CN109705383B - Anti-static film - Google Patents
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Abstract
The antistatic film comprises a base material and an antistatic layer coated on at least one surface of the base material, wherein the antistatic layer and the base material are synchronously stretched transversely and then are shaped to obtain the antistatic film, and after improvement, the antistatic layer is prepared from the following raw materials in percentage by weight: 5-25% of aqueous carbon nanotube dispersion, 2-10% of lithium salt, 3-5% of aqueous polyurethane resin, 0.1-2% of cross-linking agent, 0.01-0.1% of wetting agent and 58-86% of deionized water. The surface resistance of the antistatic layer of the antistatic film prepared by the invention can reach 10 by utilizing the synergistic effect of the lithium salt and the water-based carbon nano tube under the online coating process4Ω～105Omega, the antistatic layer forms a silicon oil layer after being coated with silicon oil subsequently, and the surface resistance of the silicon oil layer can reach 104Ω～108Omega. The antistatic film has excellent and stable antistatic property and subsequent processability, and can be widely applied to the fields of release films and the like.
Description
Technical Field
The invention relates to the technical field of films, in particular to an anti-static film which can be applied to subsequent processing of a release film.
Background
Optical films in liquid crystal display screens are more and more widely applied, and the films are polluted due to electrostatic action in the transportation and deep processing processes of the optical films, so that various defects are generated in the deep processing process, and the overall quality of the optical films is influenced. Therefore, an anti-static protective film needs to be coated on the surface of the optical film.
At present, the antistatic film can be divided into an internal addition type and a coating type, wherein the coating type antistatic film has two coating processes, one is off-line coating, and the other is on-line coating. Because the resistance value of the online coating antistatic film is higher and the application range is limited, the offline coating antistatic film is widely applied. The online coating of the anti-static film is to coat the anti-static coating liquid on the surface of the film in the film manufacturing process, but on one hand, the coating thickness is limited, and the coating thickness is low, generally dozens of nanometers; on the other hand, after coating, the coating needs to be stretched by 3-5 times, so that the antistatic performance is weakened or disappears, and the requirement on the performance of the coating is high. Therefore, most of the antistatic films applied to the industries of release films and protective films are prepared by an offline process.
The antistatic materials on the market are mainly polythiophene type and ammonium salt. After the waterborne polythiophene conductive material is coated and stretched on line, the antistatic performance is weakened or disappears, so that the waterborne polythiophene conductive material is mainly applied to an off-line coating process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an antistatic film which is prepared by utilizing the synergistic effect of lithium salt and water-based carbon nano tubes under the online coating process, and the surface resistance of the antistatic film can reach 104Ω～105Omega, thereby making up the respective defects of lithium salt and water-based carbon nano tube, the antistatic performance is excellent, the water-based environment is protected, the subsequent processing performance is good, and the surface resistance of the silicon oil layer of the prepared antistatic film can reach 10 after the prepared antistatic film is coated with silicon oil in the subsequent procedures4Ω～108Omega, and the antistatic performance is stable and is not influenced by the environment.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the antistatic film comprises a base material and an antistatic layer coated on at least one surface of the base material, wherein the antistatic layer and the base material are synchronously stretched transversely and then are shaped to obtain the antistatic film, and the antistatic layer is prepared from the following raw materials in percentage by weight:
5 to 25 percent of aqueous carbon nanotube dispersion liquid
2 to 10 percent of lithium salt
3 to 5 percent of waterborne polyurethane resin
0.1 to 2 percent of cross-linking agent
0.01 to 0.1 percent of wetting agent
58 to 86 percent of deionized water.
In the antistatic film, the weight of the carbon nanotubes in the aqueous carbon nanotube dispersion liquid accounts for 0.5-1%, and the balance is water.
In the antistatic film, the water-based carbon nanotube is one or a combination of a single wall and multiple walls.
In the antistatic film, the cross-linking agent is melamine, azapyridine or oxazoline.
The above antistatic film, the wetting agent is a nonionic surface wetting agent, and the nonionic surface wetting agent can be polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block copolymer nonionic surfactant.
In the antistatic film, the lithium salt is lithium bis (fluorosulfonyl) imide or lithium trifluoromethanesulfonate.
In the antistatic film, the thickness of the antistatic layer is 0.08-0.2 μm.
