CN114874709A - Polyurethane protective film with low film tearing voltage - Google Patents

Polyurethane protective film with low film tearing voltage Download PDF

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Publication number
CN114874709A
CN114874709A CN202210610646.6A CN202210610646A CN114874709A CN 114874709 A CN114874709 A CN 114874709A CN 202210610646 A CN202210610646 A CN 202210610646A CN 114874709 A CN114874709 A CN 114874709A
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polyurethane
ethylene
layer
film layer
protective film
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陈灏渠
李盛艺
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Huizhou Haoming Technology Co Ltd
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Huizhou Haoming Technology Co Ltd
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Priority to CN202210610646.6A priority Critical patent/CN114874709A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene 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
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate

Abstract

The invention relates to a polyurethane protective film with low tearing voltage, which comprises a base film layer, an adhesive layer and a release film layer which are sequentially laminated from top to bottom, wherein the base film layer comprises: a polyurethane resin, an ethylene-alpha-olefin copolymer, and an electrostatic agent; the adhesive layer contains: polyurethane resin, ethylene-unsaturated ester copolymer, electrostatic agent and auxiliary agent.

Description

Polyurethane protective film with low film tearing voltage
Technical Field
The invention relates to the technical field of adhesive materials, in particular to a polyurethane protective film with low film tearing voltage.
Background
The polyurethane-based protective film has been widely used in the manufacturing process and shipment protection of Touch Panels (TP). The touch panel is developed in the directions of multi-point touch, large-scale, thin and light-weight, and the like, which also puts higher requirements on the antistatic performance of the protective film used for the touch panel, and particularly, the protective film used for the touch panel during shipment must have excellent antistatic performance to avoid the loss caused by the breakdown of charges through the touch sensor of the touch panel due to the excessive static electricity when the protective film is finally torn off. The prior polyurethane protective film has the following technical problems:
1. the structure of the conventional polyurethane protective film is, in order from the outside to the inside (the side where the protective film contacts the touch panel is defined as the inside of the protective film): the touch sensor comprises a base film layer, an adhesive layer and a release film layer, wherein the base film layer is insulated from the inside, and the base film layer has a large impedance value, so that static electricity cannot be conducted when the protective film is torn off, and the voltage of the torn film often exceeds 1000V, so that the touch sensor is easily damaged;
2. an antistatic agent is usually added into the protective film in order to reduce the tearing voltage of the protective film, but the problem of pollution to the touch panel caused by precipitation of the antistatic agent is easily caused by excessive antistatic agent or unreasonable film material proportion;
3. the internal haze (measured according to ASTM1003, unit is%) of the existing polyurethane protective film is high, and the transparency is poor, so that the touch panel covered by the protective film is inconvenient to visually detect whether appearance defects exist in the manufacturing process;
4. the protective film needs to be torn off, so that the protective film is required to have low viscosity and stable viscosity, but the viscosity of the conventional polyurethane protective film is excessively increased along with the prolonging of the storage time, and the adhesive residue of the protective film can pollute the touch panel.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides the polyurethane protective film with low film tearing voltage, which simultaneously meets the requirements of low film tearing voltage, excellent antistatic performance, high transparency, no residual glue, no precipitation of antistatic agent, lower viscosity and more stable viscosity. The polyurethane protective film is suitable for manufacturing processes and shipment protection of a touch panel, a display panel and a flexible panel.
In order to achieve the purpose, the invention adopts the following technical scheme: a polyurethane protective film with low tearing voltage comprises a base film layer, an adhesive layer and a release film layer which are sequentially stacked from top to bottom. When the polyurethane protective film is used, the release film layer is separated from the adhesive layer, the base film layer is connected with an object to be protected through the adhesive layer, and the projection range of the base film layer on the object to be protected can be regarded as the protection range of the polyurethane protective film.
The base film layer contains the following components:
(a) a polyurethane resin;
(b) ethylene-alpha-olefin copolymers;
(c) an electrostatic agent.
The adhesive layer contains the following components:
(a) a polyurethane resin;
(b) ethylene-unsaturated ester copolymers;
(c) an electrostatic agent;
(d) and (4) an auxiliary agent.
