CN115386309B - Organic silicon protective film for electronic product and preparation method thereof - Google Patents

Organic silicon protective film for electronic product and preparation method thereof Download PDF

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Publication number
CN115386309B
CN115386309B CN202111268674.6A CN202111268674A CN115386309B CN 115386309 B CN115386309 B CN 115386309B CN 202111268674 A CN202111268674 A CN 202111268674A CN 115386309 B CN115386309 B CN 115386309B
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polysiloxane
adhesive
protective film
adhesive layer
layer
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CN115386309A (en
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何森财
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Guangdong Donlee New Materials Technology Lncorporated Co
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Guangdong Donlee New Materials Technology Lncorporated Co
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/25Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255Polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/10Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00Presence of polyester
    • C09J2467/006Presence of polyester in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to C09J7/38, in particular to an organic silicon protective film for electronic products and a preparation method thereof. The adhesive layer is used for connecting the substrate layer and the release film; the adhesive layer preparation raw material comprises a raw material with a weight average molecular weight of 7-10 3 ‑6*10 5 The polysiloxane of (C), a silicon hydrogen cross-linking agent, a binder, a catalyst and a solvent. The invention discloses an organosilicon protective film for electronic products, which has excellent initial adhesion and holding adhesion, is easy to attach, does not warp, has good ageing resistance and solvent resistance, is suitable for protecting electronic products, and is especially suitable for protecting curved window glass.