The surface resistance of the antistatic film is between 10 under the humidity of 23 ℃ and 50% RH4Ω～105Ω。
The antistatic film is characterized in that silicone oil is coated on the surface of the antistatic film to form a silicone oil layer, and the surface resistance of the silicone oil layer is between 104Ω～108Ω。
The dry thickness of the silicon oil layer of the antistatic film is 0.01-5 mu m.
The preparation method of the antistatic film comprises the following steps:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, and casting on a rotating cooling roller; preheating the cooled casting sheet, and longitudinally stretching with the longitudinal stretching ratio of 3-5 times; coating the prepared antistatic coating liquid on one or two surfaces of the film subjected to longitudinal stretching in one of gravure coating, wire rod coating or dip coating modes; and heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 3-5 times, and then performing heat setting and rolling to obtain the antistatic film.
The invention has the beneficial effects that:
1. the surface resistance of the antistatic film prepared by the synergistic effect of the aqueous carbon nanotube dispersion and the lithium salt under the online coating process can reach 104Ω-105Ω。
2. The antistatic layer of the antistatic film is prepared by the invention, a silicon oil layer is formed after silicon oil is coated in the subsequent working procedure, and the surface resistance of the silicon oil layer is 104Ω-108Omega, and has stable antistatic property.
Drawings
Fig. 1 is a schematic view of an interlayer structure of an antistatic film.
The reference numerals in the figures denote: 1. film support, 2, antistatic layer.
Detailed Description
The film support of the present invention is nitrocellulose, cellulose triacetate or polyester, preferably polyester.
The thickness of the antistatic coating is 0.01-0.5 mu m, the thickness of the bottom layer is too small, the antistatic performance is weakened, and the later use effect is influenced; the thickness of the bottom layer is too large, the coating cost is increased, and the energy consumption of the production process is increased, so that the thickness of the bottom layer is preferably 0.08-0.2 μm.
The antistatic agent adopts the aqueous carbon nanotube dispersion liquid, the carbon nanotubes in the aqueous carbon nanotube dispersion liquid have an excellent antistatic function, the coating technical requirement is higher due to the higher viscosity of the carbon nanotubes, and when the weight ratio of the carbon nanotubes in the aqueous carbon nanotube dispersion liquid is too high, the viscosity is too high, the coating is difficult, and the coating appearance is greatly influenced; when the weight of the carbon nanotubes in the aqueous carbon nanotube dispersion is over the bottom, the antistatic effect is poor; in order to achieve excellent antistatic effect and good coating appearance, the weight ratio of the carbon nanotubes in the aqueous carbon nanotube dispersion is preferably 0.5 to 1%, and the weight percentage of the aqueous carbon nanotube dispersion in the antistatic layer is preferably 5 to 25%.
The antistatic agent which has a synergistic effect with the aqueous carbon nanotube adopts the lithium salt, the lithium salt is the lithium bis (fluorosulfonyl) imide and the lithium trifluoromethanesulfonate, the lithium salt can play a good conductive communication role when being added into the aqueous carbon nanotube dispersion liquid, the defect caused by the antistatic function after the carbon nanotube coating is stretched is overcome, the antistatic effect can be influenced when the content of the lithium salt is too low, the viscosity of the whole coating liquid is increased and the coating is difficult to coat when the content of the lithium salt is too high, and in order to achieve the excellent antistatic effect and the good coating appearance, the weight percentage of the lithium salt in the antistatic layer is preferably 2-10%.
The wetting agent of the present invention is preferably a nonionic surface wetting agent, which can help the antistatic layer coating liquid to better spread on the surface of the polyester film during coating, but the ionic surface wetting agent easily causes agglomeration of the aqueous carbon nanotube dispersion liquid, which affects coating, so the preferred nonionic surface wetting agent of the present invention can be polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block copolymer nonionic surfactant.
The resin of the invention is selected from waterborne polyurethane resin, and in order that the waterborne carbon nanotube antistatic coating has better antistatic effect and film forming effect, the invention is preferably waterborne polyurethane resin. When the content of the waterborne polyurethane resin is too high, the antistatic effect of the coating is influenced; when the content of the waterborne polyurethane resin is too low, the film forming effect of the antistatic coating is poor; therefore, the weight percentage of the aqueous polyurethane resin in the antistatic layer is preferably 3 to 5 percent.