The following synergistic effect is generated by the component compounding of the base film layer and the component compounding of the adhesive layer:
1. the base film layer and the adhesive layer are mutually soluble between layers, so that the adhesive has excellent connection strength;
2. the first electrostatic agent in the base film layer migrates from the inside of the base film layer toward the surface where they exert their effects without being precipitated, and the base film layer is excellent in antistatic properties; the second electrostatic agent in the adhesive layer can migrate from the inside of the adhesive layer to the surface where the second electrostatic agent plays a role without precipitation, and the antistatic performance of the adhesive layer is excellent, so that the film tearing voltage of the polyurethane protective film is low, and the manufacturing process requirements of a touch panel, a display panel and a flexible panel can be met;
3. the base film layer and the adhesive layer both have excellent transparency, so that the internal haze of the polyurethane protective film is high, the light transmittance of the polyurethane protective film is not lower than 90%, and the polyurethane protective film can be used for carrying out visual detection on the touch panel/the display panel/the flexible panel;
4. the adhesive layer is compounded by components, so that the film forming processability, viscosity, initial viscosity, viscosity after placement and adhesive residue performance of the adhesive layer are improved, and the polyurethane protective film is easy to tear off from the touch panel, the display panel and the flexible panel and cannot generate residues.
From the viewpoint of promoting adhesion between the base film layer and the adhesive layer, the polyurethane resin used for the base film layer is the same as the polyurethane resin used for the adhesive layer, and the polyurethane resin is polymerized from polyether polyol, polycarbonate polyol and polyester polyol.
From the viewpoint of making the adhesive layer thickness coat low in viscosity, it is preferable that the polyurethane resin is polymerized from polyether polyol, polycarbonate polyol, polyester polyol in a mass ratio of 1-5: 5-8: 1-4.
From the viewpoint of enhancing the transparency of the base film layer and taking into consideration the surface resistance value, it is preferable that the mass ratio of the polyurethane resin and the ethylene- α -olefin copolymer in the base film layer is 1: 10 to 20. The surface impedance value of the base film layer is not less than 10 8 Omega antistatic film, and the base film layer is a double-sided antistatic film.
From the viewpoint of improving the transparency of the adhesive layer and considering no adhesive residue, it is preferable that the mass ratio of the polyurethane resin and the ethylene-unsaturated ester copolymer in the adhesive layer is 5-10: 1.
The electrostatic agent comprises one or more of quaternary ammonium salt, alkylamine compound, cyclic amine compound, amidoamine salt and imidazoline salt ethyl acrylamide salt. In the base film layer, the amount of the electrostatic agent added is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the total amount of the component (a) and the component (b) in the base film layer. In the adhesive layer, the amount of the electrostatic agent to be added is preferably 0.01 to 1 part by weight, and more preferably 0.5 to 1 part by weight, based on 100 parts by weight of the total amount of the component (a) and the component (b) in the adhesive layer. From the viewpoint of reducing the peeling voltage, it is preferable that the electrostatic agent used for the base film layer and the electrostatic agent used for the adhesive layer are the same.
The auxiliary agent comprises nonvolatile alcohol, and preferably, the alcohol is higher alcohol with more than twelve carbon atoms. The auxiliary agent can endow the adhesive layer with lower tear film voltage, better stability of viscosity over time and better wettability of the protective film. The amount of the auxiliary added is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the total amount of the component (a) and the component (b) in the adhesive layer
Preferably, the thickness of the adhesive layer is 5-200 μm, more preferably 50-100 μm, and the improvement of the thickness of the adhesive layer can improve the buffering performance of the polyurethane protective film on one hand, so that the protection effect is improved in the conveying process, and on the other hand, foreign matters on the surface of the touch panel/display panel/flexible panel can be embedded, so that the cleaning and protection effects can be realized. Preferably, the thickness of the base film layer is preferably 20 to 200 μm, and the base film layer can improve the buffering performance of the polyurethane protective film.
The polyurethane protective film provided by the invention comprises a release film layer arranged on the adhesive layer. Preferably, the surface impedance value of the release film layer is not less than 10 6 Examples of the Ω double-sided antistatic release film include an organic silicon release film, a non-silicon non-fluorine release film, and a fluorine release film. Preferably, the thickness of the release film layer is 20 to 150 μm.
The base film layer can be made by virtually any film forming process known to those skilled in the art, which is a monolayer polymer film, and thus can be made by typical casting, extrusion, coextrusion, lamination, and the like, including orientation (uniaxial or biaxial) by various methods (e.g., film blowing, mechanical stretching, and the like). The base film layer contains an electrostatic agent. Examples of the method of mixing the components of the base film layer include a method of dry-mixing the respective polymers and fine particles and a method of melt-mixing.