Description

Organic silicon protective film for electronic product and preparation method thereof
Technical Field
The invention relates to C09J7/38, in particular to an organic silicon protective film for electronic products and a preparation method thereof.
Background
The surfaces of electronic products such as a display, a tablet computer, a mobile phone, a digital camera and the like are usually protected by adopting a mode of sticking a protective film, and particularly in the current electronic consumer market, a 3D curved surface window panel becomes the main stream, no matter the manufacturing process or the product faces a consumer, the surfaces of the electronic product windows need to be stuck with the protective film to prevent surface pollution or scratch, but the existing protective film has weak cohesiveness, poor aging resistance, easy warping and cannot be effectively protected.
The wear-resistant silica gel protective film for the curved surface screen of the patent CN201811418327.5 has the advantages that the thermoplastic polyurethane film is adopted as a base material, and substances such as N-hydroxy N-octylamide and the like are added to improve the coating property and the warping problem.
The patent CN201911235140.6 discloses a protection film applied to a curved screen mobile phone, which is used for buffering the tilting stress through a PET and TPU composite film and solving the problem of tilting of the edge.
However, the above-mentioned technique does not solve the problem of aging resistance, and the protective film may still rise with time. Meanwhile, the existing protective film has poor solvent resistance, and residual glue is easy to generate during stripping.
Disclosure of Invention
In order to solve the technical problems, a first aspect of the invention provides an organic silicon protective film for an electronic product, which comprises a substrate layer, an adhesive layer and a release layer, wherein the substrate layer and the release layer are arranged betweenConnecting through an adhesive layer; the adhesive layer preparation raw material comprises a raw material with a weight average molecular weight of 7-10 3 -6*10 5 The polysiloxane of (C), a silicon hydrogen cross-linking agent, a binder, a catalyst and a solvent.
Preferably, the weight average molecular weight is 7 x 10 3 -6*10 5 Comprises a first polysiloxane and a second polysiloxane. The mass ratio of the first polysiloxane to the second polysiloxane is (1.2-1.7): (2-2.5).
Preferably, the weight average molecular weight of the first polysiloxane is 8000 to 15000.
Further preferably, the vinyl content of the first polysiloxane is 2.5 to 3% and the M/Q ratio is 0.60 to 0.80.
Preferably, the polysiloxane is vinyl silicone resin prepared by cohydrolysis of tetraalkoxysilane and dimethylethoxysilane.
Preferably, the second polysiloxane has a weight average molecular weight of 4.5 x 10 5 -5.9*10 5
Because of the application of the D curved surface window panel, the organic silicon protective film is difficult to combine with the actual shape of the electronic product, and the phenomenon of warping easily occurs, so that an effective protective effect cannot be effectively provided for the electronic product. According to the invention, unexpected researches show that by compounding polysiloxanes with different molecular weights, the molecular chain combination between the systems is tighter, the formation of a sea-island structure is promoted, the attraction between the system and molecules of an adherend is enhanced, and the initial adhesion, the holding adhesion and the peeling strength of the organosilicon protective film are improved; especially when the mass ratio of the first polysiloxane to the second polysiloxane is (1.2-1.7): (2-2.5) it is possible to avoid the effect of the silicone protective film on the adherend from being affected by excessive polysiloxane content having a large molecular weight.
Preferably, the hydrogen content of the hydrosilylation cross-linking agent is 0.02-0.05%.
Preferably, in the polysiloxane, the hydrosilylation cross-linking agent, n (Si-H): n (Si-Vi) is 0.45 to 0.6.
Preferably, the binder is an epoxy binder.
Preferably, the epoxy equivalent of the binder is 0.48-0.54.
Preferably, the viscosity of the binder is less than or equal to 2500 at 40 ℃.
Preferably, the mass ratio of the polysiloxane to the binder is 100: (0.5-1.5).
It has been found that the silicone adhesive is susceptible to electrophilic or nucleophilic agents due to the large polarity of the Si-O bond, resulting in poor adhesion and solvent resistance. According to the invention, unexpected researches show that the adhesive and polysiloxane are compounded to effectively improve the adhesive force and solvent resistance of the organosilicon protective film. It is supposed that the reaction between the active group contained in the organosilicon and the epoxy resin generates Si-O-Si molecular chain, which enhances the winding action of chain segment, shortens the curing time, forms a more compact network structure, prevents small molecules from entering and effectively prevents the invasion of solvent.
Preferably, the catalyst is a platinum-based catalyst.
Preferably, the effective platinum content in the platinum-series catalyst is 4000-5500PPM.
Preferably, the effective platinum content of the platinum-series catalyst accounts for 0.8 x 10 of the total mass of the raw materials for preparing the adhesive layer -6 -1.2*10 -6 %。
Preferably, the solvent comprises at least one of ethyl acetate, butyl acetate, isopropanol, and acetone.
Further preferably, the solvent is ethyl acetate.
Preferably, the solvent accounts for 1-2wt% of the total mass of the adhesive layer preparation raw material.
Further preferably, the raw material further comprises a silane coupling agent.
Preferably, the silane coupling agent accounts for 0.5-1% of the total weight of the adhesive layer preparation raw material.
Preferably, the silane coupling agent includes gamma-glycidoxypropyl trimethoxysilane and gamma-aminopropyl triethoxysilane. The mass ratio of the gamma-glycidoxypropyl trimethoxysilane (KH 560) to the gamma-aminopropyl triethoxysilane (KH 550) is (1.7-2.3) (0.8-1.2).
Preferably, the substrate layer is a PET film.
Preferably, the thickness of the substrate layer is 40-60um.
Preferably, the thickness of the adhesive layer is 40-80um.
Preferably, the release layer is a fluorine release film, and the thickness of the release layer is 25-35um.
The second aspect of the present invention provides a method for preparing an organic silicon protective film for an electronic product, comprising the steps of:
(1) Weighing the raw materials according to the formula, and putting the raw materials into a high-speed stirrer to be uniformly mixed to obtain an adhesive;
(2) Corona treatment is carried out on the substrate layer, a micro gravure coating method is adopted, the adhesive is uniformly coated on the substrate layer at a speed of 15m/min under the dust-free condition, and the adhesive layer is obtained through drying and curing at the temperature of 100-120 ℃;
