CN115895482A - Uncoated paint protective film and preparation method thereof - Google Patents
Uncoated paint protective film and preparation method thereof Download PDFInfo
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- CN115895482A CN115895482A CN202211196203.3A CN202211196203A CN115895482A CN 115895482 A CN115895482 A CN 115895482A CN 202211196203 A CN202211196203 A CN 202211196203A CN 115895482 A CN115895482 A CN 115895482A
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- 239000002245 particle Substances 0.000 claims abstract description 103
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- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 42
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- 238000006243 chemical reaction Methods 0.000 claims description 20
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- 230000008018 melting Effects 0.000 claims description 19
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
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- 230000005855 radiation Effects 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 230000009977 dual effect Effects 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 8
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- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
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- 230000003078 antioxidant effect Effects 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical group OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
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- 239000012974 tin catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000013329 compounding Methods 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
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- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 15
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
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- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of paint surface protective films, in particular to a coating-free paint surface protective film and a preparation method thereof. The situations of large VOC (volatile organic compound) emission and large PET (polyethylene terephthalate) protective film waste generally exist in the existing paint protective film preparation process, and in order to solve the problem, the invention provides a non-coating paint protective film and a preparation method thereof. The paint surface protective film is synthesized into functional TPU particles by introducing high-functionality resin and a curing agent in the synthesis stage of the TPU particles and simultaneously grafting unsaturated double bonds; preparing double-layer TPU films with different functional layers by double-layer coextrusion casting equipment, wherein the bottom layer is a main layer TPU, and the surface layer is a thin functional layer TPU; the UV irradiation curing is carried out on the surface of the functional layer of the double-layer co-extruded TPU film, so that the film surface crosslinking degree and the smoothness degree can be increased, and a repair coating does not need to be coated for protection, so that a paint surface protective film product is prevented from using a self-repairing coating and a PET protective film, and energy conservation and emission reduction are realized.
Description
Technical Field
The invention relates to the technical field of paint surface protective films, in particular to a coating-free paint surface protective film and a preparation method thereof.
Background
The structure of the prior paint protective film product is shown in figure 1. The common paint surface protective film generally comprises a PET release layer, an acrylic pressure-sensitive adhesive layer, a TPU casting base film, a self-repairing coating and a PET protective film. Among them, the main purpose of using the PET protective film is to protect the self-repairing coating from being scratched during curing and transportation, and users can directly tear and throw away the PET protective film when using the PET protective film, thereby causing resource waste and environmental pollution. In addition, the solvent-based self-repairing coating commonly used in the market at present contains 40 to 60 percent of volatile organic solvent, so that the self-repairing coating generates a large amount of VOC (volatile organic compound) emission during coating, and the environment is polluted. In order to solve the problems of large VOC discharge and large PET protective film waste in the existing paint protective film preparation process, the invention is very necessary to provide a non-coating paint protective film, and the effects of environmental protection, energy conservation and emission reduction are achieved.
Disclosure of Invention
The invention aims to provide a coating-free paint protective film and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a kind of uncoated lacquer surface protective film and its preparation method, including the following steps:
s1: preparation of main layer TPU particle A:
adding polyester polyol, a catalyst and a stabilizer into a vacuum reaction tank according to a ratio, mixing and stirring, gradually heating to 100 ℃, and then heating for vacuum dehydration for 30min; introducing nitrogen for protection, adding diisocyanate, continuously heating and stirring, reacting and curing for 2 hours, adding a chain extender for 2 minutes, and pouring out; putting the poured material into an oven at 100-120 ℃ for full curing for 24h, crushing into TPU granules, putting the TPU granules into granulation equipment, and melting, extruding and granulating at 140-180 ℃ to obtain main layer TPU granules A;
s2: preparation of functional layer TPU particles B:
adding polyester polyol, high-functionality polyester polyol, graft modified hydroxyl acrylate, fluorine-silicon modified acrylate, a catalyst, a photoinitiator and a stabilizer into a vacuum reaction tank according to a proportion, mixing and stirring, gradually heating to 100 ℃, and then heating for vacuum dehydration for 30min; introducing nitrogen for protection, simultaneously adding diisocyanate, polyisocyanate and a dual curing agent, continuously heating, stirring, reacting and curing for 2 hours, then adding a chain extender for 2 minutes, pouring out, putting the poured material into an oven at 100-120 ℃, fully curing for 24 hours, and crushing into TPU granules; putting the TPU granules into granulation equipment, and melting, extruding and granulating at 140-180 ℃ to obtain functional TPU granules B;
s3: preparing a TPU semi-finished film:
respectively drying and dehydrating the main layer TPU particles A and the functional layer TPU particles B in vacuum, and then carrying out casting coextrusion film forming by using a double-layer precise casting line at the casting temperature of 160 to 180 ℃, wherein the main layer TPU particles A are cast into a film and placed on the bottom layer, and the thickness of the film is 100 to 150 mu m; casting and forming a film on the surface layer by TPU particles B with the thickness of 10 to 15 mu m; after the double-layer co-extruded TPU film is cast, carrying out UV radiation crosslinking curing on the surface layer, wherein the UV radiation energy is 300 to 700mj/cm 2 (ii) a Adhering a PET protective film on the surface of the lower layer, rolling, and curing at 40-50 ℃ for 72h to obtain a TPU semi-finished film;
s4: preparing a finished product of the uncoated finish protective film:
unwinding the TPU semi-finished product film, tearing off the PET protective film at the lower layer, coating acrylic pressure-sensitive glue at the lower layer of the TPU semi-finished product film by using a precise coating line at the coating temperature of 80-120 ℃, at the coating speed of 10-15m/min and at the glue layer thickness of 15-30 mu m, and laminating the PET release film to obtain the uncoated paint surface protective film.
