CN113072890A - Self-repairing yellowing-resistant paint protective film and preparation method thereof - Google Patents
Self-repairing yellowing-resistant paint protective film and preparation method thereof Download PDFInfo
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- CN113072890A CN113072890A CN202110359872.7A CN202110359872A CN113072890A CN 113072890 A CN113072890 A CN 113072890A CN 202110359872 A CN202110359872 A CN 202110359872A CN 113072890 A CN113072890 A CN 113072890A
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- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- 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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- 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
- C09J2433/00—Presence of (meth)acrylic polymer
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- 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
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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Abstract
The invention discloses a self-repairing yellowing-resistant paint protective film and a preparation method thereof. The self-repairing coating is thermosetting functional polyurethane acrylate resin and comprises 20-50% of functional monomer modified acrylic resin, 10-30% of polymer polyol, 40-60% of diluent, 10-20% of curing agent, 0.2-0.5% of catalyst and 0.5-2% of auxiliary agent, the TPU substrate is optical-grade aliphatic TPU, the pressure-sensitive adhesive is acrylate adhesive, and the release film layer is a PET silicone oil release film. The paint protective film prepared by the invention has excellent yellowing resistance and self-repairing performance, high transparency and high glossiness, and excellent performances of scratch resistance, acid and alkali resistance, rainstain resistance and the like, so that the self-repairing yellowing resistance paint protective film is suitable for the fields of automobiles, furniture films and the like.
Description
Technical Field
The invention relates to the technical field of functional films, in particular to a self-repairing yellowing-resistant paint protective film and a preparation method thereof.
Background
In recent years, with the gradual improvement of the quality level of life of people, automobiles enter thousands of households like living necessities. However, the automobile cannot avoid the conditions of paint falling, corrosion and fading, embrittlement and cracking of the original factory caused by scraping collision, sun and rain, sand adhesion, and deposition of insect and bird feces in the use process of the automobile. In order to protect the original factory vehicle paint, a protective film (PPF) for the automobile paint surface is produced. With the upgrading of science and technology, the material of the car cover is also developed from the original PVC, TPH and PU to the current TPU, namely thermoplastic polyurethane. Compared with the prior art, the TPU has the advantages of toughness, impact resistance, puncture resistance, excellent performances of corrosion resistance, pollution resistance, hydrophobicity, oil resistance, high temperature resistance, low temperature resistance, chemical resistance and the like, and the material can be recycled and reused, and belongs to an environment-friendly material. Since the PPF originated in europe and america, especially in the united states, is leading in the development of materials, the U.S. brand is very expensive in the market. At present, the material of the domestic TPU paint surface protective film is mainly from America, Japan and China, and the domestic starting is relatively late, and the TPU paint surface protective film has strict global environmental protection standards and uneven quality unlike imported materials. From the feedback condition of the whole automobile paint surface protective film market, even if the TPU material paint surface protective film with better overall performance is used, the problems of yellowing, scratch resistance, pollution resistance, poor repairing performance and the like of the product are still more prominent.
CN108659517A discloses a base film for a TPU high-transparency paint surface protective film, which is obtained by processing raw materials comprising 80-90 parts of TPU with the hardness of 75-90A, 17531-7 parts of a slipping agent and 6-12 parts of an anti-UV-531 agent through a casting machine. Through the optimization of key parameters such as slipping agent, UV resistant auxiliary agent and the high degree of adhesion of the film and a forming roller, a TPU (thermoplastic polyurethane) painted surface base film product capable of reducing air bubbles and improving aging resistance is obtained.
CN109504142A discloses a self-repairing coating composition for a paint surface protective film, which comprises 0.1-1% of ultraviolet absorber, 5-10% of microcapsule A, 5-10% of microcapsule B, 12-36% of cross-linking curing reactive matrix, 0.5-2% of curing agent, 0.1-1% of surfactant and 40-75% of solvent, wherein after the self-repairing coating composition is applied to a base film and cross-linked and cured, the brightness, aging resistance, yellowing resistance, impact resistance, scratch resistance and other performances of the paint surface protective film can be improved, and the self-repairing of scratch can be realized through a microcapsule technology, but the microcapsule repairing technology can only realize single repairing of the same scratch position.