The lamination of the adhesive layer and the base film layer may be prepared by extrusion coating or coextrusion.
In one embodiment, the urethane protective film is prepared by the following method: mixing polyurethane resin, ethylene-unsaturated ester copolymer containing ethylene-based monomer units and unsaturated ester-based monomer units, electrostatic agent and solvent, adding auxiliary agent, and stirring to obtain mixed solution; coating the mixed solution on the base film layer, drying at 80-120 ℃, then compounding with a release film, rolling, and curing at 40-50 ℃ for 40-60h to obtain the protective film. The solid content of the mixed solution is 50-70%. The solvent is a volatile organic solvent, and examples thereof include non-methane total hydrocarbons, benzenes, volatile halogenated hydrocarbons (dichloromethane, chloroform, etc.), alcohols (ethanol, isopropanol, ethylene glycol, etc.), ethers (diethyl ether, dibutyl ether, tetrahydrofuran, etc.), fatty acids, lipids (ethyl acetate), phenols (phenol, etc.), fatty aldehydes, fatty ketones, small-molecule polymers, polymerizable polymers (formaldehyde, ethylene oxide, acrylonitrile, etc.), thiols, amines (ethylenediamine, triethylamine, etc.), and other solvents (DMF, DMSO, etc.).
Examples of the method for producing the polyurethane protective film include a lamination method in which a single-layer film composed only of an adhesive-containing layer or a multilayer film including an adhesive layer and a release film layer is laminated on a base film layer. Examples of the lamination method include a dry lamination method, a wet lamination method, and a sandwich lamination method.
In one embodiment, the composite structure of the polyurethane protective film is prepared by extrusion lamination, for example, by laying an adhesive layer between a release film layer and a base film layer moving at high speed while in contact with a cold roll. And the release film layer and/or the base film layer may be pretreated or treated on-line to improve their surface properties and impact adhesive strength. The treatment may include, but is not limited to, corona treatment, flame treatment under oxidizing conditions, or reducing conditions.
The following description will be given with reference to specific examples.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a polyurethane protective film with low tearing voltage, which comprises a base film layer, an adhesive layer and a release film layer which are sequentially laminated from the outer side to the inner side.
The base film layer contains the following components:
(a) a polyurethane resin;
(b) ethylene-alpha-olefin copolymers;
(c) an electrostatic agent.
The adhesive layer contains the following components:
(a) a polyurethane resin;
(b) ethylene-unsaturated ester copolymers;
(c) an electrostatic agent;
(d) and (4) an auxiliary agent.
In the following examples, the polyurethane resin contained in the base film layer of the polyurethane protective film is the same as the polyurethane resin contained in the adhesive layer. The polyurethane resin is prepared by polymerizing polyether polyol, polycarbonate polyol and polyester polyol according to the feeding mass ratio of 1-5: 5-8: 1-4. Wherein the polyether polyol is one or more of bifunctional polyether polyol or trifunctional polyether polyol, the number average molecular weight of the polyether polyol is 400-4000, the hydroxyl value is 34-88mgKOH/g, and the viscosity at 23 +/-2 ℃ is 50-600 cps; the polycarbonate polyol is one or more of two-functionality or three-functionality polycarbonate polyol, the number average molecular weight of the polycarbonate polyol is 300-3000, the hydroxyl value is 34-88mgKOH/g, and the viscosity at 23 +/-2 ℃ is 300-4000 cps; the polyester polyol is one or more of polyester polyol with two-functionality or three-functionality, the number average molecular weight of the polyester polyol is 300-4000, the hydroxyl value is 34-88mgKOH/g, and the viscosity at 23 +/-2 ℃ is 2000-30000 cps. The polymerization method of the polyurethane resin may be a conventional method in the art.