Further, in S1, the components of the main layer TPU particle A are as follows by weight: 30-60% of polyester polyol, 20-50% of diisocyanate, 5-20% of chain extender, 0.1-0.5% of catalyst and 8978% of stabilizer 1~5.
Further, in S2, the functional layer TPU particles B comprise, by weight: 20-50% of polyester polyol, 5-20% of high-functionality polyester polyol, 5-20% of graft modified hydroxyl acrylate, 1~2% of fluorine-silicon modified acrylate, 10-40% of diisocyanate, 0-20% of polyisocyanate, 0-20% of dual curing agent, 5-20% of chain extender, 0.1-0.5% of catalyst, 1~4% of photoinitiator, 1~5% of stabilizer, and the sum of the mass percentages of the raw materials is 100%.
Further, in S1 and S2, the polyester polyol is one or more of polycaprolactone polyol and polycarbonate polyol, and the molecular weight is 1000 to 2000; the diisocyanate is aliphatic diisocyanate and comprises one or more of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl diisocyanate; the catalyst is an organic tin catalyst; the chain extender is one or more of small molecular diol or triol, preferably propylene glycol, ethylene glycol, 1,4-butanediol, neopentyl glycol and trimethylolpropane; the stabilizer is one or more of antioxidant, light stabilizer, ultraviolet absorbent and hydrolysis stabilizer.
Further, in S2, the high-functionality polyester polyol is 6-functionality polycarbonate polyol, the molecular weight is 2000, the hydroxyl value is 120 to 170, and the structural schematic diagram is shown in FIG. 3; the graft modified hydroxyl acrylate is caprolactone graft modified hydroxyl acrylate, one side of the graft modified hydroxyl acrylate is provided with hydroxyl, one side of the graft modified hydroxyl acrylate is provided with unsaturated double bond, and the molecular formula is shown in figure 4.
Further, the fluorine-silicon modified acrylate in S2 is fluorine-silicon modified acrylate containing unsaturated double bonds.
Further, the polyisocyanate in S2 is a 6-functional aliphatic HDI trimer.
Further, the dual curing agent in S2 is isocyanate-containing urethane acrylate, and simultaneously has NCO groups and double bonds.
Further, the photoinitiator in S2 is a radical photoinitiator, including one or more of Irgacure 184D, 1173, and TPO.
Compared with the prior art, the invention has the following beneficial effects: the invention introduces high functionality resin and curing agent in the TPU particle synthesis stage, and simultaneously grafts unsaturated double bond to synthesize functional TPU particles; preparing double-layer TPU films with different functional layers by double-layer coextrusion casting equipment, wherein the bottom layer is a main layer TPU, and the surface layer is a thin functional layer TPU; the surface of the functional layer of the double-layer co-extruded TPU film is subjected to UV irradiation curing, so that the degree of crosslinking and smoothness of the film surface are increased, and the film surface is not required to be coated with a repair coating for protection, so that the film surface is not required to be coated with the repair coating, and the discharge of VOC is avoided; and the use and waste of the PET protective film are reduced, energy is saved, emission is reduced, and the carbon neutralization concept advocated by the current economic environment is met.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a protective film for a general paint surface;
FIG. 2 is a schematic view of the structure of the uncoated paint protective film of the present invention;
FIG. 3 is a schematic structural diagram of a 6-functional polycarbonate polyol according to the present invention;
FIG. 4 shows the chemical formula of caprolactone grafted modified hydroxy acrylate in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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 following examples, PCL-2205 and PCL-3207 were purchased from Haoya, guangzhou, new Material science and technology, inc.; desmodur I, available from Haoyet New Material science and technology, inc., guangzhou; WANNATE HMDI, available from wanhua chemistry; desmodur N3580BA, available from Kao Yi New Material science and technology Co., guangzhou; EB 4250, available from Shanghai Qinghong chemical industries, ltd; HPCP-200, available from Guangzhou Hao Yi New Material science and technology GmbH; FS100, available from shanghai stanza international trade ltd; GA2800Z, available from shanghai stanzoko international trade ltd; DBTDL-T12, available from Kyon chemical Co., ltd. 184D, available from kay chemical ltd, shanghai; tinuvin 292, available from shanghai kelvin chemical ltd; BDO, available from Guangzhou Hao Yi New Material science and technology GmbH; TMP, available from Guangzhou Haoyao new material science and technology GmbH.
