WO2014166339A1 - 双向拉伸聚酯亚光预涂膜及其制备方法 - Google Patents

双向拉伸聚酯亚光预涂膜及其制备方法 Download PDF

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Publication number
WO2014166339A1
WO2014166339A1 PCT/CN2014/074160 CN2014074160W WO2014166339A1 WO 2014166339 A1 WO2014166339 A1 WO 2014166339A1 CN 2014074160 W CN2014074160 W CN 2014074160W WO 2014166339 A1 WO2014166339 A1 WO 2014166339A1
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Prior art keywords
matte
coating
film
oriented polyester
biaxially oriented
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PCT/CN2014/074160
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English (en)
French (fr)
Inventor
钟玉
武俊
王慧荣
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北京康得新复合材料股份有限公司
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Publication of WO2014166339A1 publication Critical patent/WO2014166339A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/06—Polyethene
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • 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
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • 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
    • 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
    • C09J2431/00—Presence of polyvinyl acetate
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Definitions

  • the present invention relates to the field of printing technology, and in particular, the present invention relates to a biaxially stretched polyester matte precoat film and a process for the preparation thereof. Background technique
  • biaxially oriented polyester (BOPET) films are widely used for superior performance.
  • BOPET is colorless, odorless, tasteless, non-toxic, high tensile strength, toughness and good transparency. It can be well protected against water and tears after being applied to the packaging material.
  • the polyester film currently used in the packaging industry is usually bright. The matt polyester film has a special effect on the surface, and it can give a simple and heavy feeling on the packaging material. , very popular with consumers.
  • Matte polyester film is usually prepared by a multi-layer co-extrusion process, which is divided into two different preparation techniques.
  • One is to add an inorganic or organic matt additive to the surface layer of BOPET to produce a matt effect.
  • the BOPET matt film prepared by these two techniques generally has a high haze, a low light transmittance, and a poor matt effect. After being processed into a pre-coated film to cover the surface of the printed matter, the color of the printed product is easily distorted, thus limiting Its application in the packaging film industry.
  • CN102816512 discloses an anti-scratch water-based wood coating which is modified by an acrylic modified polyurethane emulsion, a film forming auxiliary agent, an antifoaming agent, a deionized water, a wetting agent, and a mass ratio of 48 to 52% aryl fluorene. It consists of a methyl mercapto silicon solution, a wax emulsion, a thickener and a preservative.
  • the coating disclosed in CN102816512 is only suitable for wood materials, forming a coating having scratch resistance on the surface of wooden furniture.
  • CN101564720 discloses a preparation method of a biaxially stretched polyester film surface abrasion resistant scratch resistant coating, comprising: polyurethane hexaacrylate, epoxy modified acrylate, dipentaerythritol monohydroxy hexaacrylate, trihydroxyl Methylpropionate triacrylate, tripropylene glycol diacrylate, butyl titanate and composite cracking photoinitiator are uniformly mixed to obtain a coating; then the coating is applied to the surface of the corona treated BOPET film and cured by ultraviolet light. , that is, the biaxially stretched polyester film surface wear-resistant scratch-resistant coating.
  • the biaxially oriented polyester film surface abrasion resistant scratch resistant coating disclosed in CN101564720 requires UV curing.
  • the present invention aims to solve at least one of the technical problems existing in the prior art.
  • one object of the present invention is A biaxially stretched polyester matte precoat film and a preparation method thereof are proposed.
  • the invention provides a biaxially oriented polyester matte precoat film.
  • the biaxially stretched polyester matte precoat film comprises: a substrate composed of a bright biaxially oriented polyester film and a matt coating, wherein the matt coating is passed Forming a matt varnish on the first surface of the bright biaxially oriented polyester film; an intermediate layer, the intermediate layer being coated with polyethylene on the second surface of the bright biaxially oriented polyester film Formed by an aqueous amine solution; and a hot melt adhesive layer, which is selected from the group consisting of ethylene-vinyl acetate, low density polyethylene, ethylene-ethyl acrylate, and ethylene-methyl acrylate by an extrusion compounding process.
  • the biaxially stretched polyester matte precoat film has high color saturation, suitable mattity, high tensile strength, high width and flatness, and improved printing. The vibrantness of the product.
  • the biaxially stretched polyester matte precoat film of the present invention is used in various materials such as wood materials, metal materials, high molecular materials, etc., and does not require ultraviolet curing during preparation.
  • the biaxially stretched polyester matte precoat film has a matte surface haze of 45-80% at a measuring angle of 60°, and the transparency of the film can be achieved. 80-95%.
  • the matt varnish comprises: 65 to 90 parts by weight of a polyurethane-based substance; 1 to 10 parts by weight of a matt auxiliary; 0 to 12 parts by weight of a crosslinking curing agent; 1 to 2 parts by weight Part of the film forming aid; 0.2 0.3 parts by weight of the antifoaming agent; and 0.05 to 0.1 part by weight of the wetting agent.
  • the polyurethane-based substance is at least one selected from the group consisting of an aqueous polyurethane emulsion and a solvent-based polyurethane dispersion.
  • the polyurethane dispersion is at least one selected from the group consisting of an acrylic modified polyurethane, a polyester modified polyurethane, a polycarbonate modified polyurethane, and an aliphatic polyurethane.
  • the matt auxiliary agent is at least one selected from the group consisting of silica, micronized wax, and organic matt auxiliary.
  • the crosslinking curing agent is at least one selected from the group consisting of polyfunctional aziridine, HDI trimer, HDI-IPDI complex trimer, and polycarbodiimide.
  • the film-forming auxiliary agent is at least one selected from the group consisting of N-methylpyrrolidone, decadiol, ethylene glycol, and diethylene glycol monobutyl ether.
  • the wetting agent is at least one selected from the group consisting of ethanol, isopropanol, polysiloxane, and modified silicone.
  • the antifoaming agent is at least one selected from the group consisting of polydimethylsiloxane, ethanol, and polyoxypropylene glyceryl ether.
  • the substrate has a thickness of from 13 to 110 microns, preferably from 13 to 75 microns.
  • the bright biaxially oriented polyester film has a thickness of 10 to 100 ⁇ m, and the matte coating layer has a thickness of 1 to 10 ⁇ m.
  • the aqueous solution of the polyethyleneimine has a solid content of from 0.5 to 1.5%.
  • the coating amount of the aqueous solution of polyethyleneimine is from 0.009 to 0.011 g/m 2
  • the thickness of the intermediate layer is from 0.01 to 0.03 ⁇ m, preferably, the aqueous solution of polyethyleneimine
  • the coating amount is from 0.009 to 0.010 g/m%.
  • the intermediate layer has a thickness of from 0.01 to 0.02 m.
  • the hot melt adhesive layer has a thickness of from 25 to 100 microns, preferably from 15 to 75 microns.
  • the matt varnish is applied by at least one selected from the group consisting of roll coating and spray coating.
  • a drying treatment is performed at 85 to 95 to form the intermediate layer.
  • the at least one selected from the group consisting of ethylene vinyl acetate, low density polyethylene, ethylene ethyl acrylate, and ethylene methyl acrylate is compounded on the intermediate layer, in an ozone atmosphere In progress.
  • the ozone atmosphere is achieved by an ozone generator having a power of 800 W, an ozone concentration of 40% in the ozone atmosphere, and a gas flow rate of 3.5 SCXFM.
  • the invention provides a method of preparing a biaxially oriented polyester matte precoat film.