The base film layer may contain only 1 component of the ethylene- α -olefin copolymer, or may contain 2 or more components of the ethylene- α -olefin copolymer. The ethylene-alpha-olefin copolymer in the base film layer includes monomer units based on ethylene and monomer units based on at least 1 alpha-olefin selected from alpha-olefins having 4 to 20 carbon atoms. Examples of the α -olefin include 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3, 3-dimethyl1-butene, 4-methyl-1-pentene, 1-octene. The α -olefin is preferably an α -olefin having 4 to 8 carbon atoms, and more preferably 1-butene, 1-hexene, 4-methyl-1-pentene, or 1-octene in view of easiness of obtaining. Examples of the ethylene- α -olefin copolymer include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-octene copolymer, an ethylene-1-butene-1-hexene copolymer, an ethylene-1-butene-4-methyl-1-pentene copolymer, an ethylene-1-butene-1-octene copolymer, and an ethylene-1-hexene-1-octene copolymer. The ethylene-alpha-olefin copolymer in the base film layer has a molecular weight distribution of 5 to 15, preferably 6 to 13, more preferably 7 to 11. The density of the ethylene-alpha-olefin copolymer used for the base film layer is preferably 900- 3 . The polymerization method of the ethylene- α -olefin copolymer used for the base film layer includes, for example, bulk polymerization, solution polymerization, slurry polymerization, gas phase polymerization, or high pressure ion polymerization, and various conditions such as polymerization temperature, polymerization pressure, monomer concentration, catalyst charge amount, and polymerization time in the polymerization step may be appropriately determined.
By adjusting the content of the ethylene-alpha-olefin copolymer in the base film layer, the internal haze of the base film layer can be controlled, the ethylene-alpha-olefin copolymer and the polyurethane resin generate a synergistic effect to enable the contact interface between the ethylene-alpha-olefin copolymer and the base film layer and the contact interface between the ethylene-alpha-olefin copolymer and the polyurethane resin to be mutually dissolved, so that the connection strength is improved, and meanwhile, the precipitation of an electrostatic agent in the base film layer is inhibited.
The adhesive layer may contain only 1 component of the ethylene-unsaturated ester copolymer, or may contain 2 or more types of the ethylene-unsaturated ester copolymer. The ethylene-unsaturated ester copolymer in the adhesive layer is a copolymer comprising an ethylene-based monomer unit and an unsaturated ester-based monomer unit. Examples of the unsaturated ester-based monomer unit include an α, β -unsaturated carboxylic acid alkyl ester-based monomer unit and a carboxylic acid vinyl ester-based monomer unit. Examples of the α, β -unsaturated carboxylic acid alkyl ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Examples of the vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate. The unsaturated ester-based monomer unit is preferably a methyl acrylate-based monomer unit, an ethyl acrylate-based monomer unit, a butyl acrylate-based monomer unit, a methyl methacrylate-based monomer unit, a vinyl acetate-based monomer unit.
Examples of the ethylene-unsaturated ester copolymer used for the adhesive layer include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl butyrate copolymer, and ethylene-vinyl benzoate copolymer, and ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-vinyl acetate copolymer are preferable, and ethylene-vinyl acetate copolymer is more preferable. A part of the monomer units of the ethylene-unsaturated ester copolymer used in the adhesive layer may be modified by hydrolysis or the like. Examples of the modified ethylene-unsaturated ester copolymer include a saponified ethylene-vinyl acetate copolymer. The ethylene-unsaturated ester copolymer used in the adhesive layer can be prepared by a high-pressure free radical polymerization method.
The content of the ethylene-unsaturated ester copolymer in the adhesive layer is adjusted, so that the internal haze of the adhesive layer can be controlled, the ethylene-unsaturated ester copolymer and the polyurethane resin generate a synergistic effect, the adhesive layer has the advantages of thick coating, low viscosity, stable viscosity over time and less residual adhesive, and the precipitation of an electrostatic agent in the adhesive layer is inhibited.
The base film layer and the adhesive layer of the polyurethane protective film may further contain additives such as an antioxidant, a lubricant, a processability improver, and the like as required. Examples of the antioxidant include a phenol-based stabilizer, a phosphite-based stabilizer, and a phenol-phosphite bifunctional stabilizer. Examples of the lubricant include erucic acid amide, higher fatty acid amide, and higher fatty acid ester. Examples of the processability improver include fatty acid metal salts such as calcium stearate.
In the following examples, the same electrostatic agent was used for the base film layer and the adhesive layer. The electrostatic agent comprises one or more of quaternary ammonium salt, alkylamine compound, cyclic amine compound, amido amine compound and imidazoline salt ethyl acrylamide salt.
