CN116854975B - Antistatic film and preparation method thereof - Google Patents
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- CN116854975B CN116854975B CN202310851077.9A CN202310851077A CN116854975B CN 116854975 B CN116854975 B CN 116854975B CN 202310851077 A CN202310851077 A CN 202310851077A CN 116854975 B CN116854975 B CN 116854975B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims abstract description 43
- 229920002635 polyurethane Polymers 0.000 claims abstract description 38
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 acrylic ester Chemical class 0.000 claims abstract description 24
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims description 113
- 239000011248 coating agent Substances 0.000 claims description 112
- 239000007788 liquid Substances 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000002041 carbon nanotube Substances 0.000 claims description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 11
- 238000009998 heat setting Methods 0.000 claims description 11
- 229920000123 polythiophene Polymers 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 229920000767 polyaniline Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002918 oxazolines Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 8
- 230000002265 prevention Effects 0.000 abstract description 2
- 230000003068 static effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 80
- 239000010410 layer Substances 0.000 description 30
- 230000001804 emulsifying effect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 9
- 238000005096 rolling process Methods 0.000 description 9
- 238000003618 dip coating Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000007756 gravure coating Methods 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920006243 acrylic copolymer Polymers 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention belongs to the field of static prevention, and particularly relates to an antistatic film and a preparation method thereof. The antistatic film comprises a base material and an antistatic layer arranged on at least one side of the base material, wherein the antistatic layer and the base material are synchronously and transversely stretched and then shaped to obtain the antistatic film, and the antistatic layer comprises a conductive material, modified polyurethane acrylate copolymer resin, a crosslinking agent and deionized water. The antistatic layer of the invention uses the modified polyurethane acrylic ester copolymer resin, and has small resistance change and good antistatic weather resistance after the antistatic layer is used.
Description
Technical Field
The invention belongs to the field of static prevention, and particularly relates to an antistatic film and a preparation method thereof.
Background
Optical films in liquid crystal display screens are increasingly widely used, and the films are polluted due to electrostatic action in the transportation and deep processing processes, so that various defects are generated in the deep processing processes, and the overall quality of the optical films is affected. Therefore, it is necessary to coat an antistatic protective film on the surface of the optical film.
Currently, antistatic films can be classified 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. The online coating antistatic film has higher resistance and limited application range, so that the offline coating antistatic film has wider application range. The online coating antistatic film is characterized in that antistatic coating liquid is coated on the surface of a film in the film manufacturing process, but on one hand, the thickness of the coating is limited, and the thickness of the coating is lower, generally tens of nanometers; on the other hand, the coating material needs to be stretched 3 to 5 times after coating, so that the antistatic performance is weakened or vanish, and the coating material has high requirements on the performance. Therefore, the antistatic film applied to the industries of release films and protective films is mostly prepared by an off-line process.
However, the antistatic film in the prior art has the problem of poor antistatic and weather resistance.
In view of this, the present invention has been made.
Disclosure of Invention
The antistatic weather resistance is closely related to the resistance change of the antistatic film, the resistance of the antistatic film changes after the antistatic film is used for a period of time, and the larger the resistance change is, the worse the antistatic weather resistance is; the smaller the resistance change, the better the antistatic weather resistance.
In order to solve the technical problems in the prior art, the invention provides an antistatic film and a preparation method thereof, wherein the antistatic layer is prepared from modified polyurethane acrylate copolymer resin, and the antistatic film has small resistance change and good antistatic weather resistance after being used.
The invention comprises the following technical scheme:
the invention provides an antistatic film, which comprises a base material and an antistatic layer arranged on at least one side of the base material, wherein the antistatic layer and the base material are synchronously stretched transversely and then shaped to obtain the antistatic film, and the antistatic layer comprises a conductive material, modified polyurethane acrylate copolymer resin, a crosslinking agent and deionized water.
