CN109735249B - Matte paint protective film - Google Patents
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- CN109735249B CN109735249B CN201811612823.4A CN201811612823A CN109735249B CN 109735249 B CN109735249 B CN 109735249B CN 201811612823 A CN201811612823 A CN 201811612823A CN 109735249 B CN109735249 B CN 109735249B
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Abstract
A matte finish protective film comprises a transparent support, wherein a matte self-repairing layer and a transparent protective film are sequentially arranged on one optical surface of the transparent support; sequentially arranging an assembly adhesive and a semitransparent release film on the other optical surface of the transparent support body, wherein the matte self-repairing layer is formed by coating self-repairing coating liquid and then heating and curing; the self-repairing coating liquid contains elastic organic particles, modified polyol resin, a curing agent and other components; the particle size of the elastic organic particles is 1-15 mu m; the curing agent is formed by mixing a curing agent 1 and a curing agent 2 in a mixing ratio of 2: 1-5: 1. The matte paint surface protective film provided by the invention has good matte effect and self-repairing effect, has yellowing resistance and antifouling property, and can be applied to the field of paint surface protection of the surface of an automobile.
Description
Technical Field
The invention relates to the technical field of films, in particular to a paint surface protective film attached to the surface of an automobile.
Background
The automobile paint surface protective film, also called invisible automobile coat, is a layer of transparent protective film adhered to the paint on the surface of an automobile, and protects the original factory paint of the automobile from being damaged. The product has very strong toughness, still has the self-repairing function, can effectually prevent to scrape and rub and the hitting of sand grain, has still completely cut off the contact of car lacquer with the air, can prevent the injury to the lacquer painting such as acid rain, asphalt, bird droppings. Meanwhile, the paint surface protective film is high in definition and high in brightness, and the color and luster of the automobile paint surface can be improved and protected.
For the purpose of individualization, a demand for a matte finish protective film is now being raised. There are two general methods for manufacturing the matte film, one is to add matting powder to the coating. After the extinction powder is added into the self-repairing layer in the paint surface protective film, the hard extinction powder counteracts the resilience of the self-repairing resin, and the self-repairing coating no longer has self-repairing performance; the other mode is that an uneven structure is stamped on the surface of the coating in a stamping mode, so that the matte effect is realized. However, the method is only suitable for the ultraviolet curing coating, and the self-repairing effect of the existing ultraviolet curing self-repairing coating is far from the effect of the heat curing self-repairing coating, so that the method cannot be applied to the protective film of the automobile paint surface.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a matte paint surface protective film aiming at the defects in the prior art, which can quickly dry the surface and quickly repair scratches, has a good self-repairing layer durability, and has good yellowing resistance and acid and alkali resistance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a matte finish protective film comprises a transparent support, wherein a matte self-repairing layer and a transparent protective film are sequentially arranged on one optical surface of the transparent support; the matte self-repairing layer is formed by coating self-repairing coating liquid and then heating and curing, and the self-repairing coating liquid comprises the following components in parts by weight:
the particle size of the elastic organic particles is 1-15 mu m;
the curing agent is formed by mixing a curing agent 1 and a curing agent 2 in a mixing ratio of 2: 1-5: 1;
the curing agent 1 is any one selected from hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate and tetramethyl m-xylylene diisocyanate.
The curing agent 2 is any one selected from isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, cyclohexane dimethylene diisocyanate and methylcyclohexyl diisocyanate.
In the matte paint surface protective film, the elastic organic particles are one of polyurethane particles, nylon particles or polybutyl acrylate particles.
In the matte paint surface protective film, the modified polyol resin is polycarbonate polyol resin or polyester polyol resin.
In the matte paint surface protective film, the reaction type leveling agent is hydroxyl-containing modified polysiloxane.
In the matte paint surface protective film, the metal drier is one of an organic tin drier, an organic bismuth drier or a rare earth drier.
The thickness of the self-repairing layer of the matte paint surface protective film is 5-30 microns.
The transparent support is a polyvinyl chloride film or a thermoplastic polyurethane film with the thickness of 100-300 mu m.