  • the method comprises the steps of: applying a matt varnish to the first surface of the bright biaxially oriented polyester film to form a matt coating, the bright biaxially oriented polyester film and the a matt coating layer forming a substrate of the biaxially stretched polyester matte precoat film; coating a second surface of the bright biaxially oriented polyester film with an aqueous solution of polyethyleneimine to form an intermediate layer;
  • at least one selected from the group consisting of ethylene-vinyl acetate, low density polyethylene, ethylene-ethyl acrylate, and ethylene-methyl acrylate is compounded on the intermediate layer to form a hot melt adhesive layer.
  • the biaxially stretched polyester matte precoat film (BOPET) obtained by the method according to the embodiment of the present invention has high color saturation, suitable mattity, high tensile strength, high stiffness and high flatness. Improve the extraordinarness of the print. Further, the biaxially stretched polyester matt precoated film obtained by the method according to the embodiment of the present invention is used for various materials such as wood materials, metal materials, polymer materials, and the like, and ultraviolet curing is not required in the preparation process.
  • the biaxially stretched polyester matte precoat film (BOPET) obtained according to a specific embodiment of the present invention has a matte surface haze of 45-80% at a measuring angle of 60°, and the transparency of the film Up to 80-95%.
  • the matt varnish comprises: 65 to 90 parts by weight of a polyurethane-based substance; 1 to 10 parts by weight of a matt auxiliary; 0 to 12 parts by weight of a crosslinking curing agent; 1 to 2 parts by weight Part of the film forming aid; 0.2 0.3 parts by weight of the antifoaming agent; and 0.05 to 0.1 part by weight of the wetting agent.
  • the polyurethane-based substance is at least one selected from the group consisting of an aqueous polyurethane emulsion and a solvent-based polyurethane dispersion.
  • the polyurethane dispersion is at least one selected from the group consisting of an acrylic modified polyurethane, a polyester modified polyurethane, a polycarbonate modified polyurethane, and an aliphatic polyurethane.
  • the matt auxiliary agent is at least one selected from the group consisting of silica, micronized wax, and organic matt auxiliary.
  • the crosslinking curing agent is at least one selected from the group consisting of polyfunctional aziridine, HDI trimer, HDI-IPDI complex trimer, and polycarbodiimide.
  • the film-forming auxiliary agent is at least one selected from the group consisting of N-methylpyrrolidone, decadiol, ethylene glycol, and diethylene glycol monobutyl ether.
  • the wetting agent is at least one selected from the group consisting of ethanol, isopropanol, polysiloxane, and modified silicone.
  • the antifoaming agent is at least one selected from the group consisting of polydimethylsiloxane, ethanol, and polyoxypropylene glyceryl ether.
  • the substrate has a thickness of from 13 to 110 microns, preferably from 13 to 75 microns.
  • the brightness biaxial stretching The polyester film has a thickness of 10 to 100 ⁇ m, and the matt coating layer has a thickness of 1 to 10 ⁇ m.
  • the aqueous solution of the polyethyleneimine has a solid content of from 0.5 to 1.5%.
  • the coating amount of the aqueous solution of polyethyleneimine is from 0.009 to 0.01 lg/m 2 , and the thickness of the intermediate layer is from 0.01 to 0.03 ⁇ m, preferably, the aqueous solution of polyethyleneimine The coating amount is from 0.009 to 0.010 g/m 2 , and the intermediate layer has a thickness of from 0.01 to 0.02 ⁇ m.
  • the hot melt adhesive layer has a thickness of from 25 to 100 microns, preferably from 15 to 75 microns.
  • the matt varnish is applied by at least one selected from the group consisting of roll coating and spray coating.
  • the ozone atmosphere is achieved using an ozone generator having a power of 800 W, an ozone concentration in the ozone atmosphere of 40%, and a gas flow rate of 3.5 SCXFM.
  • the biaxially stretched polyester (BOPET) matte precoat film may be composed of a substrate, an intermediate layer and a hot melt adhesive layer, wherein the substrate is a biaxially stretched matt polyester.
  • Film (BOPET) the middle layer is coated with a polyethyleneimine (PEI) aqueous solution having a solid content of 0.5-1.5%, and the coating amount is 0.009-0.011 g/m 2 , and the PEI is evenly distributed after drying.
  • Film surface; the hot melt adhesive layer is one or more of ethylene vinyl acetate (EVA), low density polyethylene (LDPE), ethylene ethyl acrylate (EEA), and ethylene methyl acrylate (EMA). Blended.
  • EVA ethylene vinyl acetate
  • LDPE low density polyethylene
  • EOA ethylene ethyl acrylate
  • EMA ethylene methyl acrylate
  • the thickness of the substrate is between 13-110 microns
  • the thickness of the intermediate layer is between 0.01-0.03 microns (coating amount is 0.009-0.011 g/m 2 )
  • the thickness of the hot melt adhesive layer is between 12-100 microns.
  • the thickness of the matt substrate is preferably between 13 and 75 microns
  • the thickness of the intermediate layer is preferably between 0.01 and 0.02 microns (coating amount is between 0.009 and 0.010 g/m 2 ).
  • the thickness of the hot melt adhesive layer composite is preferably between 15 and 75 microns.
  • the matt substrate is composed of a polyester (PET) layer and a matt coating.
  • the thickness of the polyester layer (4) is between 10 and 100 microns, and the thickness of the matt coating is between 1 and 10 microns.
  • the matt coating is mainly composed of a polyurethane-based substance or the like which is formed by applying a matt varnish to the surface of the film by roll coating or spraying, and drying.
  • the matt varnish described herein may be aqueous or solvent-based, and its main component comprises 60-90 parts of polyurethane dispersion: 0-10 parts of matt auxiliary; 0-12 parts of crosslinking curing agent; - 2 parts of film-forming aid; 0.05-0.1 part of wetting agent; 0.1-0.5 part of antifoaming agent.
  • the polyurethane dispersion may be one or a combination of an acrylic modified polyurethane, a polyester modified polyurethane, a polycarbonate modified polyurethane or an aliphatic polyurethane.
  • the matt auxiliary may use one or more of silica, micronized wax, and organic matt auxiliary agent, and the average particle diameter is 1-10 micrometers.
  • the matt auxiliaries selected in the invention are dispersed in the polyurethane dispersion to form a microscopic unevenness on the surface of the coating, and diffuse reflection is used to eliminate the light.
  • the crosslinking curing agent is Compounding of one or more of polyfunctional aziridine, HDI trimer or HDI-IPDI complex trimer, polycarbodiimide.
  • the cross-linking curing agent selected in the present invention can cross-link with functional groups such as a hydroxyl group and a carboxyl group in the polyurethane dispersion, thereby improving the hardness of the coating layer and its adhesion to the BOPET substrate.
  • the film forming aid is a compound of one or more of N-methylpyrrolidone, decadiol, ethylene glycol, and diethylene glycol monobutyl ether.
  • the film-forming auxiliary agent of the invention can improve the film-forming property of the polyurethane dispersion, help the film formation, and volatilize the film-forming auxiliary agent after film formation, without affecting the performance of the film.
  • the wetting agent is a compound of one or more of ethanol, isopropanol, modified or unmodified polysiloxane. This wetting leveling agent improves the wetting ability of the matt coating on the surface of the BOPET substrate, improves the adhesion of the coating to the surface of the BOPET, and also makes the surface of the coating smoother and denser.
  • the antifoaming agent is one or more of polydimethylsiloxane, ethanol, polyoxypropylene glyceryl ether.
  • the defoaming agent selected in the invention can eliminate small bubbles formed by high-speed stirring and cross-linking reaction, and eliminate the influence of bubbles on the appearance of the coating.