CN110343475A discloses a low-initial-adhesion high-adhesion paint surface protective film, wherein a pressure-sensitive adhesive layer of the protective film is composed of the following raw materials: 30-48 parts of crystalline hydroxyl polyurethane resin, 5-32 parts of polyol resin, 15-40 parts of tackifying resin, 0.5-10 parts of cross-linking agent, 0.5-3 parts of ultraviolet absorbent and 0.5-3 parts of antioxidant. The paint surface protective film prepared by the method has high light transmittance and ultraviolet absorptivity, has excellent performances of low initial adhesion, high permanent adhesion and the like, and effectively solves the problems that the adhesive film construction is not utilized due to overlarge initial adhesion of the protective film pressure-sensitive adhesive layer, and the permanent adhesion of the pressure-sensitive adhesive layer is attenuated due to photo-oxidation aging.
In conclusion, a simple and efficient functional film preparation process is explored, and a self-repairing, scratch-resistant, aging-resistant and yellowing-resistant paint surface protective film product is developed by selecting raw materials of a self-repairing coating, a TPU substrate and a pressure-sensitive adhesive layer according to a de novo design strategy, so that the method has important economic significance and practical value.
Disclosure of Invention
The invention mainly aims to solve the problems in the prior art and provides a self-repairing yellowing-resistant paint protective film and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the self-repairing yellowing-resistant paint surface protective film comprises a release film layer I, a pressure-sensitive adhesive layer, a TPU substrate, a self-repairing coating and a release film layer II from bottom to top in sequence; the self-repairing coating is formed by coating and thermally curing a functional polyurethane acrylate coating, and the functional polyurethane acrylate coating comprises the following components:
the functionalized monomer modified acrylic resin: 20 to 50 percent;
polymer polyol: 10 to 30 percent;
diluting the solvent: 40-60 percent;
curing agent: 10 to 20 percent;
0.2 to 0.5 percent of catalyst;
0.5 to 2 percent of auxiliary agent.
Preferably, the functional monomer modified acrylic resin is one or more of polyhydroxy ureido pyrimidone modified acrylate resin, polyhydroxy fluorine modified acrylate resin and polyhydroxy silicon modified acrylate resin, and the hydroxyl value is 80-130 mg KOH/g. More preferably, the functional monomer modified acrylic resin is selected from polyhydroxy ureido pyrimidone modified acrylate resin, and the hydroxyl value is about 85mg KOH/g.
Preferably, the polymer polyol is at least one of polyether polyol and polyester polyol; wherein the polyether diol is at least one of polytetrahydrofuran ether glycol and polypropylene glycol; the polyester diol is at least one of polycaprolactone diol and polycarbonate diol; the molecular weight of the polymer polyol is 1000-3000 g/mol. More preferably, the polymer polyol is at least one selected from polytetrahydrofuran ether glycol and polycaprolactone glycol with molecular weight of 2000.
Preferably, the diluting solvent is one or more of ethyl acetate, butyl acetate, butanone, propylene glycol monomethyl ether acetate and toluene.
Preferably, the curing agent is aliphatic diisocyanate or polyisocyanate thereof, including one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and corresponding trimer thereof; more preferably, the curing agent is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate trimer.
Preferably, the catalyst is at least one of organic tin catalysts and titanate catalysts.
Preferably, the auxiliary agent comprises at least one of an antioxidant, a light stabilizer and a leveling agent. More preferably, the light stabilizer is at least one of hindered amine, benzophenone and benzotriazole; the antioxidant is at least one of commercially available hindered phenol, hindered amine, thioester or phosphite antioxidant; the leveling agent is at least one of a fluorine-containing leveling agent, a silicon-containing leveling agent and a fluorine-silicon leveling agent.
Preferably, the thickness of the heat-cured self-repairing coating is 5-20 μm.
Preferably, the TPU substrate is optical grade aliphatic TPU with a thickness of 120-. Preferably, the pressure-sensitive adhesive layer is an optical-grade acrylate adhesive, and the thickness of the pressure-sensitive adhesive layer is 15-50 μm. Preferably, the release film layer I and the release film layer II are PET silicone oil release films with the thickness of 25-160 μm.