The matte paint surface protective film is characterized in that the transparent protective film is a polyester protective film with the thickness of 30-100 mu m, and the semitransparent release film is a polyester release film with the thickness of 30-100 mu m.
The assembly glue is polyurethane or polyacrylate pressure-sensitive glue with the thickness of 10-50 mu m.
The invention has the beneficial effects that:
1. according to the invention, the elastic organic particles are added in the matte self-repairing coating to achieve a good matte effect, and when the self-repairing coating is scratched by an external force, the elastic organic particles and the self-repairing coating deform together, and the scratches can be repaired by resilience, so that the problem of the self-repairing performance reduction of the coating caused by the addition of the matting powder is solved.
2. According to the invention, the elastic organic particles are added into the coating liquid, so that the antifouling performance of the matte self-repairing layer is improved, and rain marks generated by rainwater gathering on the film surface can be prevented.
3. The matte self-repairing layer adopts modified polyol resin as a cross-linking main body, adopts aliphatic isocyanate and alicyclic isocyanate as a curing agent, and forms the self-repairing layer capable of quickly drying the surface and quickly repairing scratches by matching according to a certain proportion. The self-repairing layer has good durability, and has good yellowing resistance and acid and alkali resistance. Can be applied to the field of the protection of the paint surface of the automobile.
Drawings
FIG. 1 is a schematic layer structure of a matte paint protective film according to the present invention.
In the drawings, the reference numerals denote: a transparent support 1; a matte self-repairing layer 2; a transparent protective film 3; assembling glue 4; a translucent release film 5.
Detailed Description
In order to realize the matte effect of the self-repairing layer, the elastic organic particles are added. Particles such as silicon dioxide and polymethyl acrylate are added into the matte coating to realize the matte effect, but the particles are added into the self-repairing coating to improve the hardness of the coating, and the self-repairing effect of the self-repairing coating is obviously weakened. According to the invention, the elastic organic particles are added in the matte self-repairing coating to achieve a good matte effect, and when the self-repairing coating is scratched by an external force, the elastic organic particles and the self-repairing coating deform together, and the scratches can be repaired by resilience, so that the problem of the self-repairing performance reduction of the coating caused by the addition of the matting powder is solved. The elastic organic particles are preferably one of polyurethane particles, nylon particles, and polybutyl acrylate particles. The amount of addition is preferably 1.5 to 7.5 parts by weight.
The modified polyol resin is a cross-linking main body of a self-repairing layer, and polycarbonate polyol resin and polyester polyol resin with an elastic repairing structure are selected according to the self-repairing requirement of the matte paint surface protective film. The concrete steps are as follows: LCR-100 series of NATOCO, HFC-PNS1 series of HARIMA, TRE-2-S2 series of ASIA, etc.
In the present invention, the curing agent is isocyanate. Isocyanate is a generic name for various esters of isocyanic acid and is an important raw material for the synthesis of polyurethane resins. Isocyanates are classified by chemical structure into aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and other isocyanates. In order to ensure that the matte self-repairing layer has lasting self-repairing property, yellowing resistance and acid and alkali resistance, the aliphatic isocyanate and alicyclic isocyanate are mixed for use, and the mixing ratio is preferably 2: 1-5: 1. Specifically related isocyanates are: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethylm-xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, cyclohexanedimethylene diisocyanate or methylcyclohexyl diisocyanate.
In the present invention, a leveling agent is added to the coating liquid in order to improve the flatness of the coating layer. In order to achieve the purpose of durable antifouling property of the matte self-repairing layer, the invention selects hydroxyl-containing modified polysiloxane, including hydroxyl-containing alkyl, phenyl, polyether and fluorine-modified polysiloxane. Illustrative hydroxyl-containing modified polysiloxanes are: BYK-370, BYK-373, BYK-375, BYK-377, BYK-3570, BYK-3700, Silok-359, Silok-363, Teck-2110, Teck-2120, Teck-2140, Teck-2220, DC-3667, DC-8427, KF-6002, and the like. The amount of addition is preferably 0.5 to 2.5 parts by weight.