(3) And unreeling the release layer on the adhesive layer, and reeling to obtain the organic silicon protective film for the electronic product.
The beneficial effects are that:
the existing electronic products are easy to warp, fall off and have residual glue, and have poor ageing resistance and solvent resistance. The invention sequentially comprises a substrate layer, an adhesive layer and a release layer, and by compounding polysiloxanes with different molecular weights, the adhesive is promoted to form a sea-island structure, and meanwhile, the adhesive interacts with the epoxy adhesive and the silane coupling agent, so that the winding among chain segments is enhanced to form a more compact reticular structure, the initial viscosity and the holding viscosity of the pressure-sensitive adhesive are improved, the pressure-sensitive adhesive has higher peel strength, is easy to attach and not warp, the adhesive layer is crosslinked more fully, the ageing resistance and the solvent resistance are enhanced, the silicon transfer is effectively avoided, and the adhesive is suitable for protecting electronic products, and is especially suitable for protecting curved surface window glass.
Detailed Description
Examples
Example 1
The organic silicon protective film for the electronic product comprises a substrate layer, an adhesive layer and a release film, wherein the substrate layer and the release film are connected through the adhesive layer; the adhesive layer preparation raw material comprises a raw material with a weight average molecular weight of 7-10 3 -6*10 5 Is a poly (A) of (B)Siloxane, a hydrosilylation cross-linking agent, a binder, a catalyst and a solvent.
The weight average molecular weight is 7 x 10 3 -6*10 5 Comprises a first polysiloxane and a second polysiloxane. The weight average molecular weight of the first polysiloxane is 8000-15000. The mass ratio of the first polysiloxane to the second polysiloxane is 1.5:2.3.
the vinyl content of the first polysiloxane is 2.5-3%, and the ratio of M/Q (dimethylethoxysilane units/tetraalkoxysilane units) is 0.60-0.80. The polysiloxane is vinyl silicone resin prepared by co-hydrolysis of tetraalkoxysilane and dimethylethoxysilane, and is purchased from Shanghai banquet new material science and technology Co-Ltd, model: YDSR9070.
The weight average molecular weight of the second polysiloxane is 4.5 x 10 5 -5.9*10 5 . The second polysiloxane is methyl terminated silicone rubber, and the second polysiloxane is purchased from Ningpo if silicone limited company, model: DR-110-3.
The hydrogen content of the silicon hydrogen cross-linking agent is 0.03%. The silicon hydrogen cross-linking agent is hydrogen-containing silicone oil, and is purchased from Shanghai silicon friend new material science and technology Co. The polysiloxane, in the hydrosilylation cross-linking agent, n (Si-H): n (Si-Vi) is 0.55.
The adhesive is an epoxy adhesive. The epoxy equivalent of the adhesive is 0.48-0.54. The viscosity of the binder is less than or equal to 2500 at 40 ℃. Purchased from tin-free chemical industry limited, model: CGE628. The mass ratio of the polysiloxane to the binder is 100:1.
the catalyst is a platinum-based catalyst. The effective platinum content in the platinum-series catalyst is 5000PPM. The platinum-based catalyst is purchased from the rubber plastic material limited company of Miteng, dongguan, and the effective platinum content of the platinum-based catalyst accounts for 1 x 10 of the total mass of the preparation raw materials of the adhesive layer -6 %。
The solvent is ethyl acetate. The solvent accounts for 1.4wt% of the total mass of the adhesive layer preparation raw material.
The raw materials also comprise a silane coupling agent. The silane coupling agent comprises gamma-glycidyl ether oxypropyl trimethoxy silane and gamma-aminopropyl triethoxy silane. The mass ratio of the gamma-glycidoxypropyl trimethoxysilane (KH 560) to the gamma-aminopropyl triethoxysilane (KH 550) is 2:1. The silane coupling agent accounts for 0.8 percent of the total weight of the preparation raw materials of the adhesive layer.
The substrate layer is a PET film. The thickness of the substrate layer was 50um.
The thickness of the adhesive layer is 70um.
The release layer is a fluorine release film, and the thickness of the release layer is 30um.
The PET film and the fluorine release film are both purchased from Shenzhen Gusaino technology Co.
A preparation method of an organic silicon protective film for electronic products comprises the following steps:
(1) Weighing the raw materials according to the formula, and putting the raw materials into a high-speed stirrer to be uniformly mixed to obtain an adhesive;
(2) Corona treatment is carried out on the substrate layer, a miniature gravure coating method is adopted, an adhesive is uniformly coated on the substrate layer at a speed of 15m/min under a dust-free condition, and the adhesive layer is obtained after drying and curing under a temperature of 115 ℃;
(3) And unreeling the release layer on the adhesive layer, and reeling to obtain the organic silicon protective film for the electronic product.
Example 2
An organosilicon protective film for electronic products, the specific implementation mode is the same as example 1, wherein the polysiloxane and the silicon hydride crosslinking agent are n (Si-H): n (Si-Vi) is 0.6.
Example 3
An organosilicon protective film for electronic products is provided, which is different from example 1 in that the mass ratio of the gamma-glycidoxypropyl trimethoxysilane (KH 560) to the gamma-aminopropyl triethoxysilane (KH 550) is 1.7:0.8.
Comparative example 1
The organic silicon protective film for electronic products is different from example 1 in specific embodiments in that the mass ratio of the first polysiloxane to the second polysiloxane is 1.5:4.
comparative example 2
The organic silicon protective film for electronic products is different from example 1 in specific implementation mode, and the mass ratio of polysiloxane to binder is 100:0.3.
performance testing
1.180 ° peel strength test: the test was carried out in accordance with GB/T2792-1998. 25-30 g/25mm
2. Solvent resistance test: the pressure sensitive adhesive was cut into 25mm 50mm specimens, stuck to a stainless steel plate, immersed in a toluene-filled container for 30min, and tested for peel strength.
3. Aging resistance test: and (3) attaching the protective film on a clean window glass working surface, placing the protective film in a constant temperature and humidity test box, testing according to specified test conditions, and after the test is ended, testing and checking the tested sample. Test conditions: temperature: 60 ℃, humidity: 90% rh, time: 72h.
TABLE 1 Performance test results
TABLE 2 ageing resistance test results
Aging resistance
Example 1 No phenomena of glue overflow, bubbles, falling, residual glue and dirt
Example 2 No phenomena of glue overflow, bubbles, falling, residual glue and dirt
Example 3 No phenomena of glue overflow, bubbles, falling, residual glue and dirt
Comparative example 1 Has the phenomena of glue overflow, bubbles, falling, residual glue and dirt
Comparative example 2 Has the phenomena of glue overflow, bubbles, falling, residual glue and dirt