The preparation method of the self-repairing paint protective film comprises the following steps:
(1) coating optical-grade acrylate pressure-sensitive adhesive on a PET release film layer I by adopting a slit coating method, drying at the temperature of 80-110 ℃, and then laminating with an optical-grade aliphatic TPU base film to form an acrylic pressure-sensitive adhesive layer;
(2) coating the polyurethane acrylate self-repairing coating on the other side of the semi-finished product of the paint surface protective film obtained in the step (1), coating by adopting a micro-concave roller in a coating mode, drying and curing for 3 minutes in a gradient heating mode at 80 ℃/110 ℃/120 ℃/110 ℃/80 ℃ in five sections to form a self-repairing coating, covering a PET release film layer II on the optical-grade thermosetting polyurethane acrylate, and rolling to obtain the semi-finished product of the paint surface protective film.
(3) And (3) curing the semi-finished product prepared in the step (2) at 50-60 ℃ for 48-72 hours to obtain the self-repairing yellowing-resistant paint surface protective film.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts optical-grade aliphatic TPU material as the base film, has better optical performance, strong self weather resistance and yellowing resistance, tough impact resistance and puncture resistance, and excellent performances of corrosion resistance, pollution resistance, high temperature resistance, low temperature resistance and the like. The self-repairing coating is formed by compounding ureido pyrimidone modified polyhydroxy acrylic resin and polyhydroxy polymer dihydric alcohol, and can be crosslinked and compact after being thermally cured by diisocyanate, so that the outer surface of the protective film can have high brightness, scratch resistance, dirt resistance, acid-base corrosion resistance, aging resistance and other properties, and the surface scratches can be quickly repaired under the condition that the four-fold hydrogen bonds among ureido pyrimidone groups in the molecular structure of the coating are heated for 3s by hot water or hot air at 60-90 ℃, and the repairing times can reach hundreds. The pressure-sensitive adhesive layer is made of acrylate pressure-sensitive adhesive which is easy to peel, strong in permanent adhesion and excellent in aging and yellowing resistance, the cost is low, the construction is convenient, the acrylate pressure-sensitive adhesive is firmly combined with the surface of original factory car paint, and no adhesive residue is generated when the acrylate pressure-sensitive adhesive is removed. The slit extrusion and micro-concave roller precise coating technology adopted by the invention can accurately control the application amount of the coating liquid, and the coating has high surface flatness, few flaws, good coating thickness uniformity and precision and adjustability. In conclusion, the self-repairing paint protective film has the advantages of easily available raw materials and simple preparation process, can quickly produce paint protective film products with good paint protective effect and excellent comprehensive performance, and can be applied to the paint protective field of the surfaces of automobiles, high-grade furniture and the like.
Drawings
FIG. 1 is a schematic diagram of a self-repairing yellowing-resistant paint protective film product and structures of layers thereof prepared by the invention.
Fig. 2 is a comparison picture before and after a raindrop resistance test of the self-repairing yellowing-resistant paint protective film prepared by the invention, wherein fig. 2(a) is before raindrop wiping, and fig. 2(b) is after raindrop wiping.
Fig. 3 is a comparison picture before and after a scratch repair performance test of the self-repairing yellowing-resistant paint protective film prepared by the present invention, where fig. 3(a) is before scratch repair and fig. 3(b) is after scratch repair.
The symbols in the attached figure 1 correspond to the names:
1. the self-repairing coating comprises a release film layer I, a release film layer 2, a pressure-sensitive adhesive layer, a TPU (thermoplastic polyurethane) base film, a self-repairing coating and a release film layer II.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is described in detail with the embodiment. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Example 1
The functional polyurethane acrylate self-repairing coating comprises the following components: 25 percent of polyhydroxy ureido pyrimidone modified acrylate resin (hydroxyl value is 85mg KOH/g), 20 percent of polytetrahydrofuran ether glycol (BASF PolyTHF2000), 40 percent of butyl acetate, 15 percent of isophorone diisocyanate (Desmodur I, Kostew), 0.2 percent of dibutyltin dilaurate catalyst (Dabco T-12, U.S. gas) and 0.5 percent of silicon-containing leveling agent (Silok-353).