In order to improve the curing speed of the matte self-repairing layer, the metal drier is added. The drier is a substance capable of accelerating oxidation and polymerization of paint to dry a film, and is generally classified into a tertiary amine drier and a metal drier. In order to achieve the effects of quick surface drying of the matte self-repairing layer and good self-repairing and antifouling effects, any one of an organic tin drier, an organic bismuth drier or a rare earth drier is preferably selected. Exemplary metal driers are: german chemical DY-12, American atmospheric chemical T-12, triton chemical T-20, Kasol auxiliary B1610, Kasol auxiliary B-18 and the like. The amount of addition is preferably 0.2 to 0.5 parts by weight.
The matte self-repairing coating liquid is also added with an organic solvent, wherein the organic solvent is as follows: aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone, butanone, methyl isobutyl ketone, 2-pentanone and isophorone; esters such as ethyl acetate and butyl acetate; and cellosolve-based solvents such as ethyl cellosolve. The organic solvent may be used alone or in combination of two or more.
In order to meet the requirement of high tensile property of the matte finish protective film, the transparent support is a polyvinyl chloride film or a thermoplastic polyurethane film, and the thickness of the transparent support ranges from 100 micrometers to 300 micrometers.
The assembly glue in the invention is selected from polyurethane or polyacrylate pressure-sensitive glue sold in the market; the thickness is preferably 10 μm to 50 μm.
The transparent protective film and the translucent release film described in the present invention function as a release film and a support transparent support, so a polyester release film is preferable. The thickness of the transparent protective film and the translucent release film is preferably 30 μm to 100 μm, and the release force is preferably 20gf/25mm to 200gf/25 mm.
The self-healing layer of the present invention is preferably applied by slot, comma, or microgravure coating. After the self-repairing coating liquid is coated on the supporting body, the self-repairing coating liquid is dried by a drying oven at the temperature of 80-150 ℃ for 0.5-5 min, and the solvent is simultaneously subjected to crosslinking reaction. Then putting the mixture into a curing chamber at the temperature of 40 ℃ for curing for 48 to 96 hours.
The present invention will be further described with reference to the following drawings and examples, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Preparing a semi-finished product of the paint surface protective film:
obtaining 10 mu m assembly glue on a semitransparent polyester release film with the thickness of 30 mu m by using a known technology, then covering the assembly glue with a polyvinyl chloride film with the thickness of 100 mu m, and rolling to obtain a semi-finished product of the paint surface protective film for later use.
(2) Preparation of self-repairing coating liquid:
30 kg of modified polyol resin [ LCR-100, NATOCO ], 1.5 kg of elastic organic particles [ polybutyl acrylate, average particle diameter 1 μm, accumulated water chemistry ], 0.5 kg of reactive leveling agent [ BYK-370, Big ], 0.2 kg of metal drier [ organotin drier DY-12, Delosol chemical ] and 60 kg of toluene were added to a vessel and stirred at high speed for 30 min. 6.7 kg of curing agent 1[ hexamethylene diisocyanate, Asahi chemical compound ] and 3.3 kg of curing agent 2[ isophorone diisocyanate, Wittig ] were added 30min before coating, and stirred at high speed for 10min for standby.
(3) Preparation of matte paint protective film
And coating the self-repairing coating liquid prepared above on the polyvinyl chloride film surface of the semi-finished product of the paint surface protective film in a strip and seam coating mode, drying and curing for 3min at 80 ℃/110 ℃/150 ℃/110 ℃/80 ℃ in a stepped heating mode to obtain a self-repairing layer with the thickness of 5 mu m, and then covering the self-repairing layer with a transparent polyester protective film with the thickness of 30 mu m. And finally, putting the mixture into a curing chamber at the temperature of 40 ℃ for curing for 48 hours to obtain the matte paint surface protective film. The self-healing layer was tested for performance and the results are shown in table 1.