  • the present invention also provides a method for preparing a biaxially stretched polyester (BOPET) matt pre-coated film, and the technical solution adopted by the present invention comprises coating and matt of a matt coating.
  • the preparation of BOPET pre-coated film in two aspects. One is the coating of a matt coating. On the outer surface of the ordinary bright BOPET film polyester layer, a matt coating with uniform colorlessness, good adhesion and excellent transparency is formed on the surface of the BOPET by a coating process to obtain a BOPET matt film substrate.
  • 65 to 90 parts of polyurethane dispersion, 1 to 10 parts of matt auxiliary, 0 to 12 parts of crosslinking curing agent, 1 to 2 parts of film forming aid, 0.2 0.3 parts of defoaming agent and 0.05 ⁇ 0.1 part of the wetting agent and other components are uniformly mixed in the mixing tank, added to the trough in the coating line, coated with a matt coating on the surface of the BOPET substrate by a suitable coating process, and matt after drying.
  • the thickness of the coating is between 1 and 10 microns.
  • the second is the preparation of matt BOPET precoat film.
  • the BOPET matt pre-coated film was prepared by sequentially coating and laminating the intermediate layer and the hot-melt adhesive layer (3) on the inner surface of the BOPET film polyester layer by extrusion compounding. After the substrate and the thickness of the hot melt adhesive layer are properly combined, different ones can be obtained.
  • a polyethyleneimine (PEI) aqueous solution with a solid content of 5-10% is formulated into a polyethyleneimine (PEI) aqueous solution with a solid content of 0.5-1.5%, and stirred uniformly to obtain an intermediate layer material. .
  • PEI polyethyleneimine
  • Unwinding The above coated wire treated with a matt coated BOPET matt substrate is placed on a unwinder and unwound through an inflation shaft, that is, the substrate in which the raw material is rolled is unrolled.
  • Pre-corona treatment The surface of the above-mentioned BOPET matt substrate to which the intermediate layer is to be applied is subjected to corona treatment so that the dyne value of the above matt substrate reaches 54 dyne or more.
  • the intermediate layer material is applied to the corona-treated surface of the matt BOPET substrate by a primer coating device, and the amount of the intermediate layer material is 0.009-0.010 g/m 2 .
  • Drying Drying the matt BOPET substrate coated with polyethyleneimine (PEI) aqueous solution by drying equipment, and curing polyethyleneimine (PEI) on the surface of the matt substrate.
  • the drying temperature is 85-95 ° C, the thickness of the intermediate layer after drying is about 0.01-0.03 microns.
  • Extrusion of composite hot melt adhesive layer BOPET matt substrate carrying dried polyethyleneimine (PEI), which is sent to the composite part through the guide roll of the extrusion compounding line, and the extruder extrudes the hot melt
  • PEI polyethyleneimine
  • the glue layer is applied to the matt substrate
  • an ozone generator is arranged beside the composite part of the extrusion compounding line, and ozone generated by the ozone generator is sprayed to the casting place of the hot melt adhesive layer extruded by the extruder,
  • concentration of ozone is 40%, the power is 800 W, and the gas flow rate is 3.5 SCXFM.
  • Ozone produces some polar groups on the surface of the hot melt adhesive layer, and then the matt scratch resistant substrate with polyethyleneimine (PEI) is The hot melt adhesive casting is combined with the extrusion of the engaging rolls of the composite part of the extrusion composite line to form a composite film, which is then subjected to stretching, cooling, trimming, and then sent to a thickness gauge for inspection.
  • PEI polyethyleneimine
  • the pressure of the engaging roller is 35 PSI, and the temperature setting values of the extruder are 130, 160, 190, 200, 220, 220, 220, 220, 220, 220, 220, 220, 220, 220, 220, 220, 220, respectively. 220, 220, 220 °C.
  • Thickness measurement and adjustment The thickness of the pre-coated film is measured by a beta ray measuring instrument. After the measurement, the result is fed back to the computer, and the screw speed of the extruder and the lip opening of the die part are controlled by the computer to obtain the thickness. Uniform pre-coated film.
  • Post corona treatment Corona treatment is performed on the surface of the hot melt adhesive layer to obtain a certain amount of polar groups, so that the surface of the hot melt adhesive layer (3) reaches a value of 50 or more.
  • Winding The corrugated pre-coated film after corona is collected into a coil by a winder.
  • the matt ⁇ precoat film prepared by the present invention has a matt surface haze of 45-80% and a film transparency of 80-95% at a measuring angle of 60°.
  • the matt prepreg film prepared by the invention has the characteristics of high color saturation, suitable mattity, high tensile strength, high width and high flatness, and improves the delicateness of the printed product.
  • 1 is a schematic view showing the structure of a matt precoated film according to an embodiment of the present invention, wherein: 1 indicates a substrate, 2 indicates an intermediate layer, 3 indicates a hot melt adhesive layer, and 4 indicates a bright biaxially stretched polyester film. 5 indicates a matt coating.
  • a biaxially oriented polyester (BOPET) matt precoat film having a width of 1300 mm is described in detail as an example.
  • a BOPET matt substrate 1 is prepared first.
  • the substrate 1 is composed of a polyester layer 4 and a matt coating 5.
  • the polyester layer 4 has a thickness of 12 ⁇ m and the matt coating 5 has a thickness of 3 ⁇ m.
  • the biaxially oriented polyester film 4 is first processed by using a biaxially oriented polyester production apparatus, and a matt coating is uniformly applied to one surface thereof to obtain a substrate 1, and the substrate 1 has a thickness of 15 ⁇ m.
  • the precoat film is formed by sequentially coating the inner surface of the above-mentioned BOPET matte substrate 1 with a tantalum intermediate layer 2 of ⁇ . ⁇ and a composite hot melt adhesive EVA layer 3 of 25 ⁇ m. Since the trimming is required in the process of laminating the hot melt adhesive layer 3, the specification of the final BOPET matt precoat film becomes 40 ⁇ m ⁇ *1300 ⁇ *12000 ⁇ .
  • the processing method is as follows:
  • a polyethyleneimine (hydrazine) aqueous solution having a solid content of 5% is formulated into an aqueous solution of polyethyleneimine ( ⁇ ) having a solid content of 0.95%, and uniformly stirred to obtain an intermediate layer 2 material.
  • Pre-corona treatment The surface of the above-mentioned BOPET matt substrate 1 to which the intermediate layer 2 is to be applied is subjected to corona treatment so that the dyne value of the matt substrate 1 is 54 dyne or more.
  • the intermediate layer 2 is coated on the corona treated surface of the matt BOPET substrate 1 by the primer coating device, and the amount of the intermediate layer 2 is 0.009-0.010 g. /m 2 .
  • Drying Drying matt BOPET substrate 1 coated with polyethyleneimine (PEI) aqueous solution by drying equipment, curing polyethyleneimine (PEI) on the surface of matt substrate 1, drying The temperature is 85-95 ° C, and the thickness of the intermediate layer 2 after drying is about 0.01-0.03 ⁇ m.
  • PEI polyethyleneimine
  • Extrusion of composite hot melt adhesive layer 3 BOPET matt substrate 1 carrying dried polyethyleneimine (PEI), which is sent to the composite part through the guide rolls of the extrusion compounding line, and extruded by an extruder
  • the hot melt adhesive layer 3 is applied to the matt substrate 1; an ozone generator is arranged beside the composite portion of the extrusion composite production line, and ozone generated by the ozone generator is sprayed to the hot melt adhesive layer extruded by the extruder 3
  • the casting area, the concentration of ozone is 40%, the power is 800 W, the gas flow is 3.5 SCXFM, and the ozone makes the heat
  • the surface of the melted layer 3 generates some polar groups, and then the matte anti-scratch substrate 1 carrying the polyethyleneimine (PEI) and the hot melt adhesive are cast through the extrusion roller of the composite part of the extrusion composite line.