Example 1:
s1: preparation of main layer TPU particle A:
adding 30kg of polyester polyol (PCL-2205), 0.5kg of catalyst (DBTDL-T12) and 5kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and dehydrating in vacuum for 30min; introducing nitrogen for protection, adding 50kg of diisocyanate (Desmodur I), continuously heating, stirring, reacting and curing for 2 hours, then adding 14.5kg of chain extender (BDO), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 120 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain main-layer TPU particles A;
s2: preparation of functional layer TPU particles B:
adding 20kg of polyester polyol (PCL-3207), 5kg of high-functionality polyester polyol (HPCP-200), 5kg of graft modified hydroxy acrylate (FS 100), 1kg of fluorosilicone modified acrylate (GA 2800Z), 0.5kg of catalyst (DBTDL-T12), 1kg of photoinitiator (184D) and 2.5kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 40kg of diisocyanate (WANNATE HMDI) and 20kg of polyisocyanate (Desmodur N3580 BA), continuously heating, stirring, reacting and curing for 2 hours, then adding 5kg of chain extender (TMP), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain functional TPU particles B;
s3: preparing a TPU semi-finished film:
after the main layer TPU particles A and the functional layer TPU particles B are dried and dehydrated in vacuum, carrying out casting co-extrusion film forming by using a double-layer precise casting line, wherein the casting temperature is 160 ℃, the main layer TPU particles A are cast into a film and placed on the bottom layer, and the thickness is 100 mu m; the functional layer TPU particles B are subjected to tape casting to form a film and placed on the surface layer, and the thickness is 10 mu m; after the double-layer co-extruded TPU film is cast out, the surface layer is subjected to UV radiation crosslinking curing,the UV irradiation energy is 300mj/cm 2 (ii) a Adhering a PET protective film on the surface of the lower layer for rolling, and curing at 40 ℃ for 72 hours to obtain a TPU semi-finished film;
s4: preparing a finished product of the uncoated finish protective film:
unreeling the TPU semi-finished product film, tearing off a lower PET protective film, coating acrylic acid pressure-sensitive glue on the lower layer of the TPU semi-finished product film by using a precise coating line, wherein the coating temperature is 80 ℃, the coating speed is 10m/min, the glue layer thickness is 15 mu m, and the PET protective film and the release film are combined to obtain the coating-free paint surface protective film.
Example 2:
s1: preparation of main layer TPU particle A:
adding 60kg of polyester polyol (PCL-2205), 0.5kg of catalyst (DBTDL-T12) and 4.5kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 20kg of diisocyanate (Desmodur I), continuously heating, stirring, reacting and curing for 2 hours, then adding 15kg of chain extender (BDO), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain main-layer TPU particles A;
s2: preparation of functional layer TPU particles B:
adding 30kg of polyester polyol (PCL-3207), 5kg of high-functionality polyester polyol (HPCP-200), 10kg of graft modified hydroxy acrylate (FS 100), 2kg of fluorosilicone modified acrylate (GA 2800Z), 0.1kg of catalyst (DBTDL-T12), 2kg of photoinitiator (184D) and 4kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 25kg of diisocyanate (WANNATE HMDI), 5kg of polyisocyanate (Desmodur N3580 BA) and 6.9kg of dual curing agent (EB 4250), continuously heating, stirring, reacting and curing for 2 hours, then adding 10kg of chain extender (TMP), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain functional TPU particles B;
s3: preparing a TPU semi-finished film:
after the main layer TPU particles A and the functional layer TPU particles B are dried and dehydrated in vacuum, carrying out casting co-extrusion film forming by using a double-layer precise casting line, wherein the casting temperature is 180 ℃, the main layer TPU particles A are cast into a film and placed on the bottom layer, and the thickness is 100 mu m; the functional layer TPU particles B are subjected to tape casting to form a film and placed on the surface layer, and the thickness is 15 mu m; carrying out UV radiation crosslinking curing on the surface layer after the double-layer co-extruded TPU film is cast, wherein the UV radiation energy is 500mj/cm 2 (ii) a Adhering a PET protective film on the surface of the lower layer for rolling, and curing at 45 ℃ for 72 hours to obtain a TPU semi-finished film;
s4: preparing a finished product of the uncoated finish protective film:
unreeling the TPU semi-finished product film, tearing off a lower PET protective film, coating acrylic acid pressure-sensitive glue on the lower layer of the TPU semi-finished product film by using a precise coating line, wherein the coating temperature is 100 ℃, the coating speed is 10m/min, the glue layer thickness is 25 mu m, and the PET release film and the acrylic acid pressure-sensitive glue are combined to obtain the coating-free paint surface protective film.