Claims (3)

1. The organic silicon protective film for the electronic product is characterized by comprising a substrate layer, an adhesive layer and a release layer, wherein the substrate layer and the release layer are connected through the adhesive layer; the adhesive layer is prepared from raw materials with a weight average molecular weight of 7×10 3 -6×10 5 A silicone, a hydrosilylation cross-linking agent, a binder, a catalyst, a silane coupling agent, and a solvent;
the weight average molecular weight is 7×10 3 -6×10 5 Comprises a first polysiloxane and a second polysiloxane, and the mass ratio of the first polysiloxane to the second polysiloxane is 1.5:2.3;
the first polysiloxane is a product with the model number of YDSR9070 manufactured by Shanghai Di New Material technology Co., ltd, and the weight average molecular weight is 8000-15000;
the second polysiloxane is a product of Ningchang if the model DR-110-3 is manufactured by organosilicon Co., ltd, and has a weight average molecular weight of 4.5X10 5 -5.9×10 5
The hydrogen content of the silicon-hydrogen crosslinking agent is 0.03%, and the silicon-hydrogen crosslinking agent is hydrogen-containing silicone oil;
the polysiloxane, in the hydrosilylation cross-linking agent, n (Si-H): n (Si-Vi) is 0.55;
the adhesive is an epoxy resin adhesive, and the epoxy equivalent is 0.48-0.54; the viscosity of the adhesive at 40 ℃ is less than or equal to 2500; the mass ratio of the polysiloxane to the binder is 100:1, a step of;
the catalyst is a platinum catalyst; the effective platinum content in the platinum-series catalyst is 5000 PPM;
the silane coupling agent is prepared by compounding KH560 and KH550 in a mass ratio of 2:1.
2. The silicone protective film for electronic products according to claim 1, wherein the thickness of the adhesive layer is 40-80 μm.
3. A method for producing an organosilicon protective film for electronic products according to any one of claims 1 to 2, characterized by comprising the steps of:
(1) Weighing the raw materials according to the formula, and putting the raw materials into a high-speed stirrer to be uniformly mixed to obtain an adhesive;
(2) Corona treatment is carried out on the substrate layer, a micro gravure coating method is adopted, adhesive is uniformly coated on the substrate layer at a speed of 15m/min under the dust-free condition, and the adhesive layer is obtained after drying and curing at 100-120 ℃;
(3) And unreeling the release layer on the adhesive layer, and reeling to obtain the organic silicon protective film for the electronic product.
CN202111268674.6A 2021-10-29 2021-10-29 Organic silicon protective film for electronic product and preparation method thereof Active CN115386309B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108753187A (en) * 2018-04-19 2018-11-06 广东东立新材料科技股份有限公司 A kind of silicone protective film and preparation method thereof for touch screen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108753187A (en) * 2018-04-19 2018-11-06 广东东立新材料科技股份有限公司 A kind of silicone protective film and preparation method thereof for touch screen

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