Further, the antistatic layer comprises the following raw materials in percentage by weight:
conductive material: 5% -20%;
modified urethane acrylate copolymer resin: 5% -20%;
crosslinking agent: 0.1% -5%;
deionized water: 55% -89.9%.
Further, the preparation method of the modified polyurethane propylene ester copolymer resin comprises the following steps:
adding isocyanate into polyol, and heating for reaction;
adding a chain extender to react;
sequentially adding diethylenetriamine, a small molecular cross-linking agent and an acetone solution of maleic anhydride, and heating for reaction;
adding sodium hydroxide solution for heat preservation;
adding an emulsifying agent and water, stirring, adding butyl acrylate solution containing an initiator, and heating for reaction;
and cooling to obtain the modified polyurethane acrylic ester copolymer resin.
Further, the isocyanate includes at least one of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, 4' -dicyclohexylmethane, and diisocyanate.
Further, the initiator is azobisisobutyronitrile.
Further, the small molecule cross-linking agent is trimethylolpropane.
Further, the antistatic layer has a thickness of 5nm to 2 μm.
Further, the conductive material is one or more of carbon nanotube powder, polythiophene particles, polyaniline powder and conductive metal; or the conductive material is one or more of polythiophene-like dispersion liquid, carbon nanotube dispersion liquid, polyaniline dispersion liquid, silver paste and silver wires.
Further, the cross-linking agent is one of oxazolines, isocyanates, azopyridines and melamine.
The second aspect of the present invention provides a method for preparing an antistatic film, for preparing the antistatic film, comprising the steps of:
feeding the substrate raw material into an extrusion system to melt and extrude a substrate melt;
forming said substrate melt into an amorphous cast slab on a chill roll;
preheating the cooled casting thick sheet, and longitudinally stretching for 3.0-5.0 times to obtain a membrane;
coating an antistatic layer coating liquid on one surface of the membrane;
preheating a membrane coated with an antistatic layer coating liquid, and transversely stretching the membrane by 3.0 to 5.0 times to obtain a film;
and (5) carrying out heat setting on the film to obtain the antistatic film.
By adopting the technical scheme, the invention has the following advantages:
1. the antistatic layer of the invention uses the modified polyurethane acrylic ester copolymer resin, and has small resistance change and good antistatic weather resistance after the antistatic layer is used.
2. According to the method, the antistatic layer coating liquid prepared from the modified polyurethane acrylic ester copolymer resin, the water-based conductive material and the cross-linking agent is subjected to on-line coating, and simultaneously is transversely stretched, shaped and thermally cured with a substrate to form a three-dimensional network structure; to obtainThe surface resistance obtained was 10 4 Ω-10 11 The omega antistatic film has excellent weather resistance and antistatic performance.
3. The modified polyurethane acrylate copolymer resin disclosed by the invention has the advantages of polyurethane and polyacrylate, is safe and environment-friendly, has good film forming performance and excellent physical and mechanical properties, forms an interpenetrating network with an antistatic agent through online coating, stretching and shaping, has better coating optical performance of interpenetrating network polymers, and has the characteristics of low viscosity, adjustable molecules and the like in order to improve the weather resistance and antistatic performance of the aqueous antistatic coating liquid.
4. According to the invention, through molecular structure design, polyacrylic resin is used as a mixed hard segment to be introduced into a polyurethane rubber molecular chain segment, so that the crosslinking effect is improved, and the coating has excellent antistatic performance and weather resistance. Simultaneously, the modified polyurethane acrylate copolymer resin and the water-based conductive high polymer material are transversely stretched and shaped synchronously through online coating and base material, and thermally cured to form a three-dimensional network structure, so that a compact conductive path is formed, and the surface resistance 10 of the antistatic film is obtained 4 Ω~10 11 Omega, has excellent antistatic performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view of an antistatic film according to an embodiment of the present invention;
in the accompanying drawings: 1-substrate, 2-antistatic layer.
