WO2024045782A1 - 一种超疏水自修复热固化pu胶膜制备方法及汽车保护膜 - Google Patents
一种超疏水自修复热固化pu胶膜制备方法及汽车保护膜 Download PDFInfo
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- WO2024045782A1 WO2024045782A1 PCT/CN2023/101122 CN2023101122W WO2024045782A1 WO 2024045782 A1 WO2024045782 A1 WO 2024045782A1 CN 2023101122 W CN2023101122 W CN 2023101122W WO 2024045782 A1 WO2024045782 A1 WO 2024045782A1
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- Prior art keywords
- film
- glue
- micro
- preparation
- adhesive film
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 35
- 230000001681 protective effect Effects 0.000 title claims abstract description 29
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 82
- 239000003292 glue Substances 0.000 claims abstract description 58
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 53
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 51
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 40
- 239000011737 fluorine Substances 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 38
- 239000002086 nanomaterial Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 240000002853 Nelumbo nucifera Species 0.000 claims abstract description 28
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims abstract description 28
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims description 77
- 238000001723 curing Methods 0.000 claims description 37
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 24
- 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 24
- 238000002360 preparation method Methods 0.000 claims description 23
- 229920005749 polyurethane resin Polymers 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052797 bismuth Inorganic materials 0.000 claims description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 13
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 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 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000013007 heat curing Methods 0.000 claims description 8
- 239000013638 trimer Substances 0.000 claims description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 8
- -1 polydimethylsiloxane Polymers 0.000 claims description 7
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003759 ester based solvent Substances 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 239000012974 tin catalyst Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 230000002085 persistent effect Effects 0.000 abstract 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 24
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 19
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229920002545 silicone oil Polymers 0.000 description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000004804 winding Methods 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 230000003373 anti-fouling effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Definitions
- the invention relates to the field of automobile protective films, in particular to a method for preparing a superhydrophobic self-repairing heat-curing PU adhesive film and an automobile protective film.
- the protective film is a layer of adhesive film that fits on the surface of the physical object to be protected.
- the usual structure is upper protective film + functional coating + protective film base material + pressure-sensitive adhesive layer + release film.
- Protective film for automobile paint commonly known as invisible car clothing.
- PVC polyvinyl chloride
- TPU thermoplastic polyurethane
- the protective film made of PVC is easy to precipitate out of the plasticizer and becomes brittle, and the adhesive layer is easy to fall off. The service life is about 2-3 years.
- TPU material is a type of polyurethane that can be plasticized by heating and dissolved by solvents.
- polyurethane is a block polymer composed of isocyanate hard segments and polyol soft segments, which has both plasticity and elasticity. It has a wide adjustable range of hardness and elasticity, and has excellent wear resistance, weather resistance and chemical resistance. . Therefore, through the laminated structure of self-healing, hydrophobic and anti-fouling functional coating + TPU base material + pressure-sensitive adhesive layer, it shows stable, good toughness, hydrophobic anti-fouling and automatic repair functions, making it highly sought after as an invisible car jacket. The best materials have a service life of 5-10 years.
- Superhydrophobicity is a special surface wetting phenomenon, which refers to the surface phenomenon where the contact angle between the droplet and the solid surface is >150° and the rolling contact angle is ⁇ 10°.
- superhydrophobic surfaces have important characteristics such as excellent self-cleaning, waterproofing, antifouling, and anticorrosion, and have extremely broad application prospects in many fields such as scientific research, production, and life.
- the water contact angle can only reach 100° -110 °, which cannot meet the superhydrophobic standard.
- the patent with publication number CN108728007A discloses an anti-UV invisible car film with a self-healing function and a preparation method thereof, including a TPU base material layer, a self-healing layer and a protective silica gel sequentially arranged on the upper surface of the TPU layer from bottom to top. layer, PET layer, and a pressure-sensitive adhesive layer and a release layer arranged on the lower surface of the TPU base material layer from top to bottom.
- a self-healing layer mainly composed of fluorinated polyurethane resin
- the TPU layer has excellent anti-graffiti, anti-fouling and self-healing functions, but the coating has no obvious super-hydrophobic effect.
- the patent with publication number CN112126339A discloses a method for preparing a self-healing coating for automobile paint protection films made of superhydrophobic TPU material.
- the raw materials include aliphatic diisocyanate, hydroxy polyether polyol, catalyst, chain extender, and anti-UV auxiliary.
- Agents and solvents, etc. by introducing inert silicone oil to form a low surface energy, and at the same time forming a surface micro-nano structure by mixing nanoparticles modified with sodium citrate, and finally achieving a super-hydrophobic "lotus leaf" morphology on the surface of the TPU coating.
- patent CN112126339A achieves self-healing and superhydrophobic functions on the TPU substrate, there is no need to coat a special self-healing layer or/and superhydrophobic layer on the surface of the base material layer like patent CN108728007A, which simplifies protection.
- Membrane structure and processes However, the micro-nano structure morphology on the surface of the TPU film formed by nanoparticles such as fumed silica is imperfect, and after long-term scratching and rain erosion, the nanoparticles easily fall off and lose the superhydrophobic effect.
- the existing technology has the following shortcomings: the traditional protective film is to apply a functional coating on the protective film substrate, which has a complicated production process and high production cost.
- the TPU film formed by nanoparticles such as fumed silica
- the micro-nano structure morphology on the surface is imperfect, and after long-term scratching and rain erosion, the nanoparticles easily fall off and lose the superhydrophobic effect.
- the present invention provides a superhydrophobic self-repairing heat-curing PU adhesive film preparation method and automobile protective film.
- a method for preparing a super-hydrophobic self-repairing heat-curing PU adhesive film which includes: using a coating process to coat PU glue on a fluorine release film with a lotus leaf-like micro-nano structure on the surface, and then performing curing treatment to obtain a lotus-like leaf-like micro-nano structure.
- PU glue film with micro-nano structure; the PU glue also contains a silicone oil-modified hydroxyl resin, which is a hydroxyl-containing silicone oil-modified polyester polyurethane resin and a hydroxyl-containing silicone oil-modified polyurethane resin.
- the PU glue contains a low surface free energy hydrophobic agent, and the low surface free energy hydrophobic agent is a fluorine-containing block polymer solution and silicone-modified polyacrylic acid A combination of one or both in solution.
- the hydroxyl resin has a silicon content of 1% - 6%.
- the hydroxyl resin has a hydroxyl functionality of 1 to 3, a glass transition temperature of - 10°C to 50°C, and a molecular weight of 5000 to 15000g/mol.
- the PU glue also contains catalysts, leveling agents, ultraviolet absorbers, solvents and curing agents.
- the catalyst is one of an organic bismuth catalyst and an organic tin catalyst.
- the leveling agent is one or a combination of two of polyether-modified polydimethylsiloxane and aralkyl-modified methylalkylpolysiloxane.