Among them, the quaternary ammonium salt is not particularly limited, and examples thereof include: tetraalkylammonium salts, trialkylarylammonium salts, dialkyldiarylammonium salts, alkyltriarylammonium salts, tetraarylammonium salts, cycloammonium salts, and bicyclic ammonium salts. Specific examples thereof include: tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium hydroxide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, tetraoctylammonium bromide, tetradodecylammonium bromide, tetraphenylammonium bromide, tetranaphthylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrastearylammonium bromide, lauryltrimethylammonium bromide, stearoyltrimethylammonium bromide, behenyltrimethylammonium bromide, lauryltriethylammonium bromide, phenyltrimethylammonium bromide, 3-trifluoromethylphenyltrimethylammonium bromide, benzyltrimethylammonium bromide, dibenzyldimethylammonium bromide, distearyldimethylammonium bromide, tristearylmethylammonium bromide, benzyltriethylammonium bromide, hydroxyphenyltrimethylammonium bromide and N-methylpyridinium bromide. The quaternary ammonium salt is preferably tetrabutylammonium bromide, and the tetrabutylammonium bromide is a cationic surfactant.
Among them, the alkylamine compound is preferably an alkylamine salt or a polyoxyethylene alkylamine compound, more preferably dimethyldodecylamine, which is a cationic surfactant.
Among them, the cyclic amine compound is a polymer based on cationic cyclic amine. Examples of cyclic amine compounds containing at least one nitrogen atom in a ring structure include monoaminoalkylpiperazines, di (aminoalkyl) piperazines, monoaminoalkylimidazoles, aminoalkyl morpholines, aminoalkyl piperidines and aminoalkyl pyrrolidines. Examples of the cyclic amine compound having at least two active nitrogen atoms in the ring include imidazole and C-alkyl substituted imidazoles having 1 to 25 carbon atoms in the alkyl group (e.g., 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole and 2-isobutylimidazole), C-alkyl substituted imidazolines having 1 to 25 carbon atoms in the alkyl group and aryl imidazolines, N-alkyl piperazines having 1 to 25 carbon atoms in the alkyl group, and N, N' -dialkyl piperazines having 1 to 25 carbon atoms in the alkyl group. The cyclic amine compound is preferably a cyclic amine compound having at least two active nitrogen atoms, and more preferably at least one of melamine, 2-hydroxybenzimidazole, and 2-aminobenzimidazole.
Of these, the amidoamine compound is a cationic surfactant, and preferably, the amidoamine compound is a tertiary amidoamine having an alkyl group of from about 12 to about 22 carbons. Exemplary tertiary amido amines include: stearamidopropyl dimethylamine, stearamidopropyl diethylamine, stearamidoethyl dimethylamine, palmitamidopropyl diethylamine, palmitamidoethyl dimethylamine, behenamidopropyl diethylamine, behenamidoethyl dimethylamine, arachidopropyl diethylamine, arachidoethyl dimethylamine, diethylaminoethyl stearamide.
[ examples ]
Examples 1-5 each provide a polyurethane protective film. The polyurethane protective film comprises a base film layer, an adhesive layer and a release film layer which are sequentially stacked from top to bottom.
Specific composition parameters of the polyurethane protective films provided in examples 1 to 3 are shown in table 1.
Specific composition parameters of the polyurethane protective films provided in examples 4-5 are shown in table 2.
The thicknesses of the layers of the polyurethane protective films provided in embodiments 1 to 3 are the same, the thickness of the base film layer is 100 μm, the thickness of the adhesive layer is 80 μm, the thickness of the release film layer is 30 μm, and the release film layer is an organosilicon double-sided antistatic release film.
The preparation methods of the polyurethane protective films provided in examples 1 to 3 are the same, and all the methods comprise the following steps:
step one, polyurethane resin is polymerized by polyether polyol (PPG, CAS number: 9003-11-6), polycarbonate polyol (CAS number: 29862-10-0) and polyester polyol (CAS number: 32472-85-8) according to the mass ratio of 2: 7: 2;
step two, blown film forming: the components of the base film layer were mixed with a tumble mixer as shown in table 1. The obtained mixture was molded into a base film layer by using an extruder, a die, and a blow molding machine having a die lip opening of 2.0mm under conditions of an extrusion rate of 25kg/hr at 150 ℃, a blow molding ratio of 2.0, and a film thickness of 100 μm. Performing corona discharge treatment on one surface of the obtained blow-molded film tube of the base film layer in a manner that the wetting tension is 45 dyn/cm;
step three, forming a multilayer film: using ethyl acetate as a solvent, adding the components of the adhesive layer into ethyl acetate to form a coating liquid according to table 1, wherein the solid content of the coating liquid is 70%, coating the obtained coating liquid on the base film layer by using a coating machine, pressing the obtained adhesive layer and the corona-treated surface of the base film layer obtained by the above operation, and heating in an oven at 80 ℃ for 48 hours to obtain a multilayer film;
and step four, compounding the multilayer film and the release film layer, rolling, and curing in an oven at 45 ℃ for 48 hours.