The preparation method of the self-repairing yellowing-resistant paint surface protective film comprises the following steps:
coating the Aroset 9510H acrylate pressure-sensitive adhesive on a PET release film layer I with the thickness of 50 mu m by adopting a slit coating method, drying at the temperature of 80-110 ℃, and then coating the PET release film layer I with an optical-grade Argotec aliphatic TPU base film to form an acrylic pressure-sensitive adhesive layer with the thickness of 35 mu m; coating the functional polyurethane acrylate self-repairing coating prepared in the above way on the other side of the TPU base film, coating by adopting a micro-concave roller in a coating mode, drying and curing for 3 minutes in a gradient heating mode at 80 ℃/110 ℃/120 ℃/110 ℃/80 ℃ in five sections to form a self-repairing coating with the thickness of 15 mu m, covering a PET release film layer II on the optical thermosetting polyurethane acrylate coating, rolling, and curing for 48 hours at 60 ℃ to obtain the self-repairing yellowing-resistant paint surface protective film.
Example 2
The functional polyurethane acrylate self-repairing coating comprises the following components: 20 percent of polyhydroxy ureido pyrimidone modified acrylate resin (hydroxyl value is 85mg KOH/g), 25 percent of polycaprolactone diol (BASF PCL2000), 40 percent of ethyl acetate, 15 percent of hexamethylene diisocyanate trimer (kostewa Desmodur N3300), 0.5 percent of dibutyltin dilaurate catalyst (American gas Dabco T-12) and 0.5 percent of silicon-containing leveling agent (Silok-353).
The preparation method of the self-repairing yellowing-resistant paint surface protective film comprises the following steps:
coating the Aroset 9510H acrylate pressure-sensitive adhesive on a PET release film layer I with the thickness of 50 mu m by adopting a slit coating method, drying at the temperature of 80-110 ℃, and then coating the PET release film layer I with an optical-grade Argotec aliphatic TPU base film to form an acrylic pressure-sensitive adhesive layer with the thickness of 30 mu m; coating the functional polyurethane acrylate self-repairing coating prepared in the above way on the other side of the TPU base film, coating by adopting a micro-concave roller in a coating mode, drying and curing for 3 minutes in a gradient heating mode at 80 ℃/110 ℃/120 ℃/110 ℃/80 ℃ in five sections to form a self-repairing coating with the thickness of 10 mu m, covering a PET release film layer II on the optical thermosetting polyurethane acrylate coating, rolling, and curing for 72 hours at 55 ℃ to obtain the self-repairing yellowing-resistant paint surface protective film.
Example 3
The functional polyurethane acrylate self-repairing coating comprises the following components: 25% of polyhydroxy silicon modified acrylate resin (hydroxyl value-120 mg KOH/g), 10% of polytetrahydrofuran ether glycol (BASF polyTHF2000), 45% of propylene glycol methyl ether acetate, 20% of hexamethylene diisocyanate trimer (Desmodur N3300), 0.3% of dibutyltin dilaurate catalyst (Dabco T-12 in American gas), 0.5% of benzotriazole (Tinuvin234, BASF) light stabilizer and 0.5% of hindered phenol (Irganox1076, BASF) antioxidant.
The preparation method of the self-repairing yellowing-resistant paint surface protective film comprises the following steps:
coating the Aroset 9510H acrylate pressure-sensitive adhesive on a PET release film layer I with the thickness of 50 mu m by adopting a slit coating method, drying at the temperature of 80-110 ℃, and then coating the PET release film layer I with an optical-grade Argotec aliphatic TPU base film to form an acrylic pressure-sensitive adhesive layer with the thickness of 35 mu m; coating the functional polyurethane acrylate self-repairing coating prepared in the above way on the other side of the TPU base film, coating by adopting a micro-concave roller in a coating mode, drying and curing for 3 minutes in a gradient heating mode at 80 ℃/110 ℃/120 ℃/110 ℃/80 ℃ in five sections to form a self-repairing coating with the thickness of 20 mu m, covering a PET release film layer II on the optical thermosetting polyurethane acrylate coating, rolling, and curing for 48 hours at 60 ℃ to obtain the self-repairing yellowing-resistant paint surface protective film.
Example 4
The functional polyurethane acrylate self-repairing coating comprises the following components: 25% of polyhydroxy fluorine modified acrylate resin (hydroxyl value-120 mg KOH/g), 10% of polytetrahydrofuran ether glycol (BASF polyTHF2000), 40% of butyl acetate, 25% of isophorone diisocyanate (Desmodur I, Coltsingde), 0.3% of stannous octoate catalyst (U.S. gas T-9), 0.5% of benzotriazole (Tinuvin234, BASF) light stabilizer and 0.5% of hindered phenol (Irganox1076, BASF) antioxidant.