- the solvent is one or a combination of two or more of ester solvents, amide solvents and ether solvents.
- the curing agent is one or a combination of two or more of HDI trimer, IPDI trimer, HDI biuret and HDI/IPDI addition prepolymer.
- the curing process includes placing the coated PU glue in a drying equipment at a temperature of 100-150 °C for 2-5 minutes.
- An automobile protective film including a thermally cured PU adhesive film prepared by the above preparation method.
- the preparation method of the automobile protective film is as follows: coating the side of the thermally cured PU adhesive film that does not have a lotus leaf micro-nano structure Silicone pressure-sensitive adhesive is cured and bonded to ordinary fluorine release protective film, and then die-cut to obtain a car protective film.
- the present invention improves the hydrophobic characteristics of the PU glue film itself by introducing a low surface free energy hydrophobic agent into the PU glue with silicone oil-modified hydroxyl resin as the main resin.
- the silicone oil-modified hydroxyl resin itself can It gives the PU film excellent self-healing ability.
- the low surface free energy hydrophobic agent has a low molecular weight and easily migrates to the surface of the film, showing excellent hydrophobic properties.
- the silicone oil modified hydroxyl resin can form with the low surface free energy hydrophobic agent.
- this synergistic effect can make the surface hydrophobicity of the PU glue film more durable; based on the PU glue made of silicone oil-modified hydroxyl resin and low surface free energy hydrophobic agent, a coating process is used to have charge-like properties.
- the fluorine release film with micro-nano structure is coated with PU glue, and then solidified into a PU film, thereby constructing a micro-nano multi-level structure on the PU film.
- the micro-nano multi-level structure, low surface free energy and hydrophobicity The combined effect of the agent and the silicone oil-modified hydroxyl resin achieves super hydrophobic properties on the surface of the PU film.
- the water contact angle reaches more than 150° and the rolling contact angle is less than 10°. It is different from the existing micro-nano formed by adding nanoparticles. Compared with other structures, the micro-nano multi-level structure produced by the present invention is not easy to fall off, and has durability and durability; compared with the traditional complex process of coating functional coatings on protective film substrates, the present invention simplifies the production process and reduce manufacturing cost.
- a method for preparing a super-hydrophobic self-healing heat-curing PU adhesive film using a coating process to apply heat-curing PU glue on a fluorine release film with a lotus leaf-like micro-nano structure on the surface, and bake it at 120°C for 3-4 minutes.
- the glue dries and solidifies to form a 60-100 ⁇ m thick thermally cured PU adhesive film with a fluorine release film with a lotus leaf-like micro-nano structure.
- the PU glue contains a low surface free energy hydrophobic agent.
- the low surface free energy hydrophobic agent is a combination of one or both of a fluorine-containing block polymer solution and a silicone-modified polyacrylic acid solution.
- the low surface free energy hydrophobic agent is The hydrophobic agent has a low molecular weight and can easily migrate to the surface of the film, showing excellent hydrophobic properties.
- the PU glue also includes a hydroxyl resin, which is a combination of one or both of hydroxyl-containing silicone oil-modified polyester polyurethane resin and hydroxyl-containing silicone oil-modified polyether-type polyurethane resin.
- a hydroxyl resin which is a combination of one or both of hydroxyl-containing silicone oil-modified polyester polyurethane resin and hydroxyl-containing silicone oil-modified polyether-type polyurethane resin.
- the silicone oil-modified hydroxyl resin itself can give the PU film excellent self-healing ability, and it forms different migration gradients with the low surface free energy hydrophobic agent. This synergistic effect can make the surface hydrophobicity of the PU film more durable.
- the hydroxyl resin is a silicone oil modified hydroxyl resin with a silicon content of 1% - 6%, preferably 3% - 5%.
- the hydroxyl resin has a hydroxyl functionality of 1 to 3, a glass transition temperature of - 10°C to 50°C, and a molecular weight of 5000 to 15000g/mol.
- the present invention improves the hydrophobic properties of the PU adhesive film itself by introducing a low surface free energy hydrophobic agent into the PU glue with silicone oil-modified hydroxyl resin as the main resin.
- the silicone oil-modified hydroxyl resin itself can give the PU adhesive film excellent natural properties. Repair ability, the low surface free energy hydrophobic agent has a low molecular weight and can easily migrate to the surface of the film, showing excellent hydrophobic properties.
- the silicone oil modified hydroxyl resin can form different migration gradients with the low surface free energy hydrophobic agent.
- This kind of The synergistic effect can make the surface hydrophobicity of the PU glue film more durable; based on the PU glue made of silicone oil-modified hydroxyl resin and low surface free energy hydrophobic agent, a coating process is used to add fluorine with a lotus leaf-like micro-nano structure.
- the release film is coated with PU glue and then solidified into a PU adhesive film, thereby constructing a micro-nano multi-level structure, a micro-nano multi-level structure, a low surface free energy hydrophobic agent and silicone oil modified hydroxyl groups on the PU adhesive film.
- the joint action of the resin achieves super hydrophobic properties on the surface of the PU adhesive film, with the water contact angle reaching more than 150° and the rolling contact angle lower than 10°.
- the PU film produced by the present invention The obtained micro-nano multi-level structure is not easy to fall off, and is durable and long-lasting; compared with the traditional complex process of coating functional coatings on protective film substrates, the present invention simplifies the production process and reduces production costs.
- the preparation method of the fluorine release film with a lotus leaf-like micro-nano structure using laser etching method to etch a film with a lotus leaf-like micro-nano structure on an ordinary PET film, and then using a fluorine-containing release agent. After surface treatment, a fluorine release film with lotus leaf-like micro-nano structure is obtained.
- fluorine release film with a lotus leaf-like micro-nano structure can not only impart hydrophobic properties to the surface of the PU film, but can also be reused multiple times at a lower cost.
- the fluorine release film with lotus leaf-like micro-nano structure is a fluorine release film with micron-scale pits densely distributed on the surface and nano-scale substructures present on the inner surface of the pits.
- This micro-nano structure is opposite to the micro-nano structure on the surface of the lotus leaf, so it is called lotus leaf-like micro-nano structure, and is often called a negative mold in the industry.
- the PU glue is made of raw materials with the following parts by weight: 30-50 parts of hydroxyl resin, 0.2-2 parts of low surface free energy hydrophobic agent, 0.1-1.5 parts of catalyst, and 0.2-4 parts of leveling agent. 2-4 parts of UV absorber, 40-70 parts of solvent and 15-40 parts of curing agent.
- the hydroxyl resin is one or a combination of both hydroxyl-containing silicone oil-modified polyester polyurethane resin and hydroxyl-containing silicone oil-modified polyether-type polyurethane resin.
- the hydroxyl functionality of the hydroxyl resin is 1 - 3, the glass transition temperature is - 10°C - 50°C, and the molecular weight is 5000 - 15000g/mol; the hydroxyl resin is a silicone oil modified hydroxyl resin, and the silicon content is 1% - 6%, preferably 3% - 5%.