The preparation methods of the polyurethane protective films provided in examples 4 to 5 are the same, and all the methods comprise the following steps:
step one, polyurethane resin is polymerized by polyether polyol (PPG, CAS number: 9003-11-6), polycarbonate polyol (CAS number: 29862-10-0) and polyester polyol (CAS number: 32472-85-8) according to the mass ratio of 3: 8: 2;
step two, manufacturing the components of the base film layer and the single-layer base film layer by using the existing blow molding film forming process according to the components shown in the table 2;
step three, adding the components of the adhesive layer into a mixed solution of toluene, butanone and ethyl acetate in a mass ratio of 1: 2 according to the table 2 to form a coating liquid, wherein the solid content of the coating liquid is 70%, coating the coating liquid on the base film layer, drying at 90 ℃, and obtaining a multilayer film, wherein the residual amount of the solvent in the drying oven is less than 50 PPM;
and step four, compounding the multilayer film and the release film layer, rolling, and curing in an oven at 45 ℃ for 48 hours.
TABLE 1
Figure BDA0003673095090000121
TABLE 2
Figure BDA0003673095090000122
The polyurethane protective films provided in examples 1 to 5 were subjected to the following tests.
[ haze ]
As the haze, the haze (unit:%) of the polyurethane protective film (thickness 210 μm) was measured in accordance with ASTM 1003. The smaller the haze, the more excellent the transparency. The results are shown in Table 3.
[ internal haze ]
The internal haze (unit:%) of the film in the immersed state was measured by immersing a polyurethane protective film (thickness 210 μm) in a transparent bath containing dimethyl phthalate in accordance with ASTM 1003. The smaller the internal haze, the more excellent the transparency. The results are shown in Table 3.
[ light transmittance ]
Test method according to GB/T24102008 (light transmission haze test). The temperature of the test environment was 21 to 25 ℃ and the humidity was 50 to 65% RH, the polyurethane protective film thus produced was cut into a sample of 10cm × 10cm, and the light transmittance of the sample was measured using a standard plate spectrometer (PT-103). The results are shown in Table 3.
[ blocking Property between base film layer and adhesive ]
Compounding the base film layer and the adhesive layerThe resulting multilayer film (thickness: 180 μm) was cut into pieces of 10cm X10 cm, and then placed in an oven adjusted to 40 ℃ in an oven at 400g/cm 2 Under the load of (3), the state adjustment was carried out for 7 days. After the state adjustment, the amount of load (upper and lower BL, unit: N/m) necessary for peeling in the vertical direction at a peeling load speed of 20g/min was measured using a blocking tester (McKenzie) 2 ). The larger the value, the more excellent the blocking resistance of the base film layer and the adhesive layer. The results are shown in Table 3.
[ tackiness of polyurethane protective film ]
The manufactured polyurethane protective film is torn off from the release film layer to test the viscosity, and the viscosity testing method is GB/T2792-1998. The results are shown in Table 3.
[ adhesive Strength and adhesive residue Property with glass substrate ]
The produced polyurethane protective film was peeled off from the release film layer, and then laminated (with the polyurethane protective film covering the glass substrate) in contact with a glass substrate (width × length: 10mm × 15mm), and the obtained sample was left at 23 ℃ for 24 hours or more, and then peeled off at 180 ° at a speed of 300mm/min by a tensile tester, and the adhesive strength per 15mm width was measured. If the bonding strength is 5-20N/15mm, the adhesive has sealing property and is easy to tear. After the polyurethane protective film and the glass substrate were separated, the surface of the glass substrate was observed for the presence of white haze and transfer. The results are shown in Table 4.
[ adhesive Strength and adhesive residue Property with polyimide substrate ]
The produced polyurethane protective film was peeled off from the release film layer, and then was laminated in contact with a polyimide substrate (the polyurethane protective film covered the polyimide substrate), and the polyimide substrate was cut by laser cutting to obtain a sample (width × length: 10mm × 15 mm). The sample was left to stand at an ambient temperature of 20 to 25 ℃ and an ambient humidity of 50 to 60% RH for 60 days, and then peeled off at 180 ℃ at a speed of 300mm/min by a tensile tester, and the adhesive strength per 15mm width was measured. If the bonding strength is 5-20N/15mm, the adhesive has sealing property and is easy to tear. After the polyurethane protective film and the polyimide substrate were separated, the presence or absence of white haze and transfer on the surface of the polyimide substrate was observed. The results are shown in Table 4.
