CN104774572A - Protective film for automobile and preparation method thereof - Google Patents
Protective film for automobile and preparation method thereof Download PDFInfo
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- CN104774572A CN104774572A CN201510083195.5A CN201510083195A CN104774572A CN 104774572 A CN104774572 A CN 104774572A CN 201510083195 A CN201510083195 A CN 201510083195A CN 104774572 A CN104774572 A CN 104774572A
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Abstract
The invention relates to a protective film for an automobile and a preparation method thereof. The protective film for the automobile successively comprises a PVC film, an acrylic adhesive and release paper. The acrylic adhesive is an anti-rapture and pressure-sensitive adhesive which is prepared through copolymerization of functional monomer, soft monomer and hard monomer, wherein polytetrahydrofuran acrylate is used as the functional monomer. Since the polytetrahydrofuran acrylate monomer has a long carbon chain of an ether bond, the anti-rapture and pressure-sensitive adhesive can well withstand tensile failure, and fracture of the adhesive in the processes of drawing and bending can be prevented; thus, the protective film for the automobile can be perfectly applied to the field of film pasting of automobiles.
Description
Technical field
The present invention relates to a kind of lacquer painting protective membrane and preparation method thereof, particularly relate to a kind of anti-scratch lacquer painting protective membrane and preparation method thereof.
Background technology
Since being born from automobile, the step that the mankind pursue automobile maintenance never stops.In order to make love car bright as new all the time, people design a lot of ways, and the waxing that the brightness of raising lacquer painting, minimizing lacquer painting damage has been born.In order to pursue more permanent, effective protected effect, there is the appearance of envelope glaze, coating technique.But along with the prosperity of science and technology, we also get more and more to the requirement of body of a motor car maintenance, easier, more practical, more fashion, so body paint mask is also just taken advantage of a situation and raw.
Pressure-sensitive adhesive is that a class is to pressure-sensitive sizing agent, only need apply certain pressure and just also can produce a class tackiness agent of bonding strength in the moistening adherend surface of energy, be characterized in sticky easy, that takes off is not difficult, shell and do not damage, glue-line can not be solid in a long time, so pressure sensitive adhesive is also referred to as non-setting adhesive, it is of wide application.Because automobile adhesive film is in the process of pasting, lacquer painting is not plane, the situation that the pressure sensitive adhesive existence on pad pasting stretches, and pressure sensitive adhesive exists the possibility of disconnected glue in the process stretched, and just has a strong impact on cohesiveness and the transparency of pad pasting.
Summary of the invention
The object of this invention is to provide a kind of protection film for automobile and preparation method thereof, protection film for automobile composition is followed successively by by PVC film, acrylate glue and separate-type paper, acrylate glue is a kind of anti-disconnected glue pressure sensitive adhesive, for function monomer with vinylformic acid polytetrahydrofuran ester, obtain with soft monomer and hard monomer copolymerization, vinylformic acid polytetrahydrofuran ester monomer has the Long carbon chain of ehter bond, flexible relatively good, the anti-disconnected glue pressure sensitive adhesive of gained can be good at resisting tension fracture, be conducive to the fracture etc. preventing glue in bending stretch process, thus protection film for automobile of the present invention can well be applied and automobile adhesive film field.
A kind of protection film for automobile; composition is followed successively by by PVC film, acrylate glue and separate-type paper, it is characterized in that: described acrylate glue is anti-disconnected glue pressure sensitive adhesive, obtains primarily of soft monomer, hard monomer and function monomer copolymerization; described function monomer is vinylformic acid polytetrahydrofuran ester, and its molecular structural formula is:
Wherein n=3 ~ 10;
Described anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 ~ 4.0 pounds/25mm.
A kind of protection film for automobile as above, described soft monomer is one or more in ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer; Described hard monomer is acrylamide.
A preparation method for protection film for automobile, is characterized in that comprising the following steps:
1) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of a, function monomer vinylformic acid polytetrahydrofuran ester;
PTMG is dissolved in methylene dichloride, is then added drop-wise in vinylformic acid acyl chlorides and reacts, generate vinylformic acid polytetrahydrofuran ester;
The preparation of b, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer and hard monomer are dissolved in a solvent, then add in reactor by 1/3rd of mixing solutions, be warming up to 70 ~ 90 DEG C, add initiator, then drip remaining mixing solutions, dropwise in 2 ~ 3h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.5 ~ 1h, after continuing reaction 1 ~ 2h, is cooled to room temperature; Add linking agent to stir, discharging, disconnected glue pressure sensitive adhesive must be resisted;
2) preparation of anti-disconnected shellac varnish surface protective film;
At the anti-disconnected glue pressure sensitive adhesive of PVC film single spreading, dry, last and separate-type paper carries out pressing.