- the PU adhesive film made from the above-mentioned hydroxyl resin can give the PU adhesive film excellent self-healing ability, and the silicone oil segment on the hydroxyl resin is grafted on the hydroxyl resin through chemical bonds. , forming different migration gradients with low surface free energy hydrophobic agents. This synergistic effect makes the surface hydrophobic properties excellent and more durable.
- the low surface free energy hydrophobic agent is a fluorine-containing block polymer solution or a silicone-modified polyacrylic acid solution, selected from Sinyue's KY - 108, KY - 1203, KY - 1206, Ke New material CoatFilmTM UVF - 1 0 3, one or more of BY K's SILCLEAN3700, 3710, 3720, Tego 5000, Tego 5001, introduces a low surface free energy hydrophobic agent to form a protective film similar to traditional automobile paint With similar anti-fouling properties, the water contact angle on the surface of the PU film can only reach 100° - 110° without a micro-nano structure.
- the catalyst is one of an organic bismuth catalyst (Borchi Kat 22, Bayer) and an organic tin catalyst (model 4233 catalyst produced by Shule Industrial (Shanghai) Co., Ltd.).
- the leveling agent is polyether-modified polydimethylsiloxane (BYK - 306, BYK - 331, BYK - 378), aralkyl-modified methylalkyl polysiloxane (BYK - 322) One or two or more combinations.
- the solvent is one or more of ester solvents, amide solvents, and ether solvents.
- the curing agent is an aliphatic isocyanate curing agent, such as HDI trimer (hexamethylene diisocyanate trimer, selected from Covestro Desmodur N3390, N3300), IPDI Trimer (diisophorone isocyanate trimer, selected from Covestro Desmodur Z4470), HDI biuret (hexamethylene diisocyanate biuret, selected from Covestro Desmodur N75, N3320 ), one or a combination of two or more of HDI/IPDI addition prepolymer (DI - 300B produced by Dinglisen Company).
- HDI trimer hexamethylene diisocyanate trimer, selected from Covestro Desmodur N3390, N3300
- IPDI Trimer diisophorone isocyanate trimer, selected from Covestro Desmodur Z4470
- HDI biuret hexamethylene diisocyanate biuret, selected from Covestro Desmodur N75, N3320
- the HDI/IPDI addition prepolymer (DI - 300B produced by Dinglisen Company) is composed of butyl acetate, trimethylolpropane, hexamethylene diisocyanate, isophorone diisocyanate and dibutyltin dilaurate Made; the molar ratio between the hexamethylene diisocyanate, isophorone diisocyanate and trimethylolpropane is (2.0 - 3.0): (1.2 - 1.8): ( 0.8-1.2 ); the weight percentage of dibutyltin dilaurate is 0.03-0.08 %.
- the preparation steps of the HDI/IPDI addition prepolymer curing agent are as follows: In a four-necked flask equipped with a stirrer, condenser, and thermometer, add the above-mentioned butyl acetate, trimethylolpropane, and hexamethylene dimethyl Isocyanate and isophorone diisocyanate are heated to 70 - 90°C while stirring, and then the reaction is carried out with insulation. During the insulation reaction, dibutyltin dilaurate is added in 3 - 5 times, and the reaction is continued for 2.5 - 3 hours until the system is insoluble. The substance disappears and the HDI/IPDI addition prepolymer curing agent is obtained.
- HDI/IPDI addition prepolymer curing agent Ordinary PU adhesive film has low construction solid content, poor leveling when thick coating is applied, prone to bubble spots and orange peel, and is difficult to form a film without shrinkage at the edge of the base material. And other issues.
- the HDI/IPDI addition prepolymer curing agent of the present invention uses trimethylolpropane combined with isophorone diisocyanate and hexamethylene diisocyanate to form an HDI/IPDI addition prepolymer curing agent.
- the cross-linked structure ratio Hexamethylene diisocyanate trimer is more compact.
- the self-made HDI/IPDI addition prepolymer curing agent has lower viscosity and better leveling than traditional isocyanate curing agent. It can not only improve the construction solid content during coating , solves the problems of poor leveling, easy bubble spots, orange peel lines and edge shrinkage when thick coating is applied, and can also effectively improve the hardness and toughness of the PU film.
- component A (1) Put the above-mentioned parts by weight of hydroxyl resin, low surface free energy hydrophobic agent, catalyst, leveling agent, ultraviolet absorber and solvent into a stirring tank and mix thoroughly to obtain component A, which is ready for use.
- the heat-curing PU adhesive film made by using the above-mentioned PU glue has the following advantages over the existing TPU film: the existing TPU film generally uses isocyanate components with two functionalities, which can be plasticized by heating and dissolved by solvents. of linear polyurethane resin. When silicone pressure-sensitive adhesive is directly applied to the surface, it is easily swollen and whitened by solvents. The only way is to attach the silicone pressure-sensitive adhesive that has been applied and baked to dry the surface. Cause: Thermoplastic TPU molecules do not form a cross-linked network, and direct coating of silica gel will cause it to swell and turn white due to the solvent in it.
- an intermediate isolation layer such as PET film
- an intermediate isolation layer such as PET film
- the heat-curing PU adhesive film of the present invention has the characteristics of being directly coated with silicone, and a cross-linked network is formed between its molecules.
- the surface can be directly coated with silicone pressure-sensitive adhesive without being The solvent swells and turns white, and it will not poison or deactivate the platinum catalyst in the silicone pressure-sensitive adhesive.
- the preparation method of the automobile protective film of the present invention Coating the side of the heat-cured PU adhesive film without the lotus leaf micro-nano structure with silicone pressure-sensitive adhesive, after curing, it is attached to an ordinary fluorine release protective film, and then molded After cutting, the pre-finished car protective film can be obtained. After the fluorine release film with lotus leaf-like micro-nano structure is removed from the pre-finished car protective film, its surface replicates the micro-nano multi-level structure on the fluorine release film, that is, on the top of each micron-level protrusion Rich nanoscale substructures are formed. This micro-nanostructure, which is similar to the surface structure of a lotus leaf, combines with the low surface free energy substances on the surface of the thermally cured PU adhesive film to exhibit excellent superhydrophobic properties.
- silicone oil modified polyether aliphatic hydroxyl polyurethane resin (Baojun Chemical 535-33A ), 0.05 parts by weight of organic bismuth catalyst (Borchi Kat 22, Bayer), 1 part by weight of fluorine-containing hydrophobic agent ( UVF - 103), 0.2 parts by weight of silicone leveling agent (BYK - 333), 3 parts by weight of UV absorber (Tinuvin 401), 30 parts by weight of butyl acetate and 25 parts by weight of HDI trimer Curing agent (Desmodur N3390 from Covestro).
- Example 1 Tear off the side with low release force and apply silicone. After the silicone solidifies, tear off the fluorine release film with a lotus leaf-like micro-nano structure to obtain Example 1.