Example 3:
s1: preparation of main layer TPU particle A:
adding 60kg of polyester polyol (PCL-2205), 0.5kg of catalyst (DBTDL-T12) and 4kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and dehydrating in vacuum for 30min; introducing nitrogen for protection, adding 20.5kg of diisocyanate (Desmodur I), continuously heating, stirring, reacting and curing for 2 hours, then adding 15kg of chain extender (BDO), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain main-layer TPU particles A;
s2: preparation of functional layer TPU particles B:
adding 20kg of polyester polyol (PCL-3207), 10kg of high-functionality polyester polyol (HPCP-200), 20kg of graft modified hydroxy acrylate (FS 100), 2kg of fluorosilicone modified acrylate (GA 2800Z), 0.1kg of catalyst (DBTDL-T12), 2kg of photoinitiator (184D) and 4kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 25kg of diisocyanate (WANNATE HMDI) and 6.9kg of dual curing agent (EB 4250), continuously heating, stirring, reacting and curing for 2 hours, then adding 10kg of chain extender (TMP), and pouring out after 2 min; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain functional TPU particles B;
s3: preparing a TPU semi-finished film:
after the main layer TPU particles A and the functional layer TPU particles B are dried and dehydrated in vacuum, carrying out casting co-extrusion film forming by using a double-layer precise casting line, wherein the casting temperature is 180 ℃, the main layer TPU particles A are cast into a film and placed on the bottom layer, and the thickness is 150 mu m; the functional layer TPU particles B are subjected to tape casting to form a film and placed on the surface layer, and the thickness is 10 mu m; carrying out UV radiation crosslinking curing on the surface layer after the double-layer co-extruded TPU film is cast, wherein the UV radiation energy is 700mj/cm 2 (ii) a Adhering a PET protective film on the surface of the lower layer for rolling, and curing at 45 ℃ for 72 hours to obtain a TPU semi-finished film;
s4: preparing a finished product of the uncoated finish protective film:
unreeling the TPU semi-finished product film, tearing off a lower PET protective film, coating acrylic acid pressure-sensitive glue on the lower layer of the TPU semi-finished product film by using a precise coating line, wherein the coating temperature is 100 ℃, the coating speed is 10m/min, the glue layer thickness is 25 mu m, and the PET release film and the acrylic acid pressure-sensitive glue are combined to obtain the coating-free paint surface protective film.
Example 4:
s1: preparation of main layer TPU particle A:
adding 40kg of polyester polyol (PCL-2205), 0.4kg of catalyst (DBTDL-T12) and 3kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 36.6kg of diisocyanate (Desmodur I), continuously heating, stirring, reacting and curing for 2 hours, then adding 20kg of chain extender (BDO), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 110 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 160 ℃ to obtain main-layer TPU particles A;
s2: preparation of functional layer TPU particles B:
by weight, 30kg of polyester polyol (PCL-3207), 10kg of high-functionality polyester polyol (HPCP-200), 10kg of graft modified hydroxy acrylate (FS 100), 1.5kg of fluorosilicone modified acrylate (GA 2800Z), 0.4kg of catalyst (DBTDL-T12), 2.6kg of photoinitiator (184D) and 3kg of stabilizer (Tinuvin 292) are added into a vacuum reaction tank for mixing and stirring, the temperature is gradually increased to 100 ℃, and the vacuum dehydration is carried out for 30min; introducing nitrogen for protection, adding 20kg of diisocyanate (WANNATE HMDI), 10.5kg of polyisocyanate (Desmodur N3580 BA) and 6kg of dual curing agent (EB 4250), continuously heating, stirring, reacting and curing for 2 hours, then adding 6kg of chain extender (TMP), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 110 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 160 ℃ to obtain functional TPU particles B;
s3: preparing a TPU semi-finished film:
after the main layer TPU particles A and the functional layer TPU particles B are dried and dehydrated in vacuum, carrying out casting co-extrusion film forming by using a double-layer precise casting line, wherein the casting temperature is 180 ℃, the main layer TPU particles A are cast into a film and placed on the bottom layer, and the thickness is 120 mu m; the functional layer TPU particles B are subjected to tape casting to form a film and placed on the surface layer, and the thickness is 13 mu m; carrying out UV radiation crosslinking curing on the surface layer after the double-layer co-extruded TPU film is cast, wherein the UV radiation energy is 700mj/cm 2 (ii) a Adhering a PET protective film on the surface of the lower layer for rolling, and curing at 45 ℃ for 72 hours to obtain a TPU semi-finished film;
s4: preparing a finished product of the uncoated finish protective film:
unreeling the TPU semi-finished product film and tearing off the lower layer PET protection film, coating acrylic acid pressure-sensitive glue on the lower layer of the TPU semi-finished product film by using a precise coating line, wherein the coating temperature is 100 ℃, the coating speed is 12m/min, the glue layer thickness is 25 mu m, and the coating is combined with a PET release film to obtain the uncoated finish protection film.