The preparation method of the self-repairing yellowing-resistant paint surface protective film comprises the following steps:
coating the Aroset 9510H acrylate pressure-sensitive adhesive on a PET release film layer I with the thickness of 50 mu m by adopting a slit coating method, drying at the temperature of 80-110 ℃, and then coating the PET release film layer I with an optical-grade Argotec aliphatic TPU base film to form an acrylic pressure-sensitive adhesive layer with the thickness of 35 mu m; coating the functional polyurethane acrylate self-repairing coating prepared in the above way on the other side of the TPU base film, coating by adopting a micro-concave roller in a coating mode, drying and curing for 3 minutes in a gradient heating mode at 80 ℃/110 ℃/120 ℃/110 ℃/80 ℃ in five sections to form a self-repairing coating with the thickness of 15 mu m, covering a PET release film layer II on the optical thermosetting polyurethane acrylate coating, rolling, and curing for 72 hours at 50 ℃ to obtain the self-repairing yellowing-resistant paint surface protective film.
Comparative example 1
The functional polyurethane acrylate self-repairing coating comprises the following components: polyhydroxy acrylate resin (Borier)
BM259, hydroxyl value 80mg KOH/g) 20%, polycaprolactone diol (BASF PCL2000) 25%, ethyl acetate 40%, toluene-2, 4-diisocyanate (Desmodur T80, Corsfungsa) 15%, dibutyltin dilaurate catalyst (Dabco T-12, USA gas) 0.5%.
The preparation method of the paint protective film comprises the following steps:
coating the Aroset 9510H acrylate pressure-sensitive adhesive on a PET release film layer I with the thickness of 50 mu m by adopting a slit coating method, drying at the temperature of 80-110 ℃, and then coating the PET release film layer I with an optical-grade Argotec aliphatic TPU base film to form an acrylic pressure-sensitive adhesive layer with the thickness of 30 mu m; coating the functional polyurethane acrylate self-repairing coating prepared in the above way on the other side of the TPU base film, coating by adopting a micro-concave roller in a coating mode, drying and curing for 3 minutes in a gradient heating mode at 80 ℃/110 ℃/120 ℃/110 ℃/80 ℃ in five sections to form a self-repairing coating with the thickness of 10 mu m, covering a PET release film layer II on the optical-grade thermosetting polyurethane acrylate coating, rolling, and curing for 72 hours at 55 ℃ to obtain a finished product of the paint surface protective film.
Comparative example 2
The functional polyurethane acrylate self-repairing coating comprises the following components: 35% of polytetrahydrofuran ether glycol (BASF PolyTHF2000), 45% of propylene glycol methyl ether acetate, 20% of hexamethylene diisocyanate trimer (Desmodur N3300), 0.3% of dibutyltin dilaurate catalyst (Dabco T-12, us gas), 0.5% of benzotriazole (Tinuvin234, BASF) light stabilizer and 0.5% of hindered phenol (Irganox1076, BASF) antioxidant.
The preparation method of the paint protective film comprises the following steps:
coating the Aroset 9510H acrylate pressure-sensitive adhesive on a PET release film layer I with the thickness of 50 mu m by adopting a slit coating method, drying at the temperature of 80-110 ℃, and then coating the PET release film layer I with an optical-grade Argotec aliphatic TPU base film to form an acrylic pressure-sensitive adhesive layer with the thickness of 35 mu m; coating the functional polyurethane acrylate self-repairing coating prepared in the above way on the other side of the TPU base film, coating by adopting a micro-concave roller in a coating mode, drying and curing for 3 minutes in a gradient heating mode at 80 ℃/110 ℃/120 ℃/110 ℃/80 ℃ in five sections to form a self-repairing coating with the thickness of 20 mu m, covering a PET release film layer II on the optical-grade thermosetting polyurethane acrylate coating, rolling, and curing for 48 hours at 60 ℃ to obtain a finished product of the paint surface protective film.