Example 2
(1) Preparing a semi-finished product of the paint surface protective film:
obtaining 20 mu m-thick assembly glue on a 38 mu m-thick semitransparent polyester release film by using a known technology, then covering the assembly glue with a 150 mu m-thick thermoplastic polyurethane film, and rolling to obtain a semi-finished product of the paint surface protective film for later use.
(2) Preparation of self-repairing coating liquid:
into a vessel were charged 35 kg of modified polyol resin [ HFC-PNS1, HARIMA ], 3.0 kg of elastic organic particles [ polyurethane, average particle diameter 5 μm, resin on root ], 1.0 kg of reactive leveling agent [ Silok-359, Stocko ], 0.27 kg of metal drier [ organobismuth drier B1610, Casol auxiliary ] and 51 kg of ethyl acetate, and stirred at high speed for 30 min. 10.2 kg of curing agent 1[ trimethylhexamethylene diisocyanate, basf ] and 3.8 kg of curing agent 2[ dicyclohexylmethane-4, 4' -diisocyanate, WANHUA ] were added 30min before coating, and stirred at high speed for 10min for standby.
(3) Preparation of matte paint protective film
And coating the self-repairing coating liquid prepared above on the surface of the thermoplastic polyurethane film of the semi-finished product of the paint surface protective film by adopting a comma scraper coating mode, drying and curing for 3min at 80 ℃/110 ℃/150 ℃/110 ℃/80 ℃ in a stepped heating mode to obtain a self-repairing layer with the thickness of 12 mu m, and then covering a transparent polyester protective film with the thickness of 38 mu m on the self-repairing layer. And finally, putting the mixture into a curing chamber at the temperature of 40 ℃ for curing for 48 hours to obtain the matte paint surface protective film. The self-healing layer was tested for performance and the results are shown in table 1.
Example 3
(1) Preparing a semi-finished product of the paint surface protective film:
obtaining 30 mu m-thick assembly glue on a semitransparent polyester release film with the thickness of 50 mu m by using a known technology, then covering the assembly glue with a thermoplastic polyurethane film with the thickness of 200 mu m, and rolling to obtain a semi-finished product of the paint surface protective film for later use.
(2) Preparation of self-repairing coating liquid:
40 kg of modified polyol resin [ TRE-2-S2, ASIA ], 4.5 kg of elastic organic particles [ nylon, average particle diameter 8 μm, basf ], 1.5 kg of reactive leveling agent [ Teck-2110, Tyr ], 0.35 kg of metal drier [ rare earth drier B-18, Kasol auxiliary agent ] and 42 kg of acetone were added to a vessel and stirred at high speed for 30 min. 13.6 kg of curing agent 1[ xylylene diisocyanate, mol ] and 3.9 kg of curing agent 2[ cyclohexanedimethylene diisocyanate, Sanjing Wutian ] were added 30min before coating and stirred at high speed for 10min for further use.
(3) Preparation of matte paint protective film
And coating the self-repairing coating liquid prepared above on the surface of the thermoplastic polyurethane film of the semi-finished product of the paint surface protective film by adopting a micro-gravure coating mode, drying and curing for 3min at 80 ℃/110 ℃/150 ℃/110 ℃/80 ℃ in a stepped heating mode to obtain a self-repairing layer with the thickness of 18 mu m, and then covering the self-repairing layer with a transparent polyester protective film with the thickness of 50 mu m. And finally, putting the mixture into a curing chamber at the temperature of 40 ℃ for curing for 48 hours to obtain the matte paint surface protective film. The self-healing layer was tested for performance and the results are shown in table 1.
Example 4
(1) Preparing a semi-finished product of the paint surface protective film:
obtaining assembly glue with the thickness of 40 mu m on a semitransparent polyester release film with the thickness of 75 mu m by using a known technology, then covering the assembly glue with a polyvinyl chloride film with the thickness of 250 mu m, and rolling to obtain a semi-finished product of the paint surface protective film for later use.