Example 5:
s1: preparation of main layer TPU particle A:
adding 60kg of polyester polyol (PCL-2205), 0.1kg of catalyst (DBTDL-T12) and 1kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 20kg of diisocyanate (Desmodur I), continuously heating, stirring, reacting and curing for 2 hours, then adding 18.9kg of chain extender (BDO), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 120 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain main-layer TPU particles A;
s2: preparation of functional layer TPU particles B:
adding 50kg of polyester polyol (PCL-3207), 5kg of high-functionality polyester polyol (HPCP-200), 5kg of graft modified hydroxy acrylate (FS 100), 2kg of fluorosilicone modified acrylate (GA 2800Z), 0.5kg of catalyst (DBTDL-T12), 4kg of photoinitiator (184D) and 4kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 10kg of diisocyanate (WANNATE HMDI), 10.5kg of polyisocyanate (Desmodur N3580 BA) and 4kg of dual curing agent (EB 4250), continuously heating, stirring, reacting and curing for 2 hours, then adding 5kg of chain extender (TMP), and pouring after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 120 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain functional TPU particles B;
s3: preparing a TPU semi-finished film:
after the main layer TPU particles A and the functional layer TPU particles B are dried and dehydrated in vacuum, carrying out casting co-extrusion film forming by using a double-layer precise casting line, wherein the casting temperature is 180 ℃, the main layer TPU particles A are cast into a film and placed on the bottom layer, and the thickness is 150 mu m; the functional layer TPU particles B are subjected to tape casting to form a film and placed on the surface layer, and the thickness is 15 mu m; carrying out UV radiation crosslinking curing on the surface layer after the double-layer co-extruded TPU film is cast, wherein the UV radiation energy is 400mj/cm 2 (ii) a Adhering a PET protective film on the surface of the lower layer for rolling, and curing at 50 ℃ for 72 hours to obtain a TPU semi-finished film;
s4: preparing a finished product of the uncoated finish protective film:
unreeling the TPU semi-finished product film, tearing off a lower PET protective film, coating acrylic acid pressure-sensitive glue on the lower layer of the TPU semi-finished product film by using a precise coating line, wherein the coating temperature is 120 ℃, the coating speed is 15m/min, the glue layer thickness is 30 mu m, and the PET protective film and the release film are combined to obtain the coating-free paint surface protective film.
Comparative example 1:
no functional layer was prepared.
S1: preparation of main layer TPU particle A:
adding 60kg of polyester polyol (PCL-2205), 0.5kg of catalyst (DBTDL-T12) and 4.5kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 20kg of diisocyanate (Desmodur I), continuously heating, stirring, reacting and curing for 2 hours, then adding 15kg of chain extender (BDO), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain main-layer TPU particles A;
s2: preparing a TPU semi-finished film:
after the main layer TPU particles A are dried and dehydrated in vacuum, a single-layer precise casting line is used for casting to form a film, wherein the casting temperature is 180 ℃, and the thickness is 150 mu m; adhering a PET protective film on the surface of the lower layer for rolling, and curing at 45 ℃ for 72 hours to obtain a TPU semi-finished film;
s3: preparing a finished product of the uncoated finish protective film:
unreeling the TPU semi-finished product film and tearing off a lower PET protective film, coating acrylic acid pressure-sensitive glue on the lower layer of the TPU semi-finished product film by using a precise coating line, wherein the coating temperature is 100 ℃, the coating speed is 10m/min, the glue layer thickness is 25 mu m, and covering a PET release film to obtain the coating-free paint surface protective film.
Comparative example 2:
and (3) not carrying out UV irradiation curing on the surface of the functional layer of the double-layer co-extruded TPU film.
