-10 and comparative examples 3 and 4 are subjected to performance detection, and the specific results are as follows:

furthermore, the thermoplastic polyurethane films prepared in examples 6-10 and comparative examples 3 and 4 are prepared into car clothing films. Subsequently, the car cover film prepared above was subjected to a weather resistance test (QUV test) under the conditions of ISO 11507 meth.a: 0.71W/m2, 60 ℃ and 4 h; COND, 50 ℃ for 4 h. The specific results are as follows:

from the test results, compared with the existing PVC-based and PU-based car cover films, the car cover film prepared by the method has the advantages of excellent strength and hardness, good elongation and rebound resilience, and benefits from careful selection of components in polyurethane and reasonable design of the proportion of soft segments and hard segments in chain segments. In addition, starting from raw materials, saturated aliphatic and alicyclic polyols, polyisocyanate, micromolecular alcohol and other components are selected, and meanwhile, a light stabilizing auxiliary agent and an antioxidant auxiliary agent are added in the preparation process, so that the problems of yellowing and aging of the existing car cover film are solved, and the protective capability of the car paint is greatly improved. In addition, expensive large-scale instrument equipment is not needed in the preparation process of the thermoplastic polyurethane film of the base material layer in the application, the production cost can be reduced to a certain extent, and the problem that the cost of the car clothing film is high is solved.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.