Detailed Description
The following description provides many different embodiments, or examples, for implementing different features of the invention. The elements and arrangements described in the following specific examples are presented for purposes of brevity and are provided only as examples and are not intended to limit the invention.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides an antistatic film, as shown in fig. 1, including a substrate and an antistatic layer at least arranged on one side of the substrate, wherein the antistatic layer and the substrate are synchronously stretched transversely and then shaped to obtain the antistatic film, and the antistatic layer comprises a conductive material, a modified polyurethane acrylate copolymer resin, a crosslinking agent and deionized water.
Further, the antistatic layer comprises the following raw materials in percentage by weight:
conductive material: 5% -20%;
modified urethane acrylate copolymer resin: 5% -20%;
crosslinking agent: 0.1% -5%;
deionized water: 55% -89.9%.
If the content of the conductive material is too low, the antistatic effect is poor, if the content of the conductive material is too high, the spreading performance of the coating liquid is reduced, the coating appearance is poor, and the weather resistance is also affected, so that the weight percentage of the conductive material is preferably 5-25%; if the content of the modified polyurethane acrylic ester copolymer resin is too low, the film forming effect of the conductive material on the surface of the film is poor, the coating appearance is poor, the weather resistance is also affected, if the content of the modified polyurethane acrylic ester copolymer resin is too high, the coating electric material is too tight, the conductive material exposed on the surface is too little, the antistatic performance is difficult to develop, and the antistatic effect is poor, so that the preferable weight percentage of the modified polyurethane acrylic ester copolymer resin is 5-25%; if the content of the cross-linking agent is too low, the cross-linking density of the coating is too low, the hardness and scratch resistance of the antistatic coating are reduced, the weather resistance is also reduced, if the content of the cross-linking agent is too high, the stability of the coating liquid is poor, and meanwhile, too many small molecules cause excessive cross-linking and the risks such as precipitation are easy to occur at high temperature, so the weight percentage of the cross-linking agent is preferably 0.1-5%.
Further, the preparation method of the modified polyurethane propylene ester copolymer resin comprises the following steps:
adding isocyanate into polyol, and heating for reaction;
adding a chain extender to react;
sequentially adding diethylenetriamine, a small molecular cross-linking agent and an acetone solution of maleic anhydride, and heating for reaction;
adding sodium hydroxide solution for heat preservation;
adding an emulsifying agent and water, stirring, adding butyl acrylate solution containing an initiator, and heating for reaction;
cooling to obtain modified polyurethane acrylate copolymer resin;
preferably, isocyanate is added into the polyol, and the mixture is heated to 75-85 ℃ for reaction for 1-3 hours;
adding a chain extender, and reacting for 1-3 hours;
sequentially adding diethylenetriamine, a micromolecular cross-linking agent and an acetone solution of maleic anhydride, heating to 50-70 ℃ and reacting for 1-2 h;
adding sodium hydroxide solution, and preserving heat for 0.5-1.5 h at the temperature of 45-55 ℃;
adding an emulsifying agent and water, stirring, adding butyl acrylate solution containing an initiator, emulsifying for 30min, heating to 75-85 ℃ for reaction for 2.5-3.5h, heating to 85-95 ℃ again, and reacting for 1-2 h;
and cooling to obtain the modified polyurethane acrylic ester copolymer resin.
Further, the isocyanate includes at least one of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, 4' -dicyclohexylmethane, and diisocyanate.
Further, the initiator is azobisisobutyronitrile.
Further, the small molecule cross-linking agent is trimethylolpropane.
If the antistatic thickness is too thin, the antistatic agent content of the coating in unit area is low, the antistatic effect is poor, polar groups in unit area are low, and the weather resistance is reduced; if the antistatic layer is too thick, the antistatic agent content per unit area is large, the antistatic effect is good, but the coating appearance is poor. Further, the antistatic layer has a thickness of 5nm to 2 μm.