S1: preparation of main layer TPU particle A:
adding 60kg of polyester polyol (PCL-2205), 0.5kg of catalyst (DBTDL-T12) and 4kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and dehydrating in vacuum for 30min; introducing nitrogen for protection, adding 20.5kg of diisocyanate (Desmodur I), continuously heating, stirring, reacting and curing for 2 hours, then adding 15kg of chain extender (BDO), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain main-layer TPU particles A;
s2: preparation of functional layer TPU particles B:
adding 20kg of polyester polyol (PCL-3207), 10kg of high-functionality polyester polyol (HPCP-200), 20kg of graft modified hydroxy acrylate (FS 100), 2kg of fluorosilicone modified acrylate (GA 2800Z), 0.1kg of catalyst (DBTDL-T12), 2kg of photoinitiator (184D) and 4kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 25kg of diisocyanate (WANNATE HMDI) and 6.9kg of dual curing agent (EB 4250), continuously heating, stirring, reacting and curing for 2 hours, then adding 10kg of chain extender (TMP), and pouring out after 2 min; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain functional TPU particles B;
s3: preparing a TPU semi-finished film:
after the main layer TPU particles A and the functional layer TPU particles B are respectively dried and dehydrated in vacuum, a double-layer precise casting line is used for casting and co-extruding to form a film, the casting temperature is 180 ℃, wherein the main layer TPU particles A are placed on the bottom layer in a casting mode, and the thickness is 150 mu m; the functional layer TPU particles B are subjected to tape casting to form a film and placed on the surface layer, and the thickness is 10 mu m; adhering a PET protective film on the surface of the lower layer for rolling, and curing at 45 ℃ for 72 hours to obtain a TPU semi-finished film;
s4: preparing a finished product of the uncoated finish protective film:
unreeling the TPU semi-finished product film and tearing off a lower PET protective film, coating acrylic acid pressure-sensitive glue on the lower layer of the TPU semi-finished product film by using a precise coating line, wherein the coating temperature is 100 ℃, the coating speed is 10m/min, the glue layer thickness is 25 mu m, and covering a PET release film to obtain the coating-free paint surface protective film.
Comparative example 3:
the coated finish protective film was prepared using a conventional method.
S1: preparation of main layer TPU particle A:
adding 60kg of polyester polyol (PCL-2205), 0.5kg of catalyst (DBTDL-T12) and 4.5kg of stabilizer (Tinuvin 292) into a vacuum reaction tank by weight, mixing and stirring, gradually heating to 100 ℃, and carrying out vacuum dehydration for 30min; introducing nitrogen for protection, adding 20kg of diisocyanate (Desmodur I), continuously heating, stirring, reacting and curing for 2 hours, then adding 15kg of chain extender (BDO), and pouring out after 2 minutes; putting the poured material into an oven, fully curing for 24 hours at 100 ℃, and crushing into TPU small particles; putting the TPU small particles into granulation equipment, and melting, extruding and granulating at 180 ℃ to obtain main-layer TPU particles A;
s2: preparing a TPU semi-finished film:
after the main layer TPU particles A are dried and dehydrated in vacuum, a single-layer precise casting line is used for casting to form a film, wherein the casting temperature is 180 ℃, and the thickness is 150 mu m; adhering a PET protective film on the surface of the lower layer for rolling, and curing at 45 ℃ for 72 hours to obtain a TPU semi-finished film;
s3: gluing the lower surface of the TPU semi-finished film:
unreeling the TPU semi-finished product film and tearing off a lower PET protective film, coating acrylic acid pressure-sensitive glue on the lower layer of the TPU semi-finished product film by using a precise coating line, wherein the coating temperature is 100 ℃, the coating speed is 10m/min, the glue layer thickness is 25 mu m, and covering a PET release film to obtain the TPU semi-finished product film with the glue layer.
S4: and (3) coating a self-repairing coating on the upper surface of the TPU semi-finished product film:
coating self-repairing coating on the upper surface of the TPU semi-finished film with the adhesive layer by using a precise coating line, wherein the coating temperature is 100 ℃, the coating speed is 10m/min, the thickness of the self-repairing coating is 15 mu m, a PET protective film is attached to the upper surface for rolling, and the coated paint surface protective film is obtained after curing at 45 ℃ for 72 hours.
Experiment: the following performance tests were conducted for example 1~5 and comparative example 1~3, respectively.
Stain resistance test: the film was drawn with a morning gloss oil-based marker, wiped with alcohol after 10 seconds, and the mark left on the film after wiping was observed. Wherein the film surface has no mark and is very good in stain resistance; the film surface has very shallow marks for better stain resistance; the film surface was marked with a marked poor stain resistance.
Solvent resistance: and dripping ethyl acetate solvent on the film surface, wiping the film surface with non-woven fabric after 10s, and observing the brightness of the film surface. Wherein the brightness of the film surface is good solvent resistance; the film surface lost light and became dull and was inferior in solvent resistance.
Smoothness degree: the coefficient of dynamic friction of the film surface was measured using a nonwoven fabric as a friction pair. Wherein >0.5 means that the coefficient of static friction is large and the sliding is not dynamic.
The self-repairing performance test method comprises the following steps: scraping the film surface with a copper brush repeatedly for 10 times, pouring with hot water at 60-80 ℃, and observing whether the scratch disappears.
Gloss test method: the film surface was tested for gloss using a 60 ° gloss meter.