- silicone oil modified polyether aliphatic hydroxyl polyurethane resin (Baojun Chemical 535-33A ), 0.05 parts by weight of organic bismuth catalyst (Borchi Kat 22, Bayer), 0.5 parts by weight of fluorine-containing inlaid segmented polymer solution (KY - 1203), 1 part by weight of silicone modified polyacrylate solution (BYK - 3700), 0.2 part by weight of silicone leveling agent (BYK - 333), 3 parts by weight of UV Absorbent (Tinuvin 401), 10 parts by weight of ethyl acetate, 15 parts by weight of methyl isobutyl ketone and 20 parts by weight of HDI/IPDI addition prepolymer curing agent (DI - 300B produced by Dinglisen Company) .
- silicone oil modified polyether aliphatic hydroxyl polyurethane resin (Baojun Chemical 535-33A )
- organic bismuth catalyst (Borchi Kat 22, Bayer)
- Example 2 Tear off the side with low release force and apply silicone. After the silicone solidifies, tear off the fluorine release film with a lotus leaf-like micro-nano structure to obtain Example 2.
- silicone oil modified polyether aliphatic hydroxyl polyurethane resin (Baojun Chemical 523-2 ), 0.05 parts by weight of organic bismuth catalyst (Borchi Kat 22, Bayer), 1 part by weight of fluorine-containing block polymerization solution (KY - 1203), 0.2 parts by weight of leveling agent (BYK - 333), 2 parts by weight of ultraviolet absorber (Tinuvin 401), 30 parts by weight of ethyl acetate, 30 parts by weight of butyl acetate, 10 parts by weight of HDI biuret curing agent (Desmodur N75 by Covestro) and 10 parts by weight of IPDI trimer curing agent (Desmodur Z4470 by Covestro).
- silicone oil modified polyether aliphatic hydroxyl polyurethane resin (Baojun Chemical 535-33A ), 0.05 parts by weight of organic bismuth catalyst (Borchi Kat 22, Bayer), 1 part by weight of fluorine-containing block polymerization Material solution (KY - 1203), 1 part by weight of silicone modified polyacrylate solution (BYK - 3700), 0.3 part by weight of silicone leveling agent (TEGO - 450), 2 parts by weight of UV absorber (Tinuvin 401), 25 parts by weight of butyl acetate, 25 parts by weight of methyl isobutyl ketone and 20 parts by weight of HDI trimer curing agent (Desmodur N3390 from Covestro).
- hydroxy acrylic resin (Baojun Chemical 532B - 4), 0.05 parts by weight of organic bismuth catalyst (Borchi Kat 22, Bayer), 0.2 parts by weight of silicone leveling agent (BYK - 333) , 3 parts by weight of UV absorber (Tinuvin 401), 15 parts by weight of ethyl acetate, 25 parts by weight of butyl acetate and 25 parts by weight of HDI trimer curing agent (Desmodur N3390 from Covestro).
- Examples 1 to 3 showed superhydrophobic self-healing characteristics, while Comparative Examples 1 and 2 showed ordinary high water droplet angle characteristics because they did not have micro-nano structures.