  • a composite film is formed, which is then stretched, cooled, and trimmed, and then sent to
  • the pressure of the engaging roller is 35 PSI, and the temperature setting values of the extruder are 130, 160, 190, 200, 220, 220, 220, 220, 220, 220, 220, 220, 220, 220, 220, 220, 220, respectively. 220, 220, 220 °C.
  • Thickness measurement and adjustment The thickness of the pre-coated film is measured by a beta ray measuring instrument. After the measurement, the result is fed back to the computer, and the screw speed of the extruder and the lip opening of the die part are controlled by the computer to obtain the thickness. Uniform pre-coated film.
  • Post corona treatment Corona treatment is performed on the surface of the hot melt adhesive layer 3 to obtain a certain amount of polar groups, so that the surface of the hot melt adhesive layer (3) reaches a value of 50 or more.
  • a biaxially oriented polyester (BOPET) matt precoat film having a width of 1650 mm is taken as an example for detailed description.
  • a BOPET matt substrate 1 is prepared first. 83.2 parts of aliphatic waterborne polyurethane emulsion (INCOREZ)
  • a BOPET matte precoat film Preparation of a BOPET matte precoat film.
  • the precoat film was formed by sequentially coating a ⁇ . ⁇ ⁇ intermediate layer 2, 25 ⁇ m of a composite hot melt adhesive LDPE layer on the bright surface of the above-mentioned BOPET matt substrate 1. Since the trimming is required in the process of laminating the hot melt adhesive layer 3, the final matte scratch resistant BOPET precoat film has a specification of 40 ⁇ m**1650 ⁇ *12000 ⁇ .
  • the processing method was similar to that of Example 1, except that: Example 2 used LDPE as the hot melt adhesive layer 3.
  • a biaxially oriented polyester (BOPET) matt precoat film having a width of 1650 mm is taken as an example for detailed description.
  • a BOPET matt substrate 1 was first prepared. 89.92 parts of solvent-based polycarbonate type polyurethane dispersion (B01-7), 0.03 parts of defoamer (XPT-118), 0.05 parts of leveling agent polyether modified polydimethylsiloxane (BD-3308) 6 parts of silica matting agent (OK520) and 4 parts of aliphatic polyisocyanate curing agent (Z4470 SN) are uniformly mixed in a high-speed disperser and filtered, and then coated on a commercially available bright BOPET film by roll coating (specification is 12 ⁇ * 1670mm* 12000m ) surface, after drying, BOPET matt substrate 1 is formed, and its specification becomes 15 ⁇ * 1670 ⁇ * 12000 ⁇ ⁇
  • the matte film coated with the matt coating of the present invention has a matt effect adjustable; and it has high transparency.
  • the description of the terms “one embodiment”, “some embodiments”, “example”, “specific example”, or “some examples” and the like means a specific feature described in connection with the embodiment or example.
  • a structure, material or feature is included in at least one embodiment or example of the invention.
  • the schematic representation of the above terms does not necessarily mean the same embodiment or example.
  • the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