The paint surface protective films prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to performance tests such as self-repairing and yellowing resistance, and the results of the performance tests are shown in table 1:
table 1: performance test results of the finish protective films prepared in examples and comparative examples
The performance test methods and criteria in table 1 are as follows:
(1) gloss: the test was carried out according to the specifications of GB/T9754, the test angle being 60 °. Wherein, bright type lacquer painting protection film is divided into A, B grades: the A-level glossiness is more than or equal to 140, and the B-level glossiness is more than or equal to 110 and less than 140;
(2) haze: the test was carried out according to the specifications of GB/T2410. Wherein the haze value of the bright paint protective film is required to be less than or equal to 1 percent;
(3) light transmittance: the test was carried out according to the specifications of GB/T2680. Wherein the visible light transmittance of the bright paint surface protective film is required to be more than or equal to 86.5 percent;
(4)180 ° peel strength: testing according to the GB/T2790 rule, and judging that the 180-degree peel strength value after 72 hours is more than or equal to 5N/25mm as qualified, otherwise, judging that the peel strength value is unqualified;
(5) tensile strength/elongation at break: the test was carried out according to the "5" type test specimen as specified in GB/T1040.3-2006. Wherein the tensile strength is more than or equal to 15MPa, the elongation at break is more than or equal to 150 percent, and the product is qualified, otherwise, the product is unqualified;
(6) tear strength: testing according to the GB/T529 specification, and judging that the tear strength is more than or equal to 40kN/m to be qualified, otherwise, judging that the tear strength is not more than 40kN/m to be unqualified;
(7) scratch resistance: the test is carried out according to the specification of 4.39.5 in GB/T17657-2013, the load is 5N, the test piece is scribed for one circle, and the condition of the scribed part on the surface of the test piece is observed and recorded. If no obvious scratch exists, the product is qualified, otherwise, the product is unqualified;
(8) puncture resistance: testing according to ASTM D1000, judging that the puncture resistance is more than or equal to 130N as qualified, otherwise, judging that the puncture resistance is not less than the qualified value;
(9) self-repairability: carrying out reciprocating scraping for 10 times by using a copper brush with the load of 500g, then repairing by using hot water or hot air at the temperature of 70 ℃ below zero, and recording the time for repairing the scratches;
(10) acid and alkali resistance: dilute sulfuric acid solution of pH <4 and sodium hydroxide solution of pH >10 were immersed for 120 minutes, after which they were removed for observation and their apparent mass changes were recorded. The fogging degree of the appearance after acid and alkali treatment is divided into 5 grades of A (none), B (very slight), C (slight), D (general) and E (serious);
(11) rainstain resistance: spraying natural rainwater, drying in the open air, repeating the operation for 3 times, wiping with wet cloth, observing and recording the appearance change, and judging the product to be qualified if no speck, color change and light loss exist, or else, judging the product to be unqualified;
(12) stain resistance: according to the steps in JG/T304-.
(13) Yellowing resistance: and (3) carrying out a QUV xenon lamp aging test on the sample, wherein the environmental conditions in a QUV ultraviolet aging box are set as follows: xenon lamp irradiation power 1500W/m2Internal cavity temperature 70 deg.CThe humidity was 65% and the UV irradiation was carried out for 18min water spray at 120min intervals. Testing the yellow index change delta YI of the sample before and after 3000h of QUV xenon lamp aging test according to the specification of HG/T3862-2006; testing the color parameters L, a and b before and after aging of the sample according to the specification of GB/T36142-2018 and according to the formula
Calculating color difference before and after sample test
And Δ b*. Wherein, Delta YI is less than or equal to 1.4,
Δb*not more than 0.8, no bubble, chalking, cracking and no obvious light loss are generated in the test sample after the test, the test sample is regarded as qualified, and otherwise, the test sample is not qualified.
As can be seen from the test results in table 1: the paint surface protective film prepared in the embodiments 1-2 has quick self-repairing performance, and can effectively improve the self-repairing performance of the material through multiple reversible hydrogen bonds due to the ureidopyrimidone groups introduced into the top coating; from the results of the examples 3-4 and the comparative example 1, the introduction of the silicon and fluorine modified components into the top coating brings good hydrophobic and oil repellent performance to the material, and improves the performances of the material such as stain resistance, acid and alkali corrosion resistance, raindrop resistance and the like; from the results of the examples 1-4 and the comparative example 2, it can be seen that the gloss, stain resistance, self-repair, acid-base corrosion resistance, rainstain resistance and other properties of the sample can be improved more by adopting the two-component resin (i.e., the polyhydroxy acrylate modified resin and the polymer polyol are compounded) in the top coating layer than by adopting the single-component resin (i.e., the polymer polyol) through thermosetting crosslinking, so that a more compact polyurethane acrylate crosslinked network structure can be formed after the two-component resin is cured through thermal crosslinking, and the polyurethane crosslinked network structure formed by the two-component resin has more excellent properties of permeation resistance, high barrier property, scratch resistance and the like than the polyurethane crosslinked structure formed by the single polymer polyol component; in addition, the results of examples 1 to 4 and comparative example 1 show that the introduction of the aliphatic diisocyanate or polyisocyanate curing agent can further improve the yellowing resistance, aging resistance and other performances of the material.