The invention is further illustrated by the following specific examples:
example 1
Preparing an antistatic coating liquid:
5g of aqueous carbon nanotube dispersion (with the trade name of CNTS-016, Suzhou carbon rich graphene science and technology Limited, the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 1%), 3g of aqueous polyurethane (with the trade name of PU-3407, Sanliter trade Limited in Sushan City, Sushan city), 10g of lithium salt (with the trade name of 171611-11-3, Guangdong Wenjiang chemical reagent Limited, lithium bis (fluorosulfonyl) imide), 82g of water, 0.1g of cross-linking agent (with the trade name of LF-8500, Linan energy-rich resin Limited, melamine), and 0.01g of wetting agent (with the trade name of PE-100, Guangzhou Hengcheng chemical industry Limited, polyoxyethylene alkylphenol ether). Dispersing uniformly by a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparing an antistatic film:
firstly, feeding crystallized and dried polyester slices into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled casting slices, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one surface or two surfaces of a longitudinally stretched film in one of gravure coating, wire rod coating, dip coating and the like, heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 4 times, and then carrying out heat setting and winding to obtain the antistatic film, wherein the dry thickness of the coating layer is 0.15 mu m.
Example 2
Preparing an antistatic coating liquid:
15g of aqueous carbon nanotube dispersion (trade name of XFNAO, Nanjing Xiancheng nanometer material science and technology Limited, the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 0.5%), 4g of aqueous polyurethane (trade name of XN8150, Xinnuo high polymer material Limited), 6g of lithium salt (trade name of 33454-82-9, Wuhana Nabai medicine chemical industry Limited, lithium trifluoromethanesulfonate), 72g of water, 1g of cross-linking agent (trade name of SAC-100, Shanghai Yong chemical industry Limited, aziridine), and 2g of wetting agent (trade name of EH-9/6/3, Shenzhen Shang Rongchang science and technology Limited, polyoxyethylene fatty alcohol ether). Dispersing uniformly by a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparing an antistatic film:
firstly, feeding crystallized and dried polyester slices into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled casting slices, wherein the longitudinal stretching ratio is 4 times, coating the prepared antistatic coating liquid on one surface or two surfaces of a longitudinally stretched film in one of gravure coating, wire rod coating, dip coating and the like, heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 5 times, and then carrying out heat setting and winding to obtain the antistatic film, wherein the dry thickness of the coating layer is 0.1 mu m.
Example 3
Preparing an antistatic coating liquid:
25g of aqueous carbon nanotube dispersion (brand: WDSR, New Material of Beijing Boyu Gaokou, the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 0.7%), 5g of aqueous polyurethane (brand: SP-90, Xinyang chemical Co., Ltd. of Guangzhou), 8g of lithium salt (brand: 171611-11-3, Zhang hong Qiixing energy Co., Ltd. of lithium bis (fluorosulfonylimide)), 62g of water, 2g of cross-linking agent (brand: XH-540, Aster Asahi Yi Hua chemical Co., Ltd. of Dong Aster, oxazoline), and 0.1g of wetting agent (brand: TFE-2, Sangda chemical Co., Ltd. of polyoxyethylene polyoxypropylene block copolymer). Dispersing uniformly by a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparing an antistatic film:
firstly, feeding crystallized and dried polyester slices into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled casting slices, wherein the longitudinal stretching ratio is 5 times, coating the prepared antistatic coating liquid on one surface or two surfaces of a longitudinally stretched film in one of gravure coating, wire rod coating, dip coating and the like, heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 3 times, and then carrying out heat setting and winding to obtain the antistatic film, wherein the dry thickness of the coating layer is 0.12 mu m.
Example 4
Preparing an antistatic coating liquid:
10g of aqueous carbon nanotube dispersion liquid (the trade name is CNTS-016, Suzhou carbon rich graphene science and technology limited, the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion liquid is 1%), 3.5g of aqueous polyurethane (the trade name is XN8150, Xinno high polymer material limited), 4g of lithium salt (the trade name is 33454-82-9, Wuhan La Nabai medicine chemical industry limited, lithium trifluoromethanesulfonate), 82g of water, 0.5g of cross-linking agent (the trade name is LF-8500, Liannan energy-rich resin limited, melamine), and 0.03g of wetting agent (the trade name is TFE-2, Santa chemical industry limited, polyoxyethylene polyoxypropylene block copolymer). Dispersing uniformly by a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparing an antistatic film:
firstly, feeding crystallized and dried polyester slices into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled casting slices, wherein the longitudinal stretching ratio is 4 times, coating the prepared antistatic coating liquid on one surface or two surfaces of a longitudinally stretched film in one of gravure coating, wire rod coating, dip coating and the like, heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 4 times, and then carrying out heat setting and winding to obtain the antistatic film, wherein the dry thickness of the coating layer is 0.08 mu m.