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Abstract

一种双向拉伸聚酯亚光预涂膜及其制备方法，该制备双向拉伸聚酯亚光预涂膜的方法包括：在亮光双向拉伸聚酯薄膜的第一表面涂布亚光清漆，以便形成亚光涂层，亮光双向拉伸聚酯薄膜和亚光涂层构成双向拉伸聚酯亚光预涂膜的基材（1）；在亮光双向拉伸聚酯薄膜的第二表面涂布聚乙烯亚胺水溶液，以便形成中间层（2）；以及通过挤出复合工艺，将选自乙烯−醋酸乙烯酯、低密度聚乙烯、乙烯-丙烯酸乙酯和乙烯−丙烯酸甲酯的至少一种复合于中间层（2）上，以便形成热熔胶层（3）。

Description

双向拉伸聚酯亚光预涂膜及其制备方法 技术领域
本发明涉及印刷技术领域， 特别地， 本发明涉及双向拉伸聚酯亚光预涂膜及其制备方 法。 背景技术
包装行业中， 双向拉伸聚酯 (BOPET)薄膜以优异的性能获得广泛应用。 BOPET具有无 色、 无嗅、 无味、 无毒、 高拉伸强度、 强韧性和良好的透明性， 涂胶后覆在包装材料上能 起到很好的防水、 防撕裂等保护作用。 但目前包装工业领域所使用的聚酯薄膜通常都是亮 光的， 亚光聚酯薄膜由于具有表面典雅的特殊效果， 覆在包装材料上能给人一种朴实的厚 重感， 色彩丰富而不张狂， 非常受消费者喜爱。
亚光聚酯薄膜通常采用的是多层共挤的工艺制备的， 其中又分两种不同的制备技术， 其一是在 BOPET的表层加入无机或有机的亚光助剂来产生亚光效果，如二氧化硅、碳酸钙、 滑石粉、 交联聚苯乙烯微球等； 其二是在 BOPET的表层加入两种以上的高聚物， 如 PP、 PE和 PS等。 通过这两种技术制备的 BOPET亚光薄膜通常雾度较高， 透光率较低， 亚光效 果较差， 加工成预涂膜覆到印刷品表面后， 易使印品色彩失真， 因此限制了其在包装覆膜 行业的应用。
CN102816512 公开了一种抗划伤水性木器涂料， 其由丙烯酸改性聚氨脂乳液、 成膜助 剂、 消泡剂、 去离子水、 湿润剂、 质量比 48~52%芳垸基改性聚甲基垸基硅溶液、 蜡乳液、 增稠剂和防腐剂组成。 然而， CN102816512 所公开的涂料仅适用于木器材料， 在木制家具 表面形成具有抗划伤性能的涂层。
CN101564720 公开了一种双向拉伸聚酯薄膜表面耐磨抗划伤性涂层的制备方法， 其包 括： 将聚氨酯六丙烯酸酯、 环氧改性丙烯酸酯、 二季戊四醇单羟基六丙烯酸酯、 三羟甲基 丙垸三丙烯酸酯、 二缩三丙二醇二丙烯酸酯、 钛酸丁酯和复合裂解型光引发剂均匀混合得 涂料;然后将涂料涂在电晕处理过的 BOPET薄膜表面，经紫外光固化， 即得双向拉伸聚酯薄 膜表面耐磨抗划伤性涂层。 然而， CN101564720 所公开的双向拉伸聚酯薄膜表面耐磨抗划 伤性涂层需要进行紫外固化。
目前的亚光聚酯薄膜仍有待改进。 发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。 为此， 本发明的一个目的在于 提出一种双向拉伸聚酯亚光预涂膜及其制备方法。
在本发明的一个方面， 本发明提出了一种双向拉伸聚酯亚光预涂膜。 根据本发明实施 例， 该双向拉伸聚酯亚光预涂膜包括： 基材， 所述基材由亮光双向拉伸聚酯薄膜和亚光涂 层构成， 其中所述亚光涂层是通过在所述亮光双向拉伸聚酯薄膜的第一表面涂布亚光清漆 形成的； 中间层， 所述中间层是通过在所述亮光双向拉伸聚酯薄膜的第二表面涂布聚乙烯 亚胺水溶液形成的； 以及热熔胶层， 所述热熔胶层是通过挤出复合工艺， 将选自乙烯 -醋酸 乙烯酯、低密度聚乙烯、 乙烯-丙烯酸乙酯和乙烯-丙烯酸甲酯的至少一种复合于所述中间层 上形成的。 根据本发明的实施例， 该双向拉伸聚酯亚光预涂膜 （BOPET) 具有高色彩饱和 度、 亚光度合适、 高抗张强度、 高挺阔度、 高平整度的特点， 提高了印品的精美程度。 另 夕卜， 本发明的该双向拉伸聚酯亚光预涂膜使用于多种材料， 例如木器材料、 金属材料、 高 分子材料等， 且制备过程中不需紫外固化。 根据本发明的具体实施例， 该双向拉伸聚酯亚 光预涂膜（BOPET), 在测量角度为 60°时， 其亚光面的雾度可达 45-80%， 薄膜的透明度可 达 80-95%。
根据本发明的实施例， 所述亚光清漆包含： 65~90重量份的聚氨酯类物质； 1~10重量 份的亚光助剂； 0~12重量份的交联固化剂； 1~2重量份的成膜助剂； 0.2 0.3重量份的消泡 剂； 以及 0.05~0.1重量份的润湿剂。
根据本发明的实施例， 所述聚氨酯类物质为选自水性聚氨酯乳液和溶剂型聚氨酯分散 体的至少一种。 根据本发明的实施例， 所述聚氨酯分散体为选自丙烯酸改性的聚氨酯、 聚 酯改性的聚氨酯、 聚碳酸酯改性的聚氨酯和脂肪族的聚氨酯的至少一种。 根据本发明的实 施例， 所述亚光助剂为选自二氧化硅、 微粉化蜡和有机亚光助剂的至少一种。 根据本发明 的实施例， 所述交联固化剂为选自多官能度氮丙啶、 HDI三聚体、 HDI-IPDI复合三聚体和 聚碳化二亚胺的至少一种。 根据本发明的实施例， 所述成膜助剂为选自 N-甲基吡咯垸酮、 十二醇酯、 乙二醇和二乙二醇单丁醚的至少一种。 根据本发明的实施例， 所述润湿剂为选 自乙醇、 异丙醇、 聚硅氧垸和改性聚硅氧垸的至少一种。 根据本发明的实施例， 所述消泡 剂为选自聚二甲基硅氧垸、 乙醇和聚氧丙烯甘油醚的至少一种。 根据本发明的实施例， 所 述基材的厚度为 13-110微米， 优选 13-75微米。 根据本发明的实施例， 所述亮光双向拉伸 聚酯薄膜的厚度为 10-100微米， 所述亚光涂层的厚度为 1〜10微米。根据本发明的实施例， 所述聚乙烯亚胺水溶液的固含量为 0.5-1.5%。根据本发明的实施例，所述聚乙烯亚胺水溶液 的涂布量为 0.009-0.011 g/m2， 所述中间层的厚度为 0.01-0.03微米， 优选地， 所述聚乙烯亚 胺水溶液的涂布量为 0.009-0.010 g/m% 所述中间层的厚度为 0.01-0.02微米。 根据本发明的 实施例， 所述热熔胶层的厚度为 25-100微米， 优选 15-75微米。 根据本发明的实施例， 通 过选自辊涂和喷涂的至少一种方式涂布亚光清漆。 根据本发明的实施例， 在涂布聚乙烯亚 胺水溶液之前， 进一步包括将所述亮光双向拉伸聚酯薄膜的第二表面进行电晕处理。 根据 本发明的实施例， 在所述亮光双向拉伸聚酯薄膜的第二表面涂布聚乙烯亚胺水溶液之后， 于 85-95 下进行烘干处理， 以便形成所述中间层。 根据本发明的实施例， 所述将选自乙烯 -醋酸乙烯酯、 低密度聚乙烯、 乙烯-丙烯酸乙酯和乙烯-丙烯酸甲酯的至少一种复合于所述 中间层上， 是在臭氧氛围中进行的。 根据本发明的实施例， 利用臭氧发生器实现所述臭氧 氛围， 所述臭氧发生器功率 800W , 所述臭氧氛围中的臭氧浓度为 40%， 气体流量为 3.5SCXFM。