Further, the conductive material is one or more of carbon nanotube powder, polythiophene particles, polyaniline powder and conductive metal; or the conductive material is one or more of polythiophene-like dispersion liquid, carbon nanotube dispersion liquid, polyaniline dispersion liquid, silver paste and silver wires.
In order to improve the crosslinking density of the antistatic coating, the linear molecules are ensured to be mutually connected to form a three-dimensional network structure, the weather resistance of the antistatic coating is improved, a compact conductive path is formed, and meanwhile, the stability of antistatic liquid is ensured. Further, the cross-linking agent is one of oxazolines, isocyanates, azopyridines and melamine.
Example 2
The present embodiment provides a method for preparing an antistatic film, which can be used to prepare the antistatic film described in embodiment 1, and includes the following steps:
feeding the substrate raw material into an extrusion system to melt and extrude a substrate melt;
forming said substrate melt into an amorphous cast slab on a chill roll;
preheating the cooled casting thick sheet, and longitudinally stretching for 3.0-5.0 times to obtain a membrane; the longitudinal stretching is 3.0 to 5.0, so that the longitudinal thickness uniformity can be ensured, the longitudinal stretching is not too large, the orientation degree is too high, and the film is not easy to form during transverse stretching;
coating an antistatic layer coating liquid on one surface of the membrane;
preheating a membrane coated with an antistatic layer coating liquid, and transversely stretching the membrane by 3.0 to 5.0 times to obtain a film; the transverse stretching is 3.0-5.0, so that the transverse thickness uniformity can be ensured, the compactness of the on-line coating carbon nano tube coating can be ensured, a stable conductive path is formed, if the stretching multiple is too low, the coating is thicker, the carbon nano tube is easy to lap obviously, the surface of the polyester film is unevenly distributed, and if the stretching multiple is too high, the coating breaks, the conductive path is damaged, and excellent antistatic performance cannot be formed;
and (5) carrying out heat setting on the film to obtain the antistatic film.
Example 1
Preparation of modified polyurethane propylene ester copolymer resin:
the dehydrated polyoxypropylene diol in vacuum was added to isophorone diisocyanate, reacted at 75℃for 1 hour, and then 2, 2-dimethylolpropionic acid and butanediol were added for further reaction for 1 hour. Then sequentially dripping acetone solution of diethylenetriamine, epoxy chloropropane and maleic anhydride, heating to 50 ℃, adding a proper amount of NaOH solution after reacting for 1h, maintaining the temperature at 45 ℃, preserving the heat for 0.5h, then adding butyl acrylate solution containing azo-diisobutyronitrile as an initiator, pre-emulsifying for a period of time, polymerizing at 75 ℃ for 2.5h, heating to 85 ℃ for reacting for 1h, and cooling to room temperature to obtain the modified polyurethane-propylene copolymer resin.
Preparing antistatic layer coating liquid:
5g of aqueous polythiophene dispersion A200 (Ikefa, the weight ratio of polythiophene in the aqueous polythiophene dispersion is 5%), 5g of modified polyurethane propylene copolymer resin, 89.9g of deionized water and 0.1g of oxazoline cross-linking agent WS-700 (You En chemical industry) are taken, and uniformly dispersed by a high-shear emulsifying machine to prepare the antistatic layer coating solution.
Preparation of antistatic film:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled cast chips, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic layer coating liquid on one or two sides of a film after longitudinal stretching by one of the modes of gravure coating, silk rod coating, dip coating and the like, transversely stretching the film coated with the antistatic layer coating liquid for 3 times after heating and drying, and then performing heat setting and rolling to obtain the antistatic film with the dry thickness of 5nm.