Example 5
Preparing an antistatic coating liquid:
20g of aqueous carbon nanotube dispersion (brand WDSR, New Material of Hitachi, Beijing Boyu, the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 0.6%), 4.5g of aqueous polyurethane (brand PU-3407, Sanliter trade Co., Ltd. of Sunday district, Foshan City), 2g of lithium salt (brand 171611-11-3, Zhang Jia Gangqixin energy Co., Ltd., lithium bis (fluorosulfonylimide)), 71.5g of water, 1.5g of cross-linking agent (brand SAC-100, Shanghai Yong En chemical Co., Ltd., aziridine), and 0.08g of wetting agent (brand PE-100, Guangzhou Hengyu chemical Co., Ltd., polyoxyethylene alkylphenol ether). Dispersing uniformly by a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparing an antistatic film:
firstly, feeding crystallized and dried polyester slices into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled casting slices, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one surface or two surfaces of a longitudinally stretched film in one of gravure coating, wire rod coating, dip coating and the like, heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 5 times, and then carrying out heat setting and winding to obtain the antistatic film, wherein the dry thickness of the coating layer is 0.2 mu m.
Comparative example 1
Preparing an antistatic coating liquid:
25g of aqueous carbon nanotube dispersion (with the trade name of CNTS-016, Suzhou carbofeng graphene science and technology Co., Ltd., the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 1%), 5g of aqueous polyurethane (with the trade name of SP-90, Guangzhou Xingshuan chemical Co., Ltd.), 70g of water, 2g of cross-linking agent (with the trade name of XH-540, Aster Dongyi Xuyi Hua chemical Co., Ltd., oxazoline), and 0.1g of wetting agent (with the trade name of TFE-2, Sangda chemical Co., Ltd., polyoxyethylene polyoxypropylene block copolymer). Dispersing uniformly by a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparing an antistatic film:
firstly, feeding crystallized and dried polyester slices into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled casting slices, wherein the longitudinal stretching ratio is 5 times, coating the prepared antistatic coating liquid on one surface or two surfaces of a longitudinally stretched film in one of gravure coating, wire rod coating, dip coating and the like, heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 3 times, and then carrying out heat setting and winding to obtain the antistatic film, wherein the dry thickness of the coating layer is 0.15 mu m.
Comparative example 2
Preparing an antistatic coating liquid:
4.5g of aqueous polyurethane (trade mark of PU-3407, Sanliter trade company, Ltd. in Sunday district, Fushan City), 2g of lithium salt (trade mark of 171611-11-3, Zhang Jia Youxin energy company, lithium bis (fluorosulfonyl) imide), 91.5g of water, 1.5g of cross-linking agent (trade mark of SAC-100, Shanghai Youn chemical company, aziridine), and 0.08g of wetting agent (trade mark of PE-100, Guangzhou Hengyu chemical company, polyoxyethylene alkylphenol ether). Dispersing uniformly by a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparing an antistatic film:
firstly, feeding crystallized and dried polyester slices into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled casting slices, wherein the longitudinal stretching ratio is 4 times, coating the prepared antistatic coating liquid on one surface or two surfaces of a longitudinally stretched film in one of gravure coating, wire rod coating, dip coating and the like, heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 4 times, and then carrying out heat setting and winding to obtain the antistatic film, wherein the dry thickness of the coating layer is 0.1 mu m.