(2) Preparation of self-repairing coating liquid:
45 kg of modified polyol resin [ LCR-100, NATOCO ], 6.0 kg of elastic organic particles [ polyurethane, having an average particle diameter of 10 μm, resin on the root ], 2.0 kg of a reactive leveling agent [ DC-3667, Dow Corning ], 0.43 kg of a metal drier [ organotin drier T-12, American Aikochemie ] and 33 kg of ethanol were charged in a vessel and stirred at high speed for 30 minutes. 17.8 kg of curing agent 1[ tetramethyl m-xylylene diisocyanate, Sanjing Wutian ] and 4.2 kg of curing agent 2[ methyl cyclohexyl diisocyanate, Mobay chemical ] were added 30min before coating and stirred at high speed for 10min for further use.
(3) Preparation of matte paint protective film
And coating the self-repairing coating liquid prepared above on the polyvinyl chloride film surface of the semi-finished product of the paint surface protective film in a strip and seam coating mode, drying and curing for 3min at 80 ℃/110 ℃/150 ℃/110 ℃/80 ℃ in a stepped heating mode to obtain a self-repairing layer with the thickness of 26 microns, and then covering the self-repairing layer with a transparent polyester protective film with the thickness of 75 microns. And finally, putting the mixture into a curing chamber at the temperature of 40 ℃ for curing for 48 hours to obtain the matte paint surface protective film. The self-healing layer was tested for performance and the results are shown in table 1.
Example 5
(1) Preparing a semi-finished product of the paint surface protective film:
obtaining assembly glue with the thickness of 50 microns on a semitransparent polyester release film with the thickness of 100 microns by using a known technology, then covering the assembly glue with a thermoplastic polyurethane film with the thickness of 250 microns, and rolling to obtain a semi-finished product of the paint surface protective film for later use.
(2) Preparation of self-repairing coating liquid:
50 kg of modified polyol resin [ TRE-2-S2, ASIA ], 7.5 kg of elastic organic particles [ polybutyl acrylate, average particle size 15 μm, general research ], 2.5 kg of reactive leveling agent [ BYK-3700, bike ], 0.5 kg of metal drier [ organotin drier T-20, triton chemistry ] and 25 kg of methyl isobutyl ketone were added to a vessel and stirred at high speed for 30 min. 20.8 kg of curing agent 1[ xylylene diisocyanate, mol ] and 4.2 kg of curing agent 2[ isophorone diisocyanate, winning ] were added 30min before coating, and stirred at high speed for 10min for standby.
(3) Preparation of matte paint protective film
And coating the self-repairing coating liquid prepared above on the surface of the thermoplastic polyurethane film of the semi-finished product of the paint surface protective film by adopting a micro-gravure coating mode, drying and curing for 3min at 80 ℃/110 ℃/150 ℃/110 ℃/80 ℃ in a stepped heating mode to obtain a self-repairing layer with the thickness of 30 mu m, and then covering the self-repairing layer with a transparent polyester protective film with the thickness of 100 mu m. And finally, putting the mixture into a curing chamber at the temperature of 40 ℃ for curing for 48 hours to obtain the matte paint surface protective film. The self-healing layer was tested for performance and the results are shown in table 1.
Comparative example 1
The procedure is as in example 1 except that no elastic organic particles are added to produce a matte finish protective film. The self-healing layer was tested for performance and the results are shown in table 1.
Comparative example 2
The procedure was the same as in example 1 except that the polybutyl acrylate was replaced with silica particles having an average particle diameter of 1 μm. The self-healing layer was tested for performance and the results are shown in table 1.
Table 1: test data sheet for each example
| Haze degree | Speed of repair | Resistance to rain marks | |
| Example 1 | 12％ | 2s | Qualified |
| Example 2 | 24％ | 3s | Qualified |
| Example 3 | 38％ | 3s | Qualified |
| Example 4 | 55％ | 4s | Qualified |
| Example 5 | 78％ | 5s | Qualified |
| Comparative example 1 | 2.5％ | 1s | Fail to be qualified |
| Comparative example 2 | 10％ | Can not be repaired | Qualified |
The test methods for the properties in the table are as follows:
1. determination of haze
Using a haze meter [ japan electrochromic corporation; the model is as follows: NDH2000N ] measures haze.