Example 2
Preparation of modified polyurethane propylene ester copolymer resin:
the vacuum dehydrated polyoxypropylene diol was added to diphenylmethane diisocyanate, reacted at 85℃for 3 hours, and then 2, 2-dimethylolpropionic acid and butanediol were added to continue the reaction for 3 hours. Then sequentially dripping acetone solution of diethylenetriamine, epoxy chloropropane and maleic anhydride, heating to 70 ℃, adding a proper amount of NaOH solution after reacting for 2 hours, maintaining the temperature at 55 ℃, preserving heat for 1.5 hours, then mixing PU, an emulsifying agent and water, then placing the mixture in a four-neck flask, uniformly stirring, adding butyl acrylate solution containing an initiator azo diisobutyronitrile, pre-emulsifying for a period of time, polymerizing for 3.5 hours at 85 ℃, heating to 95 ℃, reacting for 2 hours, and cooling to room temperature to obtain the modified polyurethane propylene ester copolymer resin.
Preparing antistatic layer coating liquid:
12.5g of aqueous polyaniline dispersion HS0394 (chemical product of south sea Jiang Shun in Buddha, weight ratio of polyaniline in aqueous polyaniline dispersion is 5%), 12.5g of modified polyurethane acrylic copolymer resin, 72.5g of water and 2.5g of oxazoline crosslinking agent WS-700 (chemical product You En). And uniformly dispersing by using a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparation of antistatic film:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled cast chips, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one or two sides of a film after longitudinal stretching by one of the modes of gravure coating, wire rod coating, dip coating and the like, transversely stretching the film coated with the antistatic coating liquid for 3 times after heating and drying, and then carrying out heat setting and rolling to obtain the antistatic film with the coating thickness of 1 mu m.
Example 3
Preparation of modified polyurethane propylene ester copolymer resin:
the vacuum dehydrated polyoxypropylene diol was added to toluene diisocyanate, reacted at 80℃for 2 hours, then 2, 2-dimethylolpropionic acid and butanediol were added to continue the reaction for 2 hours. Then sequentially dripping acetone solution of diethylenetriamine, epoxy chloropropane and maleic anhydride, heating to 60 ℃, adding a proper amount of NaOH solution after reacting for 1.5 hours, maintaining the temperature at 50 ℃, preserving heat for 1 hour, then mixing PU, an emulsifying agent and water, then placing the mixture in a four-neck flask, stirring uniformly, adding butyl acrylate solution containing an initiator azo diisobutyronitrile, pre-emulsifying for a period of time, polymerizing for 3 hours at 80 ℃, heating to 90 ℃ for reacting for 1.5 hours, and cooling to room temperature to obtain the modified polyurethane propylene ester copolymer resin.
Preparing antistatic layer coating liquid:
20g of aqueous carbon nano tube dispersion ML1293 (the weight ratio of carbon nano tubes in the aqueous carbon nano tube dispersion is 5 percent), 20g of modified polyurethane acrylic copolymer resin, 55g of water and 5g of oxazoline crosslinking agent WS-700 (You En chemical industry). And uniformly dispersing by using a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparation of antistatic film:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled cast chips, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one or two sides of a film after longitudinal stretching by one of the modes of gravure coating, wire rod coating, dip coating and the like, transversely stretching the film coated with the antistatic coating liquid for 3 times after heating and drying, and then carrying out heat setting and rolling to obtain the antistatic film with the coating thickness of 2 mu m.
Example 4
Preparation of modified polyurethane propylene ester copolymer resin:
the vacuum dehydrated polyoxypropylene glycol was added to 4,4' -dicyclohexylmethane diisocyanate, reacted at 77.5℃for 1.5 hours, and then 2, 2-dimethylolpropionic acid and butanediol were added thereto for further reaction for 1.5 hours. Then sequentially dripping acetone solution of diethylenetriamine, epoxy chloropropane and maleic anhydride, heating to 55 ℃, adding a proper amount of NaOH solution after reacting for 1.25 hours, maintaining the temperature at 47.5 ℃, preserving heat for 0.75 hours, then mixing PU, an emulsifying agent and water, then placing the mixture in a four-neck flask, uniformly stirring, adding butyl acrylate solution containing an initiator azo-diisobutyronitrile, pre-emulsifying for a period of time, polymerizing for 2.75 hours at 77.5 ℃, heating to 87.5 ℃, reacting for 1.25 hours, and cooling to room temperature to obtain the preparation of the modified polyurethane propylene copolymer resin.