The preparation method of a kind of protection film for automobile as above, in step a, the number-average molecular weight of PTMG is 600 ~ 2000; The PTMG concentration be dissolved in methylene dichloride is 20 ~ 30wt%; Bark the mutter mol ratio of ether glycol and vinylformic acid acyl chlorides of poly-tetrahydrochysene is 1 ~ 1.3:1; Temperature of reaction is 10 ~ 30 DEG C, and reaction times 2 ~ 3h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying.
The preparation method of a kind of protection film for automobile as above, in step b, described initiator is azo-bis-isobutyl cyanide or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described linking agent is polyisocyanates; Described solvent is ethyl acetate.
The preparation method of a kind of protection film for automobile as above, is characterized in that, step 2) in, described coating resists the amount of disconnected glue pressure sensitive adhesive to be 40 ~ 60g/m
2, bake out temperature is 40 ~ 120 DEG C, and drying time is 8 ~ 12min.
Beneficial effect:
A kind of protection film for automobile and preparation method thereof; protection film for automobile composition is followed successively by by PVC film, acrylate glue and separate-type paper; acrylate glue is a kind of anti-disconnected glue pressure sensitive adhesive; for function monomer with vinylformic acid polytetrahydrofuran ester; obtain with soft monomer and hard monomer copolymerization; vinylformic acid polytetrahydrofuran ester monomer has the Long carbon chain of ehter bond; flexible relatively good; the anti-disconnected glue pressure sensitive adhesive of gained can be good at resisting tension fracture; be conducive to the fracture etc. preventing glue in bending stretch process, thus protection film for automobile of the present invention can well be applied and automobile adhesive film field.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
A kind of protection film for automobile of the present invention; composition is followed successively by by PVC film, acrylate glue and separate-type paper; acrylate glue is anti-disconnected glue pressure sensitive adhesive; obtain primarily of one or more in soft monomer ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, hard monomer acrylamide and function monomer copolymerization; function monomer is vinylformic acid polytetrahydrofuran ester, and its molecular structural formula is:
Wherein n=3 ~ 10;
Anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 ~ 4.0 pounds/25mm.
Embodiment 1
A preparation method for protection film for automobile, comprises the following steps:
1) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of a, function monomer vinylformic acid polytetrahydrofuran ester;
Be that 600 PTMG are dissolved in methylene dichloride by number-average molecular weight, be then added drop-wise in vinylformic acid acyl chlorides and react, the PTMG concentration be dissolved in methylene dichloride is 20wt%; Bark the mutter mol ratio of ether glycol and vinylformic acid acyl chlorides of poly-tetrahydrochysene is 1:1; Temperature of reaction is 10 DEG C, and reaction times 2h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=3;
The preparation of b, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer ethyl propenoate and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 70 DEG C, add initiator azo-bis-isobutyl cyanide, then drip remaining mixing solutions, dropwise in 2h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.5h, after continuing reaction 1h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 pounds/25mm;
2) preparation of protection film for automobile;
At the anti-disconnected glue pressure sensitive adhesive of PVC film single spreading, the amount of the anti-disconnected glue pressure sensitive adhesive of coating is 40g/m
2, dry, bake out temperature is 40 DEG C, and drying time is 8min, and last and separate-type paper carries out pressing.
Embodiment 2
A preparation method for protection film for automobile, comprises the following steps:
1) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of a, function monomer vinylformic acid polytetrahydrofuran ester;
Be that 2000 PTMG are dissolved in methylene dichloride by number-average molecular weight, be then added drop-wise in vinylformic acid acyl chlorides and react, the PTMG concentration be dissolved in methylene dichloride is 30wt%; Bark the mutter mol ratio of ether glycol and vinylformic acid acyl chlorides of poly-tetrahydrochysene is 1.3:1; Temperature of reaction is 30 DEG C, and reaction times 3h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=10;
The preparation of b, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer butyl acrylate and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 90 DEG C, add initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), then drip remaining mixing solutions, dropwise in 3h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 1h, after continuing reaction 2h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 4.0 pounds/25mm;
2) preparation of protection film for automobile;
At the anti-disconnected glue pressure sensitive adhesive of PVC film single spreading, the amount of the anti-disconnected glue pressure sensitive adhesive of coating is 60g/m
2, dry, bake out temperature is 120 DEG C, and drying time is 12min, and last and separate-type paper carries out pressing.