2. Determination of repair speed
The self-healing layer was stroked vigorously with a copper brush and a stopwatch recorded the time in "s" for scratch healing.
3. Determination of "rain mark" resistance
Attaching the matte paint surface protective film to an automobile, then spraying the collected rainwater on the surface of the paint surface protective film, observing the trace of the rainwater after drying, and judging that the automobile is unqualified if the trace exists; no trace is found to be "qualified".
Claims (7)
1. A matte finish protective film comprises a transparent support, wherein a matte self-repairing layer and a transparent protective film are sequentially arranged on one optical surface of the transparent support; the matte self-repairing layer is formed by coating self-repairing coating liquid and then heating and curing, and the self-repairing coating liquid comprises the following components in parts by weight:
30 to 50 parts of modified polyol resin,
10 to 25 parts of a curing agent,
elastic organic particles 1.5 to 7.5
0.5 to 2.5 parts of a reactive leveling agent,
0.2 to 0.5 parts of metal drier,
25-60% of an organic solvent;
the particle size of the elastic organic particles is 1-15 mu m;
the curing agent is formed by mixing a curing agent 1 and a curing agent 2 in a mixing ratio of 2: 1-5: 1;
the curing agent 1 is selected from one of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate or tetramethyl m-xylylene diisocyanate;
the curing agent 2 is one selected from isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, cyclohexanedimethylene diisocyanate or methylcyclohexyl diisocyanate;
the elastic organic particles are selected from one of polyurethane particles, nylon particles or polybutyl acrylate particles;
the modified polyol resin is LCR-100 series of NATOCO, HFC-PNS1 series of HARIMA or TRE-2-S2 series of ASIA.
2. The matte finish protective film according to claim 1, wherein the reactive leveling agent is a hydroxyl-containing modified polysiloxane.
3. The matte finish protective film according to claim 1, wherein the metal drier is one of an organic tin drier, an organic bismuth drier or a rare earth drier.
4. The matte finish protective film according to claim 1, wherein the thickness of the self-repair layer is 5 to 30 μm.
5. The matte-finish protective film according to claim 1, wherein the transparent support is a polyvinyl chloride film or a thermoplastic polyurethane film having a thickness of 100 to 300 μm.
6. The matte paint protective film according to claim 1, wherein the transparent protective film is a polyester protective film having a thickness of 30 to 100 μm, and the translucent release film is a polyester release film having a thickness of 30 to 100 μm.
7. The matte finish protective film according to claim 1, wherein the assembly glue is a polyurethane or polyacrylate pressure-sensitive glue with a thickness of 10 μm to 50 μm.
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| CN110484103B (en) * | 2019-08-12 | 2021-08-06 | 广东歌丽斯化学有限公司 | Polyester elastic super-soft matte roller coating paint and preparation method and application thereof |
| CN110484102B (en) * | 2019-08-12 | 2021-08-06 | 广东歌丽斯化学有限公司 | Polyester oxidized pearl roller coating paint and preparation method and application thereof |
| CN110616049B (en) * | 2019-09-29 | 2021-09-24 | 广东鑫瑞新材料科技有限公司 | Frosted matte invisible paint surface protective film and preparation method thereof |
| CN111073535A (en) * | 2019-12-27 | 2020-04-28 | 昆山乐凯锦富光电科技有限公司 | Automobile surface protection film capable of preventing raindrops from being stained |
| CN112358805A (en) * | 2020-11-11 | 2021-02-12 | 卡秀万辉(无锡)高新材料有限公司 | High-transparency anode-like particle anti-scratching UV coating and preparation method and application thereof |
| CN114349929A (en) * | 2021-12-31 | 2022-04-15 | 广东粤港澳大湾区黄埔材料研究院 | Anti-yellowing high-transparency invisible car cover and preparation method thereof |
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| CN104072976A (en) * | 2013-03-26 | 2014-10-01 | 富士施乐株式会社 | Surface protection film |
| KR20170084518A (en) * | 2016-01-12 | 2017-07-20 | 주식회사 퍼시픽에프엔씨 | Method for preparing soft feel type self-healing film and soft feel type self-healing film |
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