Preparing antistatic layer coating liquid:
16.25g of aqueous carbon nanotube dispersion ML1293 (the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 5 percent), 16.25g of modified polyurethane acrylic copolymer resin, 64.25g of water and 3.25g of oxazoline crosslinking agent WS-700 (You En chemical industry). And uniformly dispersing by using a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparation of antistatic film:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled cast chips, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one or two sides of a film after longitudinal stretching by one of the modes of gravure coating, wire rod coating, dip coating and the like, transversely stretching the film coated with the antistatic coating liquid for 3 times after heating and drying, and then carrying out heat setting and rolling to obtain the antistatic film with the coating thickness of 1.5 mu m.
Example 5
Preparation of modified polyurethane propylene ester copolymer resin:
the dehydrated polyoxypropylene diol in vacuum was added to isophorone diisocyanate, reacted at 82.5℃for 2.5 hours, and then 2, 2-dimethylolpropionic acid and butanediol were added to continue the reaction for 2.5 hours. Then sequentially dripping acetone solution of diethylenetriamine, epoxy chloropropane and maleic anhydride, heating to 65 ℃, adding a proper amount of NaOH solution after reacting for 1.75 hours, maintaining the temperature at 52.5 ℃, preserving heat for 1.25 hours, then mixing PU, an emulsifying agent and water, then placing the mixture in a four-neck flask, uniformly stirring, adding butyl acrylate solution containing an initiator azo-diisobutyronitrile, polymerizing for 3.25 hours at 82.5 ℃ after pre-emulsifying for a period of time, heating to 92.5 ℃ for reacting for 1.75 hours, and cooling to room temperature to obtain the modified polyurethane propylene ester copolymer resin.
Preparing antistatic layer coating liquid:
8.75g of aqueous carbon nano tube dispersion ML1293 (the weight ratio of carbon nano tubes in the aqueous carbon nano tube dispersion is 5 percent), 8.75g of modified polyurethane acrylic copolymer resin, 82.25g of water and 1.25g of oxazoline cross-linking agent WS-700 (You En chemical industry). And uniformly dispersing by using a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparation of antistatic film:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled cast chips, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one or two sides of a film after longitudinal stretching by one of the modes of gravure coating, wire rod coating, dip coating and the like, transversely stretching the film coated with the antistatic coating liquid for 3 times after heating and drying, and then carrying out heat setting and rolling to obtain the antistatic film with the coating thickness of 0.5 mu m.
Comparative example 1
Preparation of antistatic coating liquid:
8.75g of aqueous carbon nanotube dispersion ML1293 (crystal antibiosis, weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 5%), 8.75g of polyurethane resin, 82.25g of water and 1.25g of oxazoline crosslinking agent WS-700 (You En chemical industry). And uniformly dispersing by using a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparation of antistatic film:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled cast chips, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one or two sides of a film after longitudinal stretching by one of the modes of gravure coating, wire rod coating, dip coating and the like, transversely stretching the film coated with the antistatic coating liquid for 3 times after heating and drying, and then carrying out heat setting and rolling to obtain the antistatic film with the coating thickness of 0.5 mu m.
Comparative example 2
Preparation of antistatic coating liquid:
5g of aqueous polythiophene dispersion A200 (Ikefa, the weight ratio of polythiophene in the aqueous polythiophene dispersion was 5%), 5g of acrylic resin, 89.9g of water, and 0.1g of oxazoline crosslinking agent WS-700 (You En chemical industry). And uniformly dispersing by using a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparation of antistatic film:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled cast chips, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one or two sides of a film after longitudinal stretching by one of the modes of gravure coating, wire rod coating, dip coating and the like, transversely stretching the film coated with the antistatic coating liquid for 3 times after heating and drying, and then carrying out heat setting and rolling to obtain the antistatic film with the coating dry thickness of 5nm.