Embodiment 3
A preparation method for protection film for automobile, comprises the following steps:
1) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of a, function monomer vinylformic acid polytetrahydrofuran ester;
Be that 1000 PTMG are dissolved in methylene dichloride by number-average molecular weight, be then added drop-wise in vinylformic acid acyl chlorides and react, the PTMG concentration be dissolved in methylene dichloride is 25wt%; Bark the mutter mol ratio of ether glycol and vinylformic acid acyl chlorides of poly-tetrahydrochysene is 1.1:1; Temperature of reaction is 20 DEG C, and reaction times 2.5h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=4;
The preparation of b, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer Isooctyl acrylate monomer and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 75 DEG C, add initiator azo-bis-isobutyl cyanide, then drip remaining mixing solutions, dropwise in 2.5h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.6h, after continuing reaction 1.5h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.5 pounds/25mm;
2) preparation of protection film for automobile;
At the anti-disconnected glue pressure sensitive adhesive of PVC film single spreading, the amount of the anti-disconnected glue pressure sensitive adhesive of coating is 45g/m
2, dry, bake out temperature is 80 DEG C, and drying time is 9min, and last and separate-type paper carries out pressing.
Embodiment 4
A preparation method for protection film for automobile, comprises the following steps:
1) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of a, function monomer vinylformic acid polytetrahydrofuran ester;
Be that 1200 PTMG are dissolved in methylene dichloride by number-average molecular weight, be then added drop-wise in vinylformic acid acyl chlorides and react, the PTMG concentration be dissolved in methylene dichloride is 22wt%; Bark the mutter mol ratio of ether glycol and vinylformic acid acyl chlorides of poly-tetrahydrochysene is 1.2:1; Temperature of reaction is 15 DEG C, and reaction times 2.2h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=5;
The preparation of b, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Wherein the mass ratio of ethyl propenoate and butyl acrylate is 1:1;
Soft monomer ethyl propenoate and butyl acrylate and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 78 DEG C, add initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), then drip remaining mixing solutions, dropwise in 2h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.8h, after continuing reaction 2h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.5 pounds/25mm;
2) preparation of protection film for automobile;
At the anti-disconnected glue pressure sensitive adhesive of PVC film single spreading, the amount of the anti-disconnected glue pressure sensitive adhesive of coating is 42g/m
2, dry, bake out temperature is 100 DEG C, and drying time is 10min, and last and separate-type paper carries out pressing.
Embodiment 5
A preparation method for protection film for automobile, comprises the following steps:
1) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of a, function monomer vinylformic acid polytetrahydrofuran ester;
Be that 1100 PTMG are dissolved in methylene dichloride by number-average molecular weight, be then added drop-wise in vinylformic acid acyl chlorides and react, the PTMG concentration be dissolved in methylene dichloride is 26wt%; Bark the mutter mol ratio of ether glycol and vinylformic acid acyl chlorides of poly-tetrahydrochysene is 1:1; Temperature of reaction is 30 DEG C, and reaction times 2h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=6;
The preparation of b, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Wherein the mass ratio of ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer is 2:1:1;
Soft monomer ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 75 DEG C, add initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), then drip remaining mixing solutions, dropwise in 2h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 1h, after continuing reaction 2h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.8 pounds/25mm;
2) preparation of protection film for automobile;
At the anti-disconnected glue pressure sensitive adhesive of PVC film single spreading, the amount of the anti-disconnected glue pressure sensitive adhesive of coating is 50g/m
2, dry, bake out temperature is 90 DEG C, and drying time is 8min, and last and separate-type paper carries out pressing.