The test results are shown in the following table:
| detecting items | Water contact angle | Resistance to soiling | Solvent resistance | Degree of smoothness | Self-repairing property | Degree of gloss |
| Example 1 | 102° | Good taste | Good taste | 0.20 | Can be repaired | 97 |
| Example 2 | 105° | Good taste | Good taste | 0.18 | Can be repaired | 97 |
| Example 3 | 107° | Is very good | Good taste | 0.12 | Can be repaired | 99 |
| Example 4 | 108° | Is very good | Good taste | 0.11 | Can be repaired | 99 |
| Example 5 | 102° | Good taste | Good taste | 0.19 | Repairable | 97 |
| Comparative example 1 | 74° | Difference (D) | Difference (D) | > 0.50 | Not repairing | 89 |
| Comparative example 2 | 86° | Difference (D) | Difference (D) | 0.45 | Is not repaired | 92 |
| Comparative example 3 | 99° | Good taste | Good taste | 0.24 | Can be repaired | 97 |
And (4) conclusion: as can be seen from the above table, the film surface of 1~5 of this embodiment has excellent gloss, stain resistance, smoothness, solvent resistance and self-repairing performance after being cross-linked and cured by UV irradiation, and does not need to be protected by a repairing coating. Wherein examples 3 and 4 further improve the stain resistance and the smoothness of the film surface by increasing the crosslinking degree. The embodiment 2 is taken as a reference group, and the comparative example 1 only has a single-layer casting base film, so that the base film has poor film surface stain resistance, solvent resistance, smoothness and the like, cannot be directly used and needs to be additionally provided with a self-repairing coating for protection; the paint surface protective film in the comparative example 1 is subjected to coating self-repairing coating treatment to obtain a comparative example 3; taking the example 3 as a control group, although the comparative example 2 has a double-layer co-extrusion casting base film, the surface functional layer is not cured by UV radiation crosslinking, so the crosslinking degree of the film surface is not high, and the stain resistance, the solvent resistance, the smoothness and the like are poor; with example 1~5 as a reference and comparative example 3 as a coated finish protective film prepared using a conventional method, it was found through testing that the film prepared in example 1~5 had better performance than comparative example 3 and did not cause VOC emission and PET protective film waste.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a non-coating paint surface protective film is characterized by comprising the following steps: the method comprises the following steps:
s1: adding polyester polyol, a catalyst and a stabilizer into a vacuum reaction tank, dehydrating, introducing nitrogen for protection, adding diisocyanate for reaction and curing, adding a chain extender for chain extension, and pouring out; putting the poured material into an oven, fully curing the material, crushing the cured material into TPU small particles, and melting, extruding and granulating the TPU small particles to obtain main-layer TPU particles A;
s2: adding polyester polyol, high-functionality polyester polyol, graft modified hydroxyl acrylate, fluorine-silicon modified acrylate, a catalyst, a photoinitiator and a stabilizer into a vacuum reaction tank, dehydrating, introducing nitrogen for protection, adding diisocyanate, polyisocyanate and a dual curing agent for reaction and curing, adding a chain extender for chain extension, and pouring out; putting the poured material into an oven, fully curing the material, crushing the cured material into TPU granules, and melting, extruding and granulating the TPU granules to obtain functional TPU granules B;
s3: after the main layer TPU particles A and the functional layer TPU particles B are dried and dehydrated in vacuum, the main layer TPU particles A are cast into a main layer and placed on the bottom layer, the functional layer TPU particles B are cast into a functional layer and placed on the surface layer, a double-layer co-extrusion TPU film is formed after compounding, the surface layer is cured by UV radiation crosslinking, the lower surface of the bottom layer is attached with a PET protective film for rolling, and a TPU semi-finished film is obtained after curing;
s4: and tearing off the PET protective film, coating acrylic acid pressure-sensitive adhesive on the lower layer of the TPU semi-finished film, and laminating the acrylic acid pressure-sensitive adhesive and the PET release film to obtain the uncoated finish protective film.
2. The method for producing an uncoated paint protective film according to claim 1, wherein: in S1, the main layer TPU particle A comprises the following components in parts by weight: 30 to 60 percent of polyester polyol, 20 to 50 percent of diisocyanate, 5 to 20 percent of chain extender, 0.1 to 0.5 percent of catalyst and 1~5 percent of stabilizer.
3. The method for producing an uncoated paint protective film according to claim 1, wherein: in S2, the functional layer TPU particle B comprises the following components in parts by weight: 20-50% of polyester polyol, 5-20% of high-functionality polyester polyol, 5-20% of graft modified hydroxyl acrylate, 1~2% of fluorine-silicon modified acrylate, 10-40% of diisocyanate, 0-20% of polyisocyanate, 0-20% of dual curing agent, 5-20% of chain extender, 0.1-0.5% of catalyst, 1~4% of photoinitiator and 1~5% of stabilizer.