Comparative example 3
Preparation of antistatic coating liquid:
20g of aqueous carbon nanotube dispersion ML1293 (the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 5 percent), 10g of polyurethane resin, 10g of acrylic resin, 55g of water and 5g of oxazoline crosslinking agent WS-700 (You En chemical industry). And uniformly dispersing by using a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparation of antistatic film:
firstly, feeding the crystallized and dried polyester chips into a corresponding extrusion system for melt extrusion, casting on a rotating cooling roller, preheating and longitudinally stretching the cooled cast chips, wherein the longitudinal stretching ratio is 3 times, coating the prepared antistatic coating liquid on one or two sides of a film after longitudinal stretching by one of the modes of gravure coating, wire rod coating, dip coating and the like, transversely stretching the film coated with the antistatic coating liquid for 3 times after heating and drying, and then carrying out heat setting and rolling to obtain the antistatic film with the coating thickness of 2 mu m.
Comparative example 4
Preparation of modified polyurethane acrylate composite resin:
the dehydrated polyoxypropylene diol in vacuum was added to isophorone diisocyanate, reacted at 82.5℃for 2.5 hours, and then 2, 2-dimethylolpropionic acid and butanediol were added to continue the reaction for 2.5 hours. Then sequentially dripping acetone solution of diethylenetriamine, epoxy chloropropane and maleic anhydride, heating to 65 ℃, adding a proper amount of NaOH solution after reacting for 1.75 hours, maintaining the temperature at 52.5 ℃, preserving heat for 1.25 hours, then mixing PU, an emulsifying agent and water, then placing the mixture in a four-neck flask, uniformly stirring, adding butyl acrylate solution containing an initiator azo-diisobutyronitrile, pre-emulsifying for a period of time, polymerizing for 3.25 hours at 82.5 ℃, heating to 92.5 ℃ for reacting for 1.75 hours, and cooling to room temperature to obtain the modified polyurethane acrylate composite emulsion.
Preparation of antistatic coating liquid:
16.25g of aqueous carbon nanotube dispersion ML1293 (the weight ratio of carbon nanotubes in the aqueous carbon nanotube dispersion is 5 percent), 16.25g of modified polyurethane acrylic copolymer resin, 64.25g of water and 3.25g of oxazoline crosslinking agent WS-700 (You En chemical industry). And uniformly dispersing by using a high-shear emulsifying machine to prepare the antistatic coating liquid.
Preparation of antistatic film:
coating the prepared antistatic coating liquid on one side or two sides of the film (the coating and the film are not stretched synchronously), and then solidifying and rolling to obtain the antistatic film, wherein the dry thickness of the coating is 5nm.
The performance test methods are as follows:
(1) Surface resistance (antistatic layer): measured according to GB/T33398;
(2) The weather resistance testing method comprises the following steps: the antistatic film was cut into A4 size, and placed in an environment of constant temperature and humidity (85 ℃ C., 85% RH) for 200 hours and 500 hours, respectively, and then the surface resistance was measured according to GB/T33398.
The test results are shown in Table 1:
table 1 test results table of examples and comparative examples
As can be seen from a comparison of comparative example 1 and example 5, in example 5, after using the modified urethane acrylic resin, the carbon tube coating layer has a surface resistance of 10 after being subjected to on-line coating biaxially oriented setting, compared with the conventional urethane 6 Omega, and the weather resistance of the carbon tube coating liquid is more excellent.
As can be seen from the comparison of comparative example 2 and example 1, the surface resistance of the polythiophene high polymer conductive coating after on-line coating and biaxial stretching shaping is more than 10 after the unmodified acrylic resin is used in comparative example 2 6 Omega, but after 200h and 500h aging test the surface resistance was > 10 12 Omega, large resistance change and poor weather resistance.