Embodiment 6
A preparation method for protection film for automobile, comprises the following steps:
1) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of a, function monomer vinylformic acid polytetrahydrofuran ester;
Be that 1800 PTMG are dissolved in methylene dichloride by number-average molecular weight, be then added drop-wise in vinylformic acid acyl chlorides and react, the PTMG concentration be dissolved in methylene dichloride is 26wt%; Bark the mutter mol ratio of ether glycol and vinylformic acid acyl chlorides of poly-tetrahydrochysene is 1.1:1; Temperature of reaction is 10 DEG C, and reaction times 3h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=8;
The preparation of b, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Wherein the mass ratio of butyl acrylate and Isooctyl acrylate monomer is 1:2;
Soft monomer butyl acrylate and Isooctyl acrylate monomer and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 88 DEG C, add initiator azo-bis-isobutyl cyanide, then drip remaining mixing solutions, dropwise in 2.8h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.8h, after continuing reaction 1h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 4.0 pounds/25mm;
2) preparation of protection film for automobile;
At the anti-disconnected glue pressure sensitive adhesive of PVC film single spreading, the amount of the anti-disconnected glue pressure sensitive adhesive of coating is 60g/m
2, dry, bake out temperature is 110 DEG C, and drying time is 11min, and last and separate-type paper carries out pressing.
Claims (6)
1. a protection film for automobile; composition is followed successively by by PVC film, acrylate glue and separate-type paper, it is characterized in that: described acrylate glue is anti-disconnected glue pressure sensitive adhesive, obtains primarily of soft monomer, hard monomer and function monomer copolymerization; described function monomer is vinylformic acid polytetrahydrofuran ester, and its molecular structural formula is:
Wherein n=3 ~ 10;
Described anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 ~ 4.0 pounds/25mm.
2. a kind of protection film for automobile according to claim 1, is characterized in that, described soft monomer is one or more in ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer; Described hard monomer is acrylamide.
3. a preparation method for protection film for automobile, is characterized in that comprising the following steps:
1) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of a, function monomer vinylformic acid polytetrahydrofuran ester;
PTMG is dissolved in methylene dichloride, is then added drop-wise in vinylformic acid acyl chlorides and reacts, generate vinylformic acid polytetrahydrofuran ester;
The preparation of b, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer and hard monomer are dissolved in a solvent, then add in reactor by 1/3rd of mixing solutions, be warming up to 70 ~ 90 DEG C, add initiator, then drip remaining mixing solutions, dropwise in 2 ~ 3h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.5 ~ 1h, after continuing reaction 1 ~ 2h, is cooled to room temperature; Add linking agent to stir, discharging, disconnected glue pressure sensitive adhesive must be resisted;
2) preparation of protection film for automobile;
At the anti-disconnected glue pressure sensitive adhesive of PVC film single spreading, dry, last and separate-type paper carries out pressing.
4. the preparation method of a kind of protection film for automobile according to claim 3, is characterized in that, in step a, the number-average molecular weight of PTMG is 600 ~ 2000; The PTMG concentration be dissolved in methylene dichloride is 20 ~ 30wt%; Bark the mutter mol ratio of ether glycol and vinylformic acid acyl chlorides of poly-tetrahydrochysene is 1 ~ 1.3:1; Temperature of reaction is 10 ~ 30 DEG C, and reaction times 2 ~ 3h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying.
5. the preparation method of a kind of protection film for automobile according to claim 3, is characterized in that, in step b, described initiator is azo-bis-isobutyl cyanide or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described linking agent is polyisocyanates; Described solvent is ethyl acetate.
6. the preparation method of a kind of protection film for automobile according to claim 3, is characterized in that, step 2) in, described coating resists the amount of disconnected glue pressure sensitive adhesive to be 40 ~ 60g/m
2, bake out temperature is 40 ~ 120 DEG C, and drying time is 8 ~ 12min.
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| CN201510083195.5A CN104774572B (en) | 2015-02-15 | 2015-02-15 | A kind of protection film for automobile and preparation method thereof |
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| CN111992477A (en) * | 2020-08-06 | 2020-11-27 | 东风汽车集团有限公司 | Method for manufacturing automobile logo |
| CN114621710A (en) * | 2020-12-10 | 2022-06-14 | 安佐化学有限公司 | Adhesive for invisible car cover and preparation method and application thereof |
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| CN106381085A (en) * | 2016-11-04 | 2017-02-08 | 太仓金煜电子材料有限公司 | Polyvinyl chloride protection film and production method thereof |
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| Publication number | Publication date |
|---|---|
| CN104774572B (en) | 2017-07-14 |
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