在本发明的第二方面， 本发明提出了一种制备双向拉伸聚酯亚光预涂膜的方法。 根据 本发明的实施例， 该方法包括以下步骤： 在亮光双向拉伸聚酯薄膜的第一表面涂布亚光清 漆， 以便形成亚光涂层， 所述亮光双向拉伸聚酯薄膜和所述亚光涂层构成所述双向拉伸聚 酯亚光预涂膜的基材； 在所述亮光双向拉伸聚酯薄膜的第二表面涂布聚乙烯亚胺水溶液， 以便形成中间层； 以及通过挤出复合工艺， 将选自乙烯-醋酸乙烯酯、 低密度聚乙烯、 乙烯- 丙烯酸乙酯和乙烯 -丙烯酸甲酯的至少一种复合于所述中间层上， 以便形成热熔胶层。 根据 本发明的实施例的方法所得到的双向拉伸聚酯亚光预涂膜 （BOPET ) 具有高色彩饱和度、 亚光度合适、 高抗张强度、 高挺阔度、 高平整度的特点， 提高了印品的精美程度。 另外， 根据本发明的实施例的方法所得到的双向拉伸聚酯亚光预涂膜使用于多种材料， 例如木器 材料、 金属材料、 高分子材料等， 且制备过程中不需紫外固化。 根据本发明的具体实施例 所得到的该双向拉伸聚酯亚光预涂膜 （BOPET ) , 在测量角度为 60°时， 其亚光面的雾度可 达 45-80%， 薄膜的透明度可达 80-95%。
根据本发明的实施例， 所述亚光清漆包含： 65~90重量份的聚氨酯类物质； 1~10重量 份的亚光助剂； 0~12重量份的交联固化剂； 1~2重量份的成膜助剂； 0.2 0.3重量份的消泡 剂； 以及 0.05~0.1重量份的润湿剂。
根据本发明的实施例， 所述聚氨酯类物质为选自水性聚氨酯乳液和溶剂型聚氨酯分散 体的至少一种。 根据本发明的实施例， 所述聚氨酯分散体为选自丙烯酸改性的聚氨酯、 聚 酯改性的聚氨酯、 聚碳酸酯改性的聚氨酯和脂肪族的聚氨酯的至少一种。 根据本发明的实 施例， 所述亚光助剂为选自二氧化硅、 微粉化蜡和有机亚光助剂的至少一种。 根据本发明 的实施例， 所述交联固化剂为选自多官能度氮丙啶、 HDI三聚体、 HDI-IPDI复合三聚体和 聚碳化二亚胺的至少一种。 根据本发明的实施例， 所述成膜助剂为选自 N-甲基吡咯垸酮、 十二醇酯、 乙二醇和二乙二醇单丁醚的至少一种。 根据本发明的实施例， 所述润湿剂为选 自乙醇、 异丙醇、 聚硅氧垸和改性聚硅氧垸的至少一种。 根据本发明的实施例， 所述消泡 剂为选自聚二甲基硅氧垸、 乙醇和聚氧丙烯甘油醚的至少一种。 根据本发明的实施例， 所 述基材的厚度为 13-110微米， 优选 13-75微米。 根据本发明的实施例， 所述亮光双向拉伸 聚酯薄膜的厚度为 10-100微米， 所述亚光涂层的厚度为 1〜10微米。根据本发明的实施例， 所述聚乙烯亚胺水溶液的固含量为 0.5-1.5%。根据本发明的实施例，所述聚乙烯亚胺水溶液 的涂布量为 0.009-0.01 lg/m2， 所述中间层的厚度为 0.01-0.03微米， 优选地， 所述聚乙烯亚 胺水溶液的涂布量为 0.009-0.010g/m2， 所述中间层的厚度为 0.01-0.02微米。 根据本发明的 实施例， 所述热熔胶层的厚度为 25-100微米， 优选 15-75微米。 根据本发明的实施例， 通 过选自辊涂和喷涂的至少一种方式涂布亚光清漆。 根据本发明的实施例， 在涂布聚乙烯亚 胺水溶液之前， 进一步包括将所述亮光双向拉伸聚酯薄膜的第二表面进行电晕处理。 根据 本发明的实施例， 在所述亮光双向拉伸聚酯薄膜的第二表面涂布聚乙烯亚胺水溶液之后， 于 85-95 下进行烘干处理， 以便形成所述中间层。 根据本发明的实施例， 所述将选自乙烯 -醋酸乙烯酯、 低密度聚乙烯、 乙烯-丙烯酸乙酯和乙烯-丙烯酸甲酯的至少一种复合于所述 中间层上， 是在臭氧氛围中进行的。 根据本发明的实施例， 利用臭氧发生器实现所述臭氧 氛围， 所述臭氧发生器功率 800 W， 所述臭氧氛围中的臭氧浓度为 40%， 气体流量为 3.5 SCXFM。
由此， 参考图 1， 本发明提供的双向拉伸聚酯 （BOPET) 亚光预涂膜， 可以由基材、 中 间层和热熔胶层构成， 其中基材采用双向拉伸亚光聚酯薄膜 (BOPET); 中间层涂覆的是固含 量为 0.5-1.5%的聚乙烯亚胺 （PEI) 水溶液， 涂覆量为 0.009-0.011 g/m2， 经烘干后 PEI均匀 分布在所述的薄膜表面； 热熔胶层是由乙烯 -醋酸乙烯酯 （EVA)、 低密度聚乙烯 （LDPE)、 乙烯 -丙烯酸乙酯 （EEA)和乙烯 -丙烯酸甲酯 （EMA) 中的一种或几种共混而成。 基材的厚 度在 13-110微米之间， 中间层的厚度在 0.01-0.03微米 （涂覆量为 0.009-0.011 g/m2) 之间， 热熔胶层的厚度在 12-100微米之间。 根据本发明的实施例， 所述的亚光基材的厚度优选在 13-75微米之间， 中间层的厚度优选在 0.01-0.02微米 （涂覆量为 0.009-0.010 g/m2 ) 之间， 热熔胶层复合的厚度优选在 15-75微米之间。根据本发明的实施例， 所述的亚光基材是由聚 酯（PET)层和亚光涂层组成。 其中， 聚酯层 (4)的厚度在 10〜100微米之间， 亚光涂层的厚 度在 1〜10微米之间。 根据本发明的实施例， 亚光涂层主要由聚氨酯类物质等组成， 该亚 光涂层是将亚光清漆通过辊涂或喷涂的方式涂覆在薄膜表面， 经干燥制成的。 这里所述的 亚光清漆可以是水性的或溶剂性的，其主体成份包括 60-90份的聚氨酯分散体： 0-10份的亚 光助剂； 0-12份的交联固化剂； 1-2份成膜助剂； 0.05-0.1份的润湿剂； 0.1-0.5份的消泡剂。 根据本发明的实施例， 该聚氨酯分散体可以是丙烯酸改性的聚氨酯、 聚酯改性的聚氨酯、 聚碳酸酯改性的聚氨酯或脂肪族的聚氨酯中的一种或几种复配。 根据本发明的实施例， 所 述亚光助剂可以使用二氧化硅、微粉化蜡、有机亚光助剂中的一种或几种，平均粒径为 1-10 微米。 本发明选用的亚光助剂分散在聚氨酯分散体中干燥后能在涂层表面形成一种微观上 凹凸不平的效果， 产生漫反射起到消光作用。 根据本发明的实施例， 所述的交联固化剂为 多官能度氮丙啶、 HDI三聚体或 HDI-IPDI复合三聚体、 聚碳化二亚胺中的一种或几种的复 配。 本发明选用的交联固化剂能够与聚氨酯分散体中的羟基和羧基等官能团发生交联反应， 从而提高涂层的硬度及其对 BOPET基材的附着力。 根据本发明的实施例， 所述成膜助剂为 N-甲基吡咯垸酮、 十二醇酯、 乙二醇、 二乙二醇单丁醚中的一种或几种的复配。 本发明所 述的成膜助剂能够改善聚氨酯分散体的成膜性能， 帮助成膜， 成膜后成膜助剂挥发， 不会 影响涂膜的性能。 所述润湿剂为乙醇、 异丙醇、 改性或未改性的聚硅氧垸中的一种或几种 的复配。 这种润湿流平剂能够改善亚光涂层在 BOPET 基材表面的润湿能力， 提高涂层与 BOPET表面的结合力， 同时也能使涂层表面更加平整、 致密。 根据本发明的实施例， 所述 消泡剂为聚二甲基硅氧垸、 乙醇、 聚氧丙烯甘油醚中的一种或多种。 本发明选用的消泡剂 能消除因高速搅拌和交联反应等形成的小气泡， 消除气泡对涂层外观的影响。
由此， 根据本发明的具体实施例， 本发明还提供了双向拉伸聚酯 （BOPET) 亚光预涂 膜的制备方法，本发明采用的技术方案包括亚光涂层的涂布和亚光 BOPET预涂膜的制备两 方面的内容。其一是亚光涂层的涂布。在普通的亮光 BOPET薄膜聚酯层的外表面通过涂布 工艺在 BOPET 的表面产生一层均匀无色差、 附着力良好、 透明度优异的亚光涂层， 得到 BOPET亚光薄膜基材。 将 65~90份的聚氨酯分散体、 1~10份的亚光助剂、 0~12份的交联 固化剂、 1~2份的成膜助剂、 0.2 0.3份的消泡剂和 0.05~0.1份的润湿剂以及其他组份在混 合罐中混合均匀， 加入涂布线中的料槽中， 采用适当的涂布工艺在 BOPET基材表面涂覆上 亚光涂层， 干燥后亚光涂层的厚度在 1〜10微米之间。 其二是亚光 BOPET预涂膜的制备。 在 BOPET 薄膜聚酯层的内表面通过挤出复合的方法依次涂布、 复合上中间层和热熔胶层 (3), 制得 BOPET亚光预涂膜。基材和热熔胶层的厚度进行适当的组合后， 可以获得不同的