- the water contact angle of the PU adhesive film prepared by the present invention is >150°C, while the rolling contact angle is ⁇ 10°, which meets the definition of a superhydrophobic coating, proving that the PU adhesive film has obvious superhydrophobic properties; compared to For example, although Comparative Example 1 uses silicone oil-modified hydroxyl polyurethane resin and introduces low surface free energy fluorine-containing and silicon-containing hydrophobic agents, there is no micro-nano structure on the surface, and the highest water contact angle is only 108°; Comparative Example 2 uses ordinary resin (hydroxy acrylic resin) and does not introduce a hydrophobic agent. The PU film produced has no self-healing function and the water contact angle is less than 90°.
- Example 2 uses Dinglisen’s self-produced
- the HDI/IPDI addition prepolymer curing agent DI - 300B has a lower viscosity, and the resulting heat-cured PU film has better leveling performance, and there are no bubble spots, orange peel lines, edge shrinkage and other problems on the surface. , and its hardness and toughness are also better.
- Example 2 using HDI/IPDI addition prepolymer curing agent is better than Example 1 and Example 3, the hydrophobicity of Example 2 is relatively better.
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Abstract
本发明公开了一种超疏水自修复热固化PU胶膜制备方法及汽车保护膜，包括采用涂布工艺在具有类荷叶微纳结构的氟素离型膜上涂布PU胶水，然后进行固化处理，得具有荷叶微纳结构的PU胶膜；PU胶水包含低表面自由能疏水剂和硅油改性的羟基树脂。本发明结合硅油改性的羟基树脂和低表面自由能疏水剂制成PU胶水，该PU胶水在具有类荷叶微纳结构的氟素离型膜上固化成PU胶膜，从而在PU胶膜上构筑了微‑纳多级结构，微‑纳多级结构、低表面自由能疏水剂和硅油改性的羟基树脂的共同作用实现了PU胶膜表面超强的疏水性能，制得的微‑纳多级结构不易脱落，胶膜表面微纳形貌复制得完善、精细和具有持久特性；与传统工艺相比，本发明简化生产工艺，降低生产成本。
Description
本发明涉及汽车保护膜领域，特别是一种超疏水自修复热固化PU胶膜制备方法及汽车保护膜。
保护膜在功能上讲是贴合在被保护的实体物品表面的一层胶膜，通常的结构为上保膜+功能涂层+保护膜基材+压敏胶层+离型膜。汽车漆面用保护膜，俗称隐形车衣，目前市场上常用的材质主要为PVC(聚氯乙烯)和TPU(热塑性聚氨酯)。PVC材质的保护膜，其中增塑剂易析出而导致偏脆，胶层容易脱落，使用寿命在2‑3年左右。TPU材质是一类加热可以塑化、溶剂可以溶解的聚氨酯，主要利用挤出机，将TPU胶粒在200℃左右的温度下进过混合、熔融塑化、挤出流延、冷却定型而得到胶膜成品。因聚氨酯是由异氰酸酯硬段和多元醇软段组成的兼具有塑性和弹性为一体的嵌段型聚合物，具有硬度和弹性可调控范围广，耐磨性、耐候性和耐化学品性优异。因此通过自修复、疏水抗污功能涂层+TPU基材+压敏胶层的层合结构，展现稳定、良好的韧性、疏水抗污和自动修复功能，让它备受追捧，是隐形车衣最好的材料，使用寿命可达5
-10年。
超疏水性是一种特殊的表面润湿现象，是指液滴与固体表面接触角＞150 °，滚动接触角＜10 °的表面现象。随着对超疏水现象的研究，发现超疏水表面具有优异的自清洁、防水、防污、防腐蚀等重要特点，在科学研究、生产和生活等诸多领域有极为广泛的应用前景。但是普通的通过引入低表面能物质的方式，水接触角只能达到100 °
-110 °，无法达到超疏水标准。
公开号为CN108728007A的专利公开了具有自修复功能的防紫外线隐形车衣膜及其制备方法，包括TPU基材层，还包括从下到上依次设置在TPU层上表面的自修复层、保护硅胶层、PET层，以及从上到下依次设置在TPU基材层下表面的压敏胶层、离型层。通过在TPU基材层表面上涂布以氟化聚氨酯树脂为主体的自修复层，使得TPU层具有优异的防涂鸦、防污和自修复功能，但该涂层没有明显的超疏水效果。
公开号为CN112126339A的专利公开了一种超疏水TPU材料汽车漆面保护膜自修复涂层的制备方法，其原料包括脂肪族二异氰酸酯、羟基聚醚多元醇、催化剂、扩链剂、抗紫外助剂和溶剂等，通过引入惰性硅油形成低表面能，同时通过混合经过柠檬酸钠修饰的纳米粒子形成表面微纳结构，最终实现TPU涂层表面具有超疏水“荷叶”形貌，实施例中水接触角＞150℃。
专利CN112126339A所提供的方法虽然在TPU基材上实现了自修复功能和超疏水功能，无需像专利CN108728007A一样在基材层表面上涂布特殊的自修复层或/和超疏水层，简化了保护膜的结构和工序。但是，通过气相二氧化硅等纳米粒子形成的TPU薄膜表面的微纳结构形貌不完善，且经过长期刮擦和雨水冲刷后，纳米粒子容易脱落而失去超疏水效果。
综上所述，现有技术存在如下缺点：传统的保护膜是在保护膜基材上涂布功能涂层，生产工艺复杂，生产成本高，而通过气相二氧化硅等纳米粒子形成的TPU薄膜表面的微纳结构形貌不完善，且经过长期刮擦和雨水冲刷后，纳米粒子容易脱落而失去超疏水效果。
为了克服现有技术的不足，本发明提供一种超疏水自修复热固化PU胶膜制备方法及汽车保护膜。
本发明解决其技术问题所采用的技术方案是：
一种超疏水自修复热固化PU胶膜制备方法，包括：采用涂布工艺在表面具有类荷叶微纳结构的氟素离型膜上涂布PU胶水，然后进行固化处理，得具有类荷叶微纳结构的PU胶膜；所述PU胶水还包含硅油改性的羟基树脂，所述硅油改性的羟基树脂为含羟基的硅油改性聚酯型聚氨酯树脂和含羟基的硅油改性聚醚型聚氨酯树脂中的一种或两种的组合物；所述PU胶水包含低表面自由能疏水剂，所述低表面自由能疏水剂为含氟嵌段聚合物溶液和有机硅改性聚丙烯酸溶液中的一种或两种的组合物。
所述羟基树脂的硅含量为1％
-6％。
所述羟基树脂的羟基官能度为1
-3、玻璃化转变温度为
-10℃
-50℃ ，分子量为5000
-15000g/mol。
所述PU胶水还包含催化剂、流平剂、紫外线吸收剂、溶剂和固化剂。
所述催化剂为有机铋类催化剂和有机锡类催化剂中的一种。