Comparative example 3 As can be seen from the comparison of example 3, comparative example 3 uses a polyurethane resin and acrylic resin formulation, with a surface resistance > 10 12 Ω。
Comparative example 4 As can be seen from a comparison of example 4, the antistatic coating of comparative example 4 was not stretched and set in the transverse direction in synchronization with the substrate, and the surface resistance was 10 6 Omega, but after 200h ageing test surface resistance 10 9 Omega, surface resistance after aging test is more than 10 9 Omega, large resistance change and poor weather resistance.
As can be seen from the comparison of example 3 and example 5, example 3 has more modified urethane acrylic resin than example 5 coating, so that the dispersibility of the carbon nanotubes is better and the antistatic effect is better.
As can be seen from table 1, compared with the antistatic film prepared by the comparative example, the antistatic film prepared by the embodiment of the invention is significantly improved in both antistatic performance and weather resistance of the antistatic layer, which indicates that the antistatic polyester film of the invention is excellent in antistatic performance, excellent in coating liquid stability, good in continuous processing performance and good in application prospect.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (9)
1. An antistatic film comprises a base material (1) and an antistatic layer (2) arranged on at least one surface of the base material (1), wherein the antistatic layer and the base material (1) are synchronously and transversely stretched and then shaped to obtain the antistatic film, and the antistatic film is characterized in that the antistatic layer comprises a conductive material, a modified polyurethane acrylate copolymer resin, a crosslinking agent and deionized water;
the preparation method of the modified polyurethane acrylate copolymer resin comprises the following steps:
adding isocyanate into polyol, and heating for reaction;
adding a chain extender to react;
sequentially adding diethylenetriamine, a small molecular cross-linking agent and an acetone solution of maleic anhydride, and heating for reaction;
adding sodium hydroxide solution for heat preservation;
adding an emulsifying agent and water, stirring, adding a butyl acrylate solution containing an initiator, and heating for reaction;
and cooling to obtain the modified polyurethane acrylic ester copolymer resin.
2. An antistatic film according to claim 1, characterized in that the antistatic layer (2) comprises the following raw materials in weight percent:
conductive material: 5% -20%;
modified urethane acrylate copolymer resin: 5% -20%;
crosslinking agent: 0.1% -5%;
deionized water: 55% -89.9%.
3. An antistatic film according to claim 1, wherein,
the isocyanate includes at least one of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
4. An antistatic film as in claim 1 wherein said initiator is azobisisobutyronitrile.
5. An antistatic film as in claim 1 wherein said small molecule cross-linking agent is trimethylol propane.
6. An antistatic film according to claim 1 or 2, characterized in that the antistatic layer (2) has a thickness of between 5nm and 2 μm.
7. An antistatic film according to claim 1 or 2, wherein the conductive material is one or more of carbon nanotube powder, polythiophene particles, polyaniline powder and conductive metal; or the conductive material is one or more of aqueous polythiophene dispersion liquid, carbon nano tube dispersion liquid, polyaniline dispersion liquid, silver paste and silver wires.
8. An antistatic film according to claim 1 or 2, wherein the cross-linking agent is one of oxazolines, isocyanates, azopyridines, melamine.
9. A method for producing an antistatic film, characterized by being used for producing the antistatic film according to any one of claims 1 to 8, comprising the steps of:
feeding the substrate raw material into an extrusion system to melt and extrude a substrate melt;
forming said substrate melt into an amorphous cast slab on a chill roll;
preheating the cooled casting thick sheet, and longitudinally stretching for 3.0-5.0 times to obtain a membrane;
coating an antistatic layer coating liquid on one surface of the membrane;
preheating a membrane coated with an antistatic layer coating liquid, and transversely stretching the membrane by 3.0 to 5.0 times to obtain a film;
and (5) carrying out heat setting on the film to obtain the antistatic film.
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