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广 PR
具体地， 包括以下步骤：
1) 中间料的配制： 将固含量为 5-10%的聚乙烯亚胺 (PEI)水溶液调配成固含量为 0.5-1.5%的聚乙烯亚胺 (PEI)水溶液， 搅拌均匀得到中间层用料。
2) 放卷： 将上述经涂布线处理涂有亚光涂层的 BOPET亚光基材， 安放到放卷机上并 通过气胀轴放卷， 即将原材料为卷状的基材展开。
3) 前电晕处理： 对上述的 BOPET亚光基材准备涂覆中间层的表面进行电晕处理， 使 上述亚光基材的达因值达到 54 dyne以上。
4) 涂覆中间层： 通过底涂剂涂覆设备， 在上述的亚光 BOPET基材的电晕处理面涂覆 中间层用料， 中间层物料的使用量为 0.009-0.010 g/m2。
5) 烘干： 利用烘干设备将涂覆有聚乙烯亚胺 (PEI)水溶液的亚光 BOPET基材烘干， 使 聚乙烯亚胺 (PEI)固化在亚光基材表面， 烘干温度为 85-95 °C， 烘干后中间层的厚度约为 0.01-0.03微米。
6) 挤压复合热熔胶层： 载有已烘干聚乙烯亚胺 (PEI)的 BOPET亚光基材， 通过挤出复 合生产线的导辊被送至复合部位， 挤出机挤出热熔胶层用料到亚光基材上； 在挤出复合生 产线的复合部位旁边有臭氧发生器， 由臭氧发生器产生的臭氧喷吹到挤出机挤出的热熔胶 层的流延处， 臭氧的浓度为 40%， 功率 800 W， 气体流量为 3.5SCXFM,臭氧使热熔胶层表 面产生一些极性基团， 然后载有聚乙烯亚胺 (PEI)的亚光抗划伤基材与热熔胶流延通过挤出 复合生产线复合部位的啮合辊的挤压相结合， 形成复合膜， 再经过拉伸、 冷却、 修边后， 被送入测厚仪检测。
期间， 啮合辊的压力为 35 PSI, 挤出机的温度设定值分别为 130、 160、 190、 200、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220°C。
7) 厚度测量与调整： 利用 β射线测量仪测量预涂膜的厚度， 测量后将其结果反馈给计 算机， 计算机控制挤出机的螺杆转速和模头部位的模唇开度， 以便获得厚度均匀一致的预 涂膜。
8) 后电晕处理： 对热熔胶层表面进行电晕处理， 以获得一定量的极性基团， 使热熔胶 层 （3 ) 的表面达因值达到 50以上。
9) 收卷： 利用收卷机将电晕后的 ΒΟΡΕΤ亚光预涂膜收成卷材。
10)分切： 根据客户的需求， 将收卷机收成卷材的预涂膜分切成客户所需宽度和长度的 分切卷。
通过本发明制备的亚光 ΒΟΡΕΤ 预涂膜， 在测量角度为 60°时， 其亚光面的雾度可达 45-80%, 薄膜的透明度可达 80-95%。 通过本发明制备的亚光 ΒΟΡΕΤ预涂膜具有高色彩饱 和度、 亚光度合适、 高抗张强度、 高挺阔度、 高平整度的特点， 提高了印品的精美程度。
本发明的附加方面和优点将在下面的描述中部分给出， 部分将从下面的描述中变得明 显， 或通过本发明的实践了解到。 附图说明
本发明的上述和 /或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和 容易理解， 其中：
图 1显示了根据本发明一个实施例的亚光 ΒΟΡΕΤ预涂膜的结构示意图， 其中： 1表示基材， 2表示中间层， 3表示热熔胶层， 4表示亮光双向拉伸聚酯薄膜， 5表示亚 光涂层。 具体实施方式 下面详细描述本发明的实施例， 对本发明进行描述。 需要说明的是， 这些实施例仅仅 用于说明本发明， 而不以任何方式限制本发明。 另外， 在下列实施例中所涉及的材料均为 市售可得的， 以及未明确说明的处理方法均为本领域技术人员已知的。
实施例 1
以宽度为 1300mm的双向拉伸聚酯 （BOPET) 亚光预涂膜为例进行详细说明。
参照图 1， 先制备 BOPET亚光基材 1。 基材 1是由聚酯层 4和亚光涂层 5组成。 其中， 聚酯层 4的厚度为 12微米， 亚光涂层 5的厚度为 3微米。 先利用双向拉伸聚酯生产设备加 工出双向拉伸聚酯薄膜 4， 在其一个表面均匀涂布一层亚光涂层 5即获得基材 1， 基材 1的 厚度为 15微米。 将 83.3份脂肪族水性聚氨酯乳液 （118001 )、 1.3份十二醇酯、 0.3份聚氧 丙烯甘油醚、 0.1份 BYK-346、 3份二氧化硅消光粉和 12份 HDI-IPDI复合三聚体（XD803 ) 在高速分散机中混合均匀并过滤后， 通过辊涂的方式涂在市售亮光 BOPET 薄膜 （规格为 12 m*1320mm*18000m ) 表面， 烘干后形成 BOPET 亚光基材 1， 其规格变为 15μιη* 1320mm* 18000m。
参照图 1 : 制备 BOPET亚光预涂膜。 该预涂膜是在上述的 BOPET亚光基材 1的内表 面依次涂布 Ο.ΟΙμιη的 ΡΕΙ中间层 2和 25μιη的复合热熔胶 EVA层 3形成的。因为在复合热 熔胶层 3 的过程中需要切边， 所以最终的 BOPET 亚光预涂膜的规格变为 40μιη*1300ιηιη*12000ιη。 其加工方法如下：
1) 中间料的配制： 将固含量为 5%的聚乙烯亚胺 (ΡΕΙ)水溶液调配成固含量为 0.95%的 聚乙烯亚胺 (ΡΕΙ)水溶液， 搅拌均匀得到中间层 2用料。
2) 放卷：将上述经涂布线处理涂有亚光涂层 5的 BOPET亚光基材 1，安放到放卷机上 并通过气胀轴放卷， 即将原材料为卷状的基材展开。
3) 前电晕处理： 对上述的 BOPET亚光基材 1准备涂覆中间层 2的表面进行电晕处理， 使上述亚光基材 1的达因值达到 54dyne以上。
4) 涂覆中间层 2:通过底涂剂涂覆设备，在上述的亚光 BOPET基材 1的电晕处理面涂 覆中间层 2用料， 中间层 2物料的使用量为 0.009-0.010 g/m2。
5) 烘干： 利用烘干设备将涂覆有聚乙烯亚胺 (PEI)水溶液的亚光 BOPET基材 1烘干， 使聚乙烯亚胺 (PEI)固化在亚光基材 1表面， 烘干温度为 85-95°C， 烘干后中间层 2的厚度约 为 0.01-0.03微米。
6) 挤压复合热熔胶层 3 : 载有已烘干聚乙烯亚胺 (PEI)的 BOPET亚光基材 1， 通过挤出 复合生产线的导辊被送至复合部位， 挤出机挤出热熔胶层 3用料到亚光基材 1上； 在挤出 复合生产线的复合部位旁边有臭氧发生器， 由臭氧发生器产生的臭氧喷吹到挤出机挤出的 热熔胶层 3的流延处， 臭氧的浓度为 40%， 功率 800 W, 气体流量为 3.5 SCXFM,臭氧使热 熔胶层 3表面产生一些极性基团， 然后载有聚乙烯亚胺 (PEI)的亚光抗划伤基材 1与热熔胶 流延通过挤出复合生产线复合部位的啮合辊的挤压相结合， 形成复合膜， 再经过拉伸、 冷 却、 修边后， 被送入测厚仪检测。
期间， 啮合辊的压力为 35 PSI, 挤出机的温度设定值分别为 130、 160、 190、 200、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220、 220 °C。