所述流平剂为聚醚改性聚二甲基硅氧烷和芳烷基改性甲基烷基聚硅氧烷中的一种或两种的组合物。
所述溶剂为酯类溶剂、酰胺类溶剂和醚类溶剂中的一种或两种以上的组合物。
所述固化剂为HDI三聚体、IPDI三聚体、HDI缩二脲和HDI/IPDI加成预聚物中的一种或两种以上的组合物。
所述固化处理包括将涂布后的PU胶水放置在温度为100
-150℃的烘干设备中烘烤2
-5min。
一种汽车保护膜，包括如上所述的制备方法制得的热固化PU胶膜，该汽车保护膜的制备方法如下：在所述热固化PU胶膜不具有荷叶微纳结构的一面涂布有机硅压敏胶，固化后贴合普通氟素离型保护膜，再经过模切后得汽车保护膜。
本发明的有益效果是：本发明通过在以硅油改性的羟基树脂为主体树脂的PU胶水中引入低表面自由能疏水剂来改善PU胶膜自身的疏水特性，硅油改性的羟基树脂本身能够赋予PU胶膜优异的自修复能力，低表面自由能疏水剂分子量较低，容易迁移到胶膜表面，表现出优异的疏水特性，而硅油改性的羟基树脂能与低表面自由能疏水剂形成不同的迁移梯度，这种协同效应能使PU胶膜表面疏水特性更持久；结合硅油改性的羟基树脂和低表面自由能疏水剂制成的PU胶水的基础上采用涂布工艺在具有类荷叶微纳结构的氟素离型膜上涂布PU胶水，然后固化成PU胶膜，从而在PU胶膜上构筑了微‑纳多级结构，微‑纳多级结构、低表面自由能疏水剂和硅油改性的羟基树脂的共同作用实现了PU胶膜表面超强的疏水性能，水接触角达到150 °以上，滚动接触角低于10 °，与现有的通过添加纳米粒子形成微纳结构相比，本发明制得的微‑纳多级结构不易脱落，具备持久性和耐用性；与传统在保护膜基材上涂布功能涂层的复杂工艺相比，本发明简化生产工艺，降低生产成本。
在本发明所有实施例中，关于温度和压力没有特别强调的，均为常温常压，关于设备使用没有特别说明的，均按常规设置来使用即可。
一种超疏水自修复热固化PU胶膜制备方法：采用涂布工艺在表面具有类荷叶微纳结构的氟素离型膜上涂布热固化PU胶水，在120℃烘烤3
-4min使胶水表干、固化，形成60
-100μm厚的带具有类荷叶微纳结构的氟素离型膜的热固化PU胶膜。
所述PU胶水包含低表面自由能疏水剂，所述低表面自由能疏水剂为含氟嵌段聚合物溶液和有机硅改性聚丙烯酸溶液中的一种或两种的组合物，低表面自由能疏水剂分子量较低，容易迁移到胶膜表面，表现出优异的疏水特性。
所述PU胶水还包含羟基树脂，所述羟基树脂为含羟基的硅油改性聚酯型聚氨酯树脂和含羟基的硅油改性聚醚型聚氨酯树脂中的一种或两种的组合物。硅油改性的羟基树脂本身能够赋予PU胶膜优异的自修复能力，其与低表面自由能疏水剂形成不同的迁移梯度，这种协同效应能使PU胶膜表面疏水特性更持久。
更进一步的，为了与易迁移的低表面自由能疏水剂形成协同效应，达到优异且持久的超疏水效果，所述羟基树脂为硅油改性的羟基树脂，硅含量为1％
-6％，优选3％
-5％。
更进一步的，为了达到优异的自修复效果，所述羟基树脂的羟基官能度为1
-3、玻璃化转变温度为
-10℃
-50℃，分子量为5000
-15000g/mol。
本发明通过在以硅油改性的羟基树脂为主体树脂的PU胶水中引入低表面自由能疏水剂来改善PU胶膜自身的疏水特性，硅油改性的羟基树脂本身能够赋予PU胶膜优异的自修复能力，低表面自由能疏水剂分子量较低，容易迁移到胶膜表面，表现出优异的疏水特性，而硅油改性的羟基树脂能与低表面自由能疏水剂形成不同的迁移梯度，这种协同效应能使PU胶膜表面疏水特性更持久；结合硅油改性的羟基树脂和低表面自由能疏水剂制成的PU胶水的基础上采用涂布工艺在具有类荷叶微纳结构的氟素离型膜上涂布PU胶水，然后固化成PU胶膜，从而在PU胶膜上构筑了微‑纳多级结构，微‑纳多级结构、低表面自由能疏水剂和硅油改性的羟基树脂的共同作用实现了PU胶膜表面超强的疏水性能，水接触角达到150 ° 以上，滚动接触角低于10 °，与现有的通过添加纳米粒子形成微纳结构相比，本发明制得的微‑纳多级结构不易脱落，具备持久性和耐用性；与传统在保护膜基材上涂布功能涂层的复杂工艺相比，本发明简化生产工艺，降低生产成本。
所述具有类荷叶微纳结构的氟素离型膜的制备方法：利用激光刻蚀法在普通PET膜上刻蚀得到具有类荷叶微纳结构的薄膜，然后用含氟离型剂进行表面处理，得到具有类荷叶微纳结构的氟素离型膜。
采用具有类荷叶微纳结构的氟素离型膜不仅可以赋予PU胶膜表面疏水性能，其本身可多次重复使用，成本较低。
所述具有类荷叶微纳结构的氟素离型膜是表面密集分布有微米级凹坑和凹坑内表面存在纳米级亚结构的氟素离型膜。这种微纳米结构与荷叶表面的微纳米结构相反，因此称作类荷叶微纳米结构，行业中也常称作阴模。
所述PU胶水由如下重量份数的原料制成：羟基树脂30
-50份、低表面自由能疏水剂0.2
-2份、催化剂0 .1
-1 .5份、流平剂0 .2
-4份、紫外线吸收剂2
-4份、溶剂40
-70份和固化剂15
-40份。
所述羟基树脂为含羟基的硅油改性聚酯型聚氨酯树脂和含羟基的硅油改性聚醚型聚氨酯树脂中的一种或两种的组合物。所述羟基树脂的羟基官能度为1
-3、玻璃化转变温度为
-10℃
-50℃，分子量为5000
-15000g/mol；所述羟基树脂为硅油改性羟基树脂，硅含量为1％
-6％，优选3％
-5％。与普通的树脂相比(如羟基丙烯酸树脂)，由上述羟基树脂制得的PU胶膜能赋予PU胶膜优异的自修复能力，且羟基树脂上的硅油链段通过化学键接枝在羟基树脂上，与低表面自由能疏水剂形成不同的迁移梯度，这种协同效应，使表面疏水特性优异且更持久。
所述低表面自由能疏水剂为含氟嵌段聚合物溶液或有机硅改性聚丙烯酸溶液，选自信越的 K Y
-1 0 8 、K Y
-1 2 0 3 、K Y
-1 2 0 6 ，柯紐新材CoatFilmTM UVF
-1 0 3 ，BY K公司的SILCLEAN3700、3710、3720、Tego 5000、Tego 5001中的一种或两种以上，引入低表面自由能疏水剂，形成与传统汽车漆面保护膜类似的抗污特性，在不具备微纳结构的前提下PU胶膜表面的水接触角只能达到100°
-110°。
所述催化剂为有机铋类催化剂(Borchi Kat 22 ,拜尔)和有机锡类催化剂(曙乐实业(上海)有限公司生产的、型号为4233催化剂)中的一种。
所述流平剂为聚醚改性聚二甲基硅氧烷(BYK
-306、BYK
-331、BYK
-378)、芳烷基改性甲基烷基聚硅氧烷(BYK
-322)中的一种或两种以上的组合物。
所述溶剂为酯类溶剂、酰胺类溶剂、醚类溶剂中的一种或多种。
为了达到较好的耐户外老化特性，所述固化剂为脂肪族异氰酸酯固化剂，如HDI三聚体(六亚甲基二异氰酸酯三聚体，选自科思创公司Desmodur N3390、N3300)、IPDI三聚体(二异氟尔酮异氰酸酯三聚体物，选自科思创公司Desmodur Z4470)、HDI缩二脲(六亚甲基二异氰酸酯缩二脲，选自科思创公司Desmodur N75、N3320)、HDI/IPDI加成预聚物(鼎立森公司自产DI
-300B)中的一种或两种以上的组合物。
所述HDI/IPDI加成预聚物(鼎立森公司自产DI