In conclusion, the paint protective film prepared by the invention has excellent yellowing resistance and self-repairing performance, high transparency and high glossiness, excellent performances of scratch resistance, acid and alkali resistance, rainstain resistance and the like, and simple production process, and is easy for industrial batch production, so that the self-repairing yellowing resistance paint protective film prepared by the invention is suitable for various fields of automobiles, furniture films and the like.
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 (12)
1. The self-repairing yellowing-resistant paint surface protective film is characterized by comprising a release film layer I, a pressure-sensitive adhesive layer, a TPU substrate, a self-repairing coating and a release film layer II from bottom to top in sequence; the self-repairing coating is formed by coating and thermally curing a functional polyurethane acrylate coating, and comprises the following components:
the functionalized monomer modified acrylic resin: 20 to 50 percent;
polymer polyol: 10 to 30 percent;
diluting the solvent: 40-60 percent;
curing agent: 10 to 20 percent;
0.2 to 0.5 percent of catalyst;
0.5 to 2 percent of auxiliary agent.
2. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the functional monomer modified acrylic resin is one or more of polyhydroxy ureido pyrimidone modified acrylate resin, polyhydroxy fluorine modified acrylate resin and polyhydroxy silicon modified acrylate resin.
3. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the polymer polyol is at least one of polyether polyol and polyester polyol; wherein the polyether diol is at least one of polytetrahydrofuran ether glycol and polypropylene glycol; the polyester diol is at least one of polycaprolactone diol and polycarbonate diol; the molecular weight of the polymer polyol is 1000-3000 g/mol.
4. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the diluting solvent is one or more of ethyl acetate, butyl acetate, butanone, propylene glycol methyl ether acetate and toluene.
5. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the curing agent is aliphatic diisocyanate or polyisocyanate thereof, and comprises one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and corresponding trimer thereof.
6. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the catalyst is at least one of an organotin catalyst and a titanate catalyst.
7. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the auxiliary comprises at least one of an antioxidant, a light stabilizer and a leveling agent, and the light stabilizer is at least one of hindered amine, benzophenone and benzotriazole light stabilizers; the antioxidant is at least one of commercially available hindered phenol, hindered amine, thioester or phosphite antioxidant; the leveling agent is at least one of a fluorine-containing leveling agent, a silicon-containing leveling agent and a fluorine-silicon leveling agent.
8. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the thickness of the self-repairing coating is 5-20 μm.
9. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the TPU substrate is optical-grade aliphatic TPU, and the thickness of the TPU substrate is 120-200 μm.
10. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the pressure-sensitive adhesive layer is an optical acrylate adhesive and has a thickness of 15-50 μm.
11. The self-repairing yellowing-resistant paint protective film according to claim 1, wherein the release film layer I and the release film layer II are PET silicone oil release films with a thickness of 25-160 μm.
12. The preparation method of the self-repairing yellowing-resistant paint protective film of any one of claims 1 to 11, characterized by comprising the following steps:
(1) coating optical-grade acrylate pressure-sensitive adhesive on a PET release film layer I by adopting a slit coating method, drying at the temperature of 80-110 ℃, and then laminating with an optical-grade aliphatic TPU substrate to form an acrylate pressure-sensitive adhesive layer;
(2) coating the polyurethane acrylate self-repairing coating on the other side of the semi-finished product of the paint surface protective film obtained in the step (1), coating by adopting a micro-concave roller in a coating mode, drying and curing for 3 minutes in a gradient heating mode at 80 ℃/110 ℃/120 ℃/110 ℃/80 ℃ in five sections to form a self-repairing coating, covering a PET release film layer II on the optical-grade thermosetting polyurethane acrylate, and rolling to obtain the semi-finished product of the paint surface protective film.
(3) And (3) curing the semi-finished product prepared in the step (2) at 50-60 ℃ for 48-72 hours to obtain the self-repairing yellowing-resistant paint surface protective film.
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