[ tear film Voltage test ]
The test method is in accordance with GB/T33375-2016 (tear-off Voltage test). Placing the prepared polyurethane protective film for 2H under the conditions that the environmental temperature is 20-25 ℃ and the environmental humidity is 50-60% RH, then cutting the polyurethane protective film into samples of 8cm multiplied by 15cm, tearing off the release film layer of the samples, and then attaching the samples to a clean test screen of a tear film voltage tester (FMX-003). And (3) wearing the anti-static gloves and the hand ring by a tester, tearing the sample from the test screen at a speed of not more than 20cm/s, and measuring the highest static value on the test screen at the moment of stripping. The results are shown in Table 4
It can be seen from tables 3 and 4 that the polyurethane protective film provided by the present invention can simultaneously satisfy low tear film voltage, excellent antistatic property, high transparency, no adhesive residue, no precipitation of antistatic agent, low viscosity and stable viscosity. The polyurethane protective film is suitable for manufacturing processes and shipment protection of a touch panel, a display panel and a flexible panel.
TABLE 3
Figure BDA0003673095090000151
TABLE 4
Figure BDA0003673095090000152
Note: "×" "Δ" "o" indicates a degree of severe NG, mild, OK, respectively. Specifically, the method comprises the following steps: residual adhesive property: x represents that white fog of residual gum is obvious; Δ indicates, slight cull; and o indicates no adhesive residue.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (7)

1. The utility model provides a polyurethane protection film of low dyestripping voltage, includes by last base membrane layer, gluing agent layer and the release film layer that stacks gradually under to, its characterized in that, base membrane layer contains: a polyurethane resin, an ethylene-alpha-olefin copolymer, and an electrostatic agent; the adhesive layer contains: polyurethane resin, ethylene-unsaturated ester copolymer, electrostatic agent and auxiliary agent.
2. The polyurethane protective film according to claim 1, wherein the polyurethane resin is formed by polymerizing polyether polyol, polycarbonate polyol, and polyester polyol in a mass ratio of 1-5: 5-8: 1-4.
3. The protective polyurethane film according to claim 1, wherein the mass ratio of the polyurethane resin to the ethylene- α -olefin copolymer in the base film layer is 1: 10 to 20.
4. The polyurethane protective film according to claim 1, wherein the mass ratio of the polyurethane resin to the ethylene-unsaturated ester copolymer in the adhesive layer is 5-10: 1.
5. The protective polyurethane film of claim 1, wherein the electrostatic agent comprises one or more of quaternary ammonium salt, alkylamine compound, cyclic amine compound, salt of amidoamine, and imidazolinium salt of ethylacrylamide.
6. The protective polyurethane film of claim 1, wherein the auxiliary agent comprises a nonvolatile alcohol, and the alcohol is a higher alcohol having twelve carbon atoms or more.
7. The polyurethane protective film according to claim 1, wherein the thickness of the base film layer is 20 to 200 μm, the thickness of the adhesive layer is 5 to 200 μm, and the thickness of the release film layer is 20 to 150 μm.
CN202210610646.6A 2022-05-31 2022-05-31 Polyurethane protective film with low film tearing voltage Withdrawn CN114874709A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109111868A (en) * 2018-07-16 2019-01-01 苏州大胜电材有限公司 A kind of ultralow dyestripping voltage polyurethane protective film and preparation method thereof
CN109952355A (en) * 2016-11-10 2019-06-28 汉高股份有限及两合公司 Reactive hot melt adhesive composition and application thereof
CN111303789A (en) * 2020-03-24 2020-06-19 广东硕成科技有限公司 Anti-static wafer cutting protective film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109952355A (en) * 2016-11-10 2019-06-28 汉高股份有限及两合公司 Reactive hot melt adhesive composition and application thereof
CN109111868A (en) * 2018-07-16 2019-01-01 苏州大胜电材有限公司 A kind of ultralow dyestripping voltage polyurethane protective film and preparation method thereof
CN111303789A (en) * 2020-03-24 2020-06-19 广东硕成科技有限公司 Anti-static wafer cutting protective film and preparation method thereof

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