-300B)由乙酸丁酯、三羟甲基丙烷、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和二月桂酸二丁基锡制成；所述六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和三羟甲基丙烷之间的摩尔比为(2 .0
-3 .0) ：(1 .2
-1 .8) ： (0 .8
-1 .2)；所述二月桂酸二丁基锡的重量百分比为0 .03
-0 .08％。
所述HDI/IPDI加成预聚物固化剂的制备步骤如下：在装有搅拌器、冷凝器、温度计的四口烧瓶中，加入上述乙酸丁酯、三羟甲基丙烷、六亚甲基二异氰酸酯与异佛尔酮二异氰酸酯，边搅拌边加热至70
-90℃，然后保温反应，在保温反应过程中分3
-5次加入二月桂酸二丁基锡，反应2 .5
-3h直至体系内不溶物质消失，得到HDI/IPDI加成预聚物固化剂。
经过探究实验发现，HDI、IPDI与TMP的摩尔比为2 .5:1 .5:1，催化剂DBTDL用量为0.05％，反应温度为80℃，反应时间3h时可获得低粘度、
-NCO含量最接近理论
-NCO含量的固化剂(理论NCO％为18 .26％，实测约为18 .40％)。
HDI/IPDI加成预聚物固化剂的作用：普通的PU胶膜，施工固含低，厚涂时流平不佳，易出现气泡点、橘皮纹，涂无基材边缘收缩不易成膜等问题。本发明的HDI/IPDI加成预聚物固化剂通过使用三羟甲基丙烷结合异佛尔酮二异氰酸酯与六亚甲基二异氰酸酯形成HDI/IPDI加成预聚物固化剂，交联结构比六亚甲基二异氰酸酯三聚体更紧密，自制的HDI/ IPDI加成预聚物固化剂比传统的异氰酸酯固化剂粘度要低，流平性更好，不仅能提高涂布时的施工固含，解决厚涂时流平不佳、易出现气泡点、橘皮纹和边缘收缩等问题，而且还能有效提高PU胶膜的硬度和韧性。
所述PU胶水的制备方法：
(1)、将上述重量份数的羟基树脂、低表面自由能疏水剂、催化剂、流平剂、紫外线吸收剂和溶剂放入搅拌釜中充分混合，得A组分，待用。
(2)、将上述重量份数的固化剂加入到搅拌釜中与A组分充分混合，获得PU胶水。
利用上述PU胶水制得的热固化PU胶膜相对现有的TPU薄膜存在如下优点：现有的TPU薄膜一般选用的是两官能度的异氰酸酯组分，是一类加热可以塑化、溶剂可以溶解的线性聚氨酯树脂。在其表面直接涂布有机硅压敏胶时，易被溶剂溶胀发白，只能通过贴合已涂布并烘烤表干的有机硅压敏胶。导致原因：热塑性的TPU分子间没有形成交联网络，直接涂覆硅胶会被其中的溶剂溶胀发白。一般需要贴合中间隔离层(如PET薄膜) ，这增加了保护膜制造端的工序和成本；或者只能通过贴合已涂布并烘烤表干的有机硅压敏胶。本发明的热固化PU胶膜具有可直涂硅胶的特性，其分子之间形成了交联网络，相比传统的TPU薄膜，表面可直接涂布有机硅压敏胶胶水，而不会因被溶剂溶胀而发白，也不会使有机硅压敏胶中的铂金催化剂中毒失活，无需贴合中间隔离层，结构简单、施工方便。
本发明的汽车保护膜的制备方法：在上述热固化PU胶膜的不具有荷叶微纳结构的一面涂布有机硅压敏胶，固化后贴合普通氟素离型保护膜，再经过模切后，可得汽车保护膜预成品。该汽车保护膜预成品撕去具有类荷叶微纳结构的氟素离型膜后，其表面复制了氟素离型膜上的微‑纳多级结构，即在每个微米级凸起顶部形成丰富的纳米级亚结构，这种与荷叶表面结构类似的微纳米结构结合热化固PU胶膜表面的低表面自由能物质，表现出优异的超疏水特性。
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式，对本发明进一步详细说明。需要说明的是，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。
该理解，这些描述只是示例性的，而并非要限制本发明的范围。
实施例1：
40重量份的硅油改性聚醚型脂肪族羟基聚氨酯树脂(宝骏化工535
-33A)、0 .05重量份的有机铋催化剂(Borchi Kat 22 ,拜尔)、1重量份的含氟疏水剂(UVF
-103)、0 .2重量份的硅氧烷流平剂(BYK
-333)、3重量份紫外线吸收剂(Tinuvin 401)、30重量份的乙酸丁酯和25重量份的HDI三聚体固化剂(科思创公司Desmodur N3390)。
实施例1的制备方法：
(1)、将上述重量份的聚醚型脂肪族羟基聚氨酯树脂、有机铋催化剂、含氟疏水剂、硅氧烷流平剂、紫外线吸收剂、和乙酸丁酯混合，获得胶水A组分待用。
(2)、将胶水A组分与25重量份的HDI三聚体固化剂充分混合，获得PU胶膜胶水。
(3)、在50μm的具有类荷叶微纳结构的氟素离型膜上涂布上述PU胶膜胶水，在120 ℃烘烤4min使胶水固化，形成60
-100μm厚的软膜层，用50μm低离型力的普通离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天。
(5)、撕开低离型力的一面涂布硅胶，待硅胶固化后再撕开具有类荷叶微纳结构的氟素离型膜，得实施例1。
实施例2：
30重量份的硅油改性聚醚型脂肪族羟基聚氨酯树脂(宝骏化工535
-33A)、0 .05重量份的有机铋催化剂(Borchi Kat 22 ,拜尔) 、0 .5重量份的含氟嵌段聚合物溶液 (KY
-1203) 、1重量份的有机硅改性聚丙烯酸酯溶液(BYK
-3700) 、0 .2重量份的硅氧烷流平剂(BYK
-333)、3重量份紫外线吸收剂(Tinuvin 401)、10重量份的乙酸乙酯、15重量份的甲基异丁基酮和20重量份的HDI/IPDI加成预聚物固化剂(鼎立森公司自产DI
-300B)。
实施例2的制备方法：
(1)、将上述重量份的聚醚型脂肪族羟基聚氨酯树脂、有机铋催化剂、含氟嵌段聚合物溶液、有机硅改性聚丙烯酸酯溶液、硅氧烷流平剂、紫外线吸收剂、乙酸乙酯和甲基异丁基酮混合，获得胶水A组分待用。
(2)、将胶水A组分与20重量份的HDI/IPDI加成预聚物固化剂充分混合，获得PU胶膜胶水。
(3)、在50μm的具有类荷叶微纳结构的氟素离型膜上涂布上述PU胶膜胶水，在120 ℃烘烤4min使胶水固化，形成60
-100μm厚的软膜层，用50μm低离型力的普通离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天。
(5)、撕开低离型力的一面涂布硅胶，待硅胶固化后再撕开具有类荷叶微纳结构的氟素离型膜，得实施例2。
实施例3：
40重量份的硅油改性聚醚型脂肪族羟基聚氨酯树脂(宝骏化工523
-2)、0 .05重量份的有机铋催化剂(Borchi Kat 22 ,拜尔)、1重量份的含氟嵌段聚合物溶液(KY
-1203)、0 .2 重量份的流平剂(BYK
-333)、2重量份紫外线吸收剂(Tinuvin 401)、30重量份的乙酸乙酯、30重量份的乙酸丁酯、10重量份的HDI缩二脲固化剂(科思创公司Desmodur N75)和10重量份的IPDI三聚体固化剂(科思创公司Desmodur Z4470)。
实施例3的制备方法：
(1)、将上述重量份的聚醚型脂肪族羟基聚氨酯树脂、有机铋催化剂、含氟嵌段聚合物溶液、流平剂、紫外线吸收剂、乙酸乙酯和乙酸丁酯混合，获得胶水A组分待用。
(2)、将胶水A组分与10重量份的HDI缩二脲固化剂和10重量份的IPDI三聚体固化剂充分混合，获得PU胶膜胶水。