Comparative example 3
Preparing an antistatic coating liquid:
20g of aqueous carbon nanotube dispersion (brand WDSR, New Material of Hitachi, Beijing Boyu, the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 0.6%), 4.5g of aqueous polyurethane (brand PU-3407, Sanliter trade Co., Ltd. of Sunday district, Foshan City), 2g of lithium salt (brand 171611-11-3, Zhang Jia Gangqixin energy Co., Ltd., lithium bis (fluorosulfonylimide)), 71.5g of water, 1.5g of cross-linking agent (brand SAC-100, Shanghai Yong En chemical Co., Ltd., aziridine), and 0.08g of wetting agent (brand PE-100, Guangzhou Hengyu chemical Co., Ltd., polyoxyethylene alkylphenol ether). Dispersing uniformly by a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparing an antistatic film:
coating the prepared antistatic coating liquid on one or two surfaces of a polyester film by one of the modes of gravure coating, wire rod coating, dip coating and the like, and heating and drying to obtain the antistatic film, wherein the dry thickness of the coating is 0.2 mu m.
The performance test methods are as follows:
(1) surface resistance of the film: GB/T33398;
(2) coating adhesion (adhesion of antistatic layer to silicone oil layer): ASTM D3359.
TABLE 1
As can be seen from the above table, the surface resistance of the antistatic film of the present invention can reach 105Within omega, then coating silicon oil on the antistatic layer to form a silicon oil layer, wherein the dry thickness of the silicon oil layer is 0.01-5 mu m, and the surface resistance can reach 108Within omega, good coating adhesion and excellent performance.
Claims (6)
1. The antistatic film comprises a base material and an antistatic layer coated on at least one surface of the base material, wherein the antistatic layer and the base material are synchronously stretched transversely and then are sized to obtain the antistatic film, and the antistatic film is characterized in that the antistatic layer is prepared from the following raw materials in percentage by weight:
5 to 25 percent of aqueous carbon nanotube dispersion liquid
2 to 10 percent of lithium salt
3 to 5 percent of waterborne polyurethane resin
0.1 to 2 percent of cross-linking agent
0.01 to 0.1 percent of wetting agent
58% -86% of deionized water;
the weight ratio of the carbon nanotubes in the aqueous carbon nanotube dispersion liquid is 0.5-1%, and the balance of the dispersion liquid is water;
the lithium salt is lithium bis (fluorosulfonyl) imide and lithium trifluoromethanesulfonate;
the surface resistance of the antistatic film is between 104Ω～105Ω；
Coating silicon oil on the surface of the anti-static film to form a silicon oil layer, wherein the surface resistance of the silicon oil layer is between 104Ω～105Omega; the dry thickness of the silicon oil layer is 0.01-1 mu m.
2. The antistatic film of claim 1, wherein the water-based carbon nanotubes are one or a combination of single-walled or multi-walled carbon nanotubes.
3. The antistatic film of claim 1 wherein said wetting agent is a non-ionic wetting agent.
4. The antistatic film of claim 1 wherein the thickness of the antistatic layer is 0.08 to 0.2 μm.
5. The antistatic film of claim 1 wherein the cross-linking agent is melamine, azapyridine or oxazoline.
6. A method for preparing the antistatic film according to any one of claims 1 to 5, characterized in that the preparation is carried out by the following steps:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, and casting on a rotating cooling roller; preheating the cooled casting sheet, and longitudinally stretching with the longitudinal stretching ratio of 3-5 times; coating the prepared antistatic coating liquid on one or two surfaces of the film subjected to longitudinal stretching in one of gravure coating, wire rod coating or dip coating modes; and heating and drying the film coated with the antistatic coating liquid, transversely stretching the film by 3-5 times, and then performing heat setting and rolling to obtain the antistatic film.
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| CN110211483B (en) * | 2019-05-24 | 2021-05-28 | 深圳昌茂粘胶新材料有限公司 | Printable surface adhesive double-anti-static label material and preparation method thereof |
| CN110606978B (en) * | 2019-10-10 | 2022-07-08 | 上海玉城高分子材料股份有限公司 | Polypropylene composite foamed bead containing graphene permanent antistatic coating and preparation method and application thereof |
| CN111703096A (en) * | 2020-06-09 | 2020-09-25 | 浙江康润新材料有限公司 | Manufacturing process of TPU waterproof film |
| CN113308011B (en) * | 2021-06-10 | 2022-12-27 | 太湖金张科技股份有限公司 | Anti-static release film and preparation method thereof |
| CN114106386A (en) * | 2021-12-07 | 2022-03-01 | 合肥乐凯科技产业有限公司 | Anti-static polyester film and preparation method thereof |
| CN115850773B (en) * | 2022-12-09 | 2023-09-15 | 合肥乐凯科技产业有限公司 | Antistatic film and preparation method thereof |
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