4. The method for producing an uncoated paint protective film according to claim 1, wherein: in S1 and S2, the polyester polyol is one or more of polycaprolactone polyol and polycarbonate polyol, and the molecular weight is 1000-2000; the diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl diisocyanate; the catalyst is an organic tin catalyst; the chain extender is one or more of propylene glycol, ethylene glycol, 1,4-butanediol, neopentyl glycol and trimethylolpropane; the stabilizer is one or more of an antioxidant, a light stabilizer, an ultraviolet absorbent and a hydrolysis stabilizer.
5. The method for producing an uncoated paint protective film according to claim 1, wherein: in S2, the high-functionality polyester polyol is 6-functionality polycarbonate polyol, the molecular weight is 2000, and the hydroxyl value is 120 to 170; the fluorine-silicon modified acrylate is fluorine-silicon modified acrylate containing unsaturated double bonds; the polyisocyanate is 6-functionality aliphatic HDI trimer; the dual curing agent is urethane acrylate containing isocyanate groups; the photoinitiator is one or more of Irgacure 184D, 1173 and TPO.
6. The method for producing an uncoated paint protective film according to claim 1, wherein: in S2, the graft-modified hydroxy acrylate is caprolactone graft-modified hydroxy acrylate, and the structural formula is as follows:
7. the method for producing an uncoated paint protective film according to claim 1, wherein: in S1 and S2, curing at 100 to 120 ℃ for 24 hours; the melting temperature is 140 to 180 ℃.
8. The method of claim 1 wherein the protective film is uncoatedThe preparation method is characterized by comprising the following steps: in S3, the casting temperature is 160 to 180 ℃; the thickness of the main layer is 100 to 150 mu m; the thickness of the functional layer is 10 to 15 mu m; the UV irradiation energy is 300 to 700mj/cm 2 (ii) a The curing temperature is 40 to 50 ℃.
9. The method for producing an uncoated paint protective film according to claim 1, wherein: s4, in the coating process, the coating temperature is 80 to 120 ℃, the coating speed is 10 to 15m/min, and the glue line thickness is 15 to 30 mu m.
10. The uncoated finish protective film prepared by the method of any one of claims 1~9.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522417A (en) * | 2006-10-04 | 2009-09-02 | 3M创新有限公司 | Method of making multilayer polyurethane protective film |
| US20110281037A1 (en) * | 2010-05-11 | 2011-11-17 | Jae Woo Lee | One-part dual curing clear coating composition comprising acrylic modified acrylate for cars and dual curing process employing the same |
| US20160318289A1 (en) * | 2015-04-30 | 2016-11-03 | Impact Protection Technology Ag | Multilayer polyurethane protective films |
| CN113056531A (en) * | 2018-11-20 | 2021-06-29 | 乐金华奥斯有限公司 | Self-repairable coating composition and sheet using same |
| CN113072891A (en) * | 2021-04-01 | 2021-07-06 | 南阳金牛彩印集团有限公司 | Thermosetting self-repairing paint protective film and preparation method thereof |
| CN113320119A (en) * | 2021-06-21 | 2021-08-31 | 南通纳科达聚氨酯科技有限公司 | Preparation method of TPU (thermoplastic polyurethane) car cover protective film |
| CN114806392A (en) * | 2022-05-23 | 2022-07-29 | 江苏易米新材料科技有限公司 | Super-hydrophilic anti-fouling self-repairing coating, preparation method of coating and coating |
-
2022
- 2022-09-29 CN CN202211196203.3A patent/CN115895482A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522417A (en) * | 2006-10-04 | 2009-09-02 | 3M创新有限公司 | Method of making multilayer polyurethane protective film |
| US20110281037A1 (en) * | 2010-05-11 | 2011-11-17 | Jae Woo Lee | One-part dual curing clear coating composition comprising acrylic modified acrylate for cars and dual curing process employing the same |
| US20160318289A1 (en) * | 2015-04-30 | 2016-11-03 | Impact Protection Technology Ag | Multilayer polyurethane protective films |
| CN113056531A (en) * | 2018-11-20 | 2021-06-29 | 乐金华奥斯有限公司 | Self-repairable coating composition and sheet using same |
| CN113072891A (en) * | 2021-04-01 | 2021-07-06 | 南阳金牛彩印集团有限公司 | Thermosetting self-repairing paint protective film and preparation method thereof |
| CN113320119A (en) * | 2021-06-21 | 2021-08-31 | 南通纳科达聚氨酯科技有限公司 | Preparation method of TPU (thermoplastic polyurethane) car cover protective film |
| CN114806392A (en) * | 2022-05-23 | 2022-07-29 | 江苏易米新材料科技有限公司 | Super-hydrophilic anti-fouling self-repairing coating, preparation method of coating and coating |
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