(3)、在50μm的具有类荷叶微纳结构的氟素离型膜上涂布上述PU胶膜胶水，在120 ℃烘烤4min使胶水固化，形成60
-100μm厚的软膜层，用50μm低离型力的普通离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天。
(5)、撕开低离型力的一面涂布硅胶，待硅胶固化后再撕开具有类荷叶微纳结构的氟素离型膜，得实施例3。
对比例1：
45重量份的硅油改性聚醚型脂肪族羟基聚氨酯树脂(宝骏化工535
-33A)、0 .05重量份的有机铋催化剂(Borchi Kat 22 ,拜尔)、1重量份的含氟嵌段聚合物溶液(KY
-1203)、1重量份的有机硅改性聚丙烯酸酯溶液(BYK
-3700)、0 .3重量份的硅氧烷流平剂(TEGO
-450)、2重量份紫外线吸收剂(Tinuvin 401)、25重量份的乙酸丁酯、25重量份的甲基异丁基酮和20重量份的HDI三聚体固化剂(科思创公司Desmodur N3390)。
对比例1的制备方法：
(1)、将上述重量份的聚醚型脂肪族羟基聚氨酯树脂、有机铋催化剂、含氟嵌段聚合物溶液、有机硅改性聚丙烯酸酯溶液、流平剂、紫外线吸收剂、乙酸丁酯和甲基异丁基酮混合，获得胶水A组分待用。
(2)、将胶水A组分与20重量份的HDI三聚体固化剂充分混合，获得PU胶膜胶水。
(3)、在50μm的高离型力离型膜上涂布PU胶膜胶水，在120℃烘烤4min使胶水固化，形成60
-100μm厚的软膜层，用50μm低离型力的普通离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天。
(5)、撕开低离型力的一面涂布硅胶，待硅胶固化后再撕开高离型力的离型膜，得对比例1。
对比例2：
50重量份的羟基丙烯酸树脂 (宝骏化工532B
-4) 、0 .05重量份的有机铋催化剂 (Borchi Kat 22 ,拜尔)、0 .2重量份的硅氧烷流平剂(BYK
-333)、3重量份的紫外线吸收剂 (Tinuvin 401)、15重量份的乙酸乙酯、25重量份的乙酸丁酯和25重量份的HDI三聚体固化剂(科思创公司Desmodur N3390)。
对比例2的制备方法：
(1)、将上述重量份的羟基丙烯酸树脂、有机铋催化剂、硅氧烷流平剂、紫外线吸收剂、乙酸乙酯和乙酸丁酯混合，获得胶水A组分待用。
(2)、将胶水A组分与25重量份的HDI三聚体固化剂充分混合，获得PU胶膜胶水。
(3)、在50μm的高离型力离型膜上涂布PU胶膜胶水，在120℃烘烤4min使胶水固化，形成60
-100μm厚的软膜层，用50μm低离型力的普通离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天。
(5)、撕开低离型力的一面涂布硅胶，待硅胶固化后再撕开高离型力的离型膜，得对比例2。
其中，实施例1
-3表面呈现出超疏水自修复的特性，而对比例1和对比例2由于没有微纳结构，呈现出普通高水滴角特性。
申请人对上述得到的实施例1
-3和对比例1
-2作了相关的性能测试，结果如下表所示。
| 序号 | 厚度 | 水接触角 | 滚动接触角 | 自修复 | 动摩擦系数 | 老化试验 |
| 实施例1 | 80μ m | 151° | 6.1° | <5s | 0.11 | 3000h不黄变 |
| 实施例2 | 80μ m | 158° | 4.3° | <5s | 0.06 | 3000h不黄变 |
| 实施例3 | 80μ m | 153° | 5.6° | <30s | 0.09 | 2500h不黄变 |
| 对比例1 | 80μ m | 108° | 13.3° | <5s | 0.30 | 2500h不黄变 |
| 对比例2 | 80μ m | 87° | 19.5° | 不修复 | 0.70 | 3000h不黄变 |
从上表可见，本发明制备的PU胶膜的水接触角＞150℃，而滚动接触角＜10 °，满足超疏水涂层的定义，证明该PU胶膜具有明显的超疏水特性；相比而言，对比例1虽然使用了硅油改性的羟基聚氨酯树脂，并同时引入了低表面自由能的含氟和含硅疏水剂，但表面没有微纳结构，水接触角最高仅为108 °；对比例2为普通的树脂(羟基丙烯酸树脂) ，并且没有引入疏水剂，制得的PU胶膜无自修复功能，且水接触角不足90 °。同时，数据表明，本发明的PU胶膜不仅具有优异的自修复能力和超疏水性能，同时具有耐紫外老化性能，可直涂硅胶不发白等特点，此外实施例2选用鼎立森自产的的HDI/IPDI加成预聚物固化剂DI
-300B，其粘度较低，所制得的热固化PU胶膜的流平性表现更佳，表面无气泡点、橘皮纹和边缘收缩等问题，且其硬度和韧性也更好。
通过对比实施例1
-3的PU胶膜的疏水性，固化剂种类对PU胶膜疏水性也存在一定的影响，采用HDI/IPDI加成预聚物固化剂的实施例2相对实施例1和实施例3，实施例2的疏水性相对更好。
以上的实施方式不能限定本发明创造的保护范围，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。
Claims (10)
- 一种超疏水自修复热固化PU胶膜制备方法，其特征在于：包括：采用涂布工艺在表面具有类荷叶微纳结构的氟素离型膜上涂布PU胶水，然后进行固化处理，得具有类荷叶微纳结构的PU胶膜；所述PU胶水还包含硅油改性的羟基树脂，所述硅油改性的羟基树脂为含羟基的硅油改性聚酯型聚氨酯树脂和含羟基的硅油改性聚醚型聚氨酯树脂中的一种或两种的组合物；所述PU胶水包含低表面自由能疏水剂，所述低表面自由能疏水剂为含氟嵌段聚合物溶液和有机硅改性聚丙烯酸溶液中的一种或两种的组合物。
- 根据权利要求1所述的制备方法，其特征在于：所述羟基树脂的硅含量为1％ -6％。
- 根据权利要求2所述的制备方法，其特征在于：所述羟基树脂的羟基官能度为1 -3、玻璃化转变温度为 -10℃ -50℃，分子量为5000 -15000g/mol。
- 根据权利要求1所述的制备方法，其特征在于：所述PU胶水还包含催化剂、流平剂、紫外线吸收剂、溶剂和固化剂。
- 根据权利要求4所述的制备方法，其特征在于：所述催化剂为有机铋类催化剂和有机锡类催化剂中的一种。
- 根据权利要求4所述的制备方法，其特征在于：所述流平剂为聚醚改性聚二甲基硅氧烷和芳烷基改性甲基烷基聚硅氧烷中的一种或两种的组合物。
- 根据权利要求4所述的制备方法，其特征在于：所述溶剂为酯类溶剂、酰胺类溶剂和醚类溶剂中的一种或两种以上的组合物。
- 根据权利要求4所述的制备方法，其特征在于：所述固化剂为HDI三聚体、IPDI三聚体、HDI缩二脲和HDI/IPDI加成预聚物中的一种或两种以上的组合物。
- 根据权利要求1 -8任一所述的制备方法，其特征在于：所述固化处理包括将涂布后的PU胶水放置在温度为100 -150℃的烘干设备中烘烤2 -5min。
- 一种汽车保护膜，包括如权利要求1 -8任一所述的制备方法制得的热固化PU胶膜，其特征在于：该汽车保护膜的制备方法如下：在所述热固化PU胶膜不具有荷叶微纳结构的一面涂布有机硅压敏胶，固化后贴合普通氟素离型保护膜，再经过模切后得汽车保护膜。
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