7) 厚度测量与调整： 利用 β射线测量仪测量预涂膜的厚度， 测量后将其结果反馈给计 算机， 计算机控制挤出机的螺杆转速和模头部位的模唇开度， 以便获得厚度均匀一致的预 涂膜。
8) 后电晕处理： 对热熔胶层 3表面进行电晕处理， 以获得一定量的极性基团， 使热熔 胶层 （3 ) 的表面达因值达到 50以上。
9) 收卷： 利用收卷机将电晕后的 ΒΟΡΕΤ亚光预涂膜收成卷材。 实施例 2
以宽度为 1650mm的双向拉伸聚酯 （BOPET) 亚光预涂膜为例进行详细说明。
参照图 1， 先制备 BOPET亚光基材 1。 将 83.2份脂肪族水性聚氨酯乳液 （INCOREZ
W2400), 1.2份二乙二醇单丁醚、 0.4份乙醇、 0.2份 BYK-345、 5份聚甲基脲醛聚合物粉末 和 10份 HDI三聚体（XM501 )放入高速搅拌机中， 在高速分散机中混合均匀并过滤后， 通 过辊涂的方式涂在市售亮光 BOPET薄膜 （规格为 12μιη* 1670mm* 12000m) 表面， 烘干后 形成 BOPET亚光基材 1， 其规格变为 15 m*1670mm*12000m。
参照图 1 : 制备 BOPET亚光预涂膜。 该预涂膜是在上述的 BOPET亚光基材 1的亮光 面依次涂布 Ο.ΟΙμιη的 ΡΕΙ中间层 2， 25μιη的复合热熔胶 LDPE层形成的。因为在复合热熔 胶层 3 的过程中需要切边， 所以最终的亚光抗划伤 BOPET 预涂膜的规格变为 40μιη*1650ιηιη*12000ιη。 其加工方法与实施例 1类似， 不同点在于： 实施例 2使用 LDPE 作为热熔胶层 3。 实施例 3
以宽度为 1650mm的双向拉伸聚酯 （BOPET) 亚光预涂膜为例， 进行详细说明。
参照图 1， 先制备 BOPET 亚光基材 1。 将 89.92 份溶剂型聚碳酸酯型聚氨酯分散体 (B01-7), 0.03份消泡剂 （XPT-118)、 0.05份流平剂聚醚改性聚二甲基硅氧垸 （BD-3308)、 6份二氧化硅消光剂（OK520)和 4份脂肪族多异氰酸酯固化剂（Z4470 SN)在高速分散机 中混合均匀并过滤后， 通过辊涂的方式涂在市售亮光 BOPET 薄膜 （规格为 12μηι* 1670mm* 12000m ) 表面， 烘干后形成 BOPET 亚光基材 1， 其规格变为 15μηι* 1670ηιηι* 12000ηΐ ο
参照图 1 : 制备 ΒΟΡΕΤ亚光预涂膜。 其加工方法与实施例 2相同。 将实施例 1-3所述涂料涂覆于 ΒΟΡΕΤ薄膜表面， 涂层的性能测试结果如表 1所示。
表 1 ΒΟΡΕΤ薄膜涂层性能指标
Figure imgf000010_0001
由表 1可以得出， 涂覆有本发明所述亚光涂层的 ΒΟΡΕΤ薄膜， 其亚光效果可以调节； 而且其具有很高的透明度。
在本说明书的描述中， 参考术语"一个实施例"、 "一些实施例"、 "示例"、 "具体示例"、 或"一些示例"等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含 于本发明的至少一个实施例或示例中。 在本说明书中， 对上述术语的示意性表述不一定指 的是相同的实施例或示例。 而且， 描述的具体特征、 结构、 材料或者特点可以在任何的一 个或多个实施例或示例中以合适的方式结合。
尽管已经示出和描述了本发明的实施例， 本领域的普通技术人员可以理解： 在不脱离 本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、 修改、 替换和变型， 本发 明的范围由权利要求及其等同物限定。

Claims

权利要求书
I、 一种制备双向拉伸聚酯亚光预涂膜的方法， 其特征在于， 包括以下步骤： 在亮光双向拉伸聚酯薄膜的第一表面涂布亚光清漆， 以便形成亚光涂层， 所述亮光 双向拉伸聚酯薄膜和所述亚光涂层构成所述双向拉伸聚酯亚光预涂膜的基材；
在所述亮光双向拉伸聚酯薄膜的第二表面涂布聚乙烯亚胺水溶液， 以便形成中间 层； 以及
通过挤出复合工艺， 将选自乙烯-醋酸乙烯酯、 低密度聚乙烯、 乙烯-丙烯酸乙酯和 乙烯 -丙烯酸甲酯的至少一种复合于所述中间层上， 以便形成热熔胶层。
2、 根据权利要求 1所述的方法， 其特征在于， 所述亚光清漆包含：
65-90重量份的聚氨酯类物质；
1-10重量份的亚光助剂；
0- 12重量份的交联固化剂；
1- 2重量份的成膜助剂；
0. 2-0. 3重量份的消泡剂； 以及
0. 05-0. 1重量份的润湿剂。
3、 根据权利要求 2所述的方法， 其特征在于， 所述聚氨酯类物质为选自水性聚氨 酯乳液和溶剂型聚氨酯分散体的至少一种。
4、 根据权利要求 3所述的方法， 其特征在于， 所述聚氨酯分散体为选自丙烯酸改 性的聚氨酯、聚酯改性的聚氨酯、聚碳酸酯改性的聚氨酯和脂肪族的聚氨酯的至少一种。
5、 根据权利要求 2所述的方法， 其特征在于， 所述亚光助剂为选自二氧化硅、 微 粉化蜡和有机亚光助剂的至少一种。
6、 根据权利要求 2所述的方法， 其特征在于， 所述交联固化剂为选自多官能度氮 丙啶、 HDI三聚体、 HDI-IPDI复合三聚体和聚碳化二亚胺的至少一种。
7、 根据权利要求 2所述的方法， 其特征在于， 所述成膜助剂为选自 N-甲基吡咯垸 酮、 十二醇酯、 乙二醇和二乙二醇单丁醚的至少一种。
8、 根据权利要求 2所述的方法， 其特征在于， 所述润湿剂为选自乙醇、 异丙醇、 聚硅氧垸和改性聚硅氧垸的至少一种。
9、 根据权利要求 2所述的方法， 其特征在于， 所述消泡剂为选自聚二甲基硅氧垸、 乙醇和聚氧丙烯甘油醚的至少一种。
10、 根据权利要求 1所述的方法， 其特征在于， 所述基材的厚度为 13-110微米， 优选 13-75微米。
I I、 根据权利要求 1所述的方法， 其特征在于， 所述亮光双向拉伸聚酯薄膜的厚度 为 10-100微米， 所述亚光涂层的厚度为 1〜10微米。
12、 根据权利要求 1所述的方法， 其特征在于， 所述聚乙烯亚胺水溶液的固含量为
13、 根据权利要求 1所述的方法， 其特征在于， 所述聚乙烯亚胺水溶液的涂布量为 0. 009-0. O i l g/m2 , 所述中间层的厚度为 0. 01-0. 03微米，
优选地， 所述聚乙烯亚胺水溶液的涂布量为 0. 009-0. 010 g/m2 , 所述中间层的厚 度为 0. 01-0. 02微米。
14、 根据权利要求 1所述的方法， 其特征在于， 所述热熔胶层的厚度为 25-100微 米， 优选 15-75微米。
15、 根据权利要求 1所述的方法， 其特征在于， 通过选自辊涂和喷涂的至少一种方 式涂布亚光清漆。
16、 根据权利要求 1所述的方法， 其特征在于， 在涂布聚乙烯亚胺水溶液之前， 进 一步包括将所述亮光双向拉伸聚酯薄膜的第二表面进行电晕处理。
17、 根据权利要求 1所述的方法， 其特征在于， 形成所述中间层进一步包括： 在所述亮光双向拉伸聚酯薄膜的第二表面涂布聚乙烯亚胺水溶液， 并于 85-95 °C下 进行烘干处理。
18、 根据权利要求 1所述的方法， 其特征在于， 所述将选自乙烯-醋酸乙烯酯、 低 密度聚乙烯、 乙烯 -丙烯酸乙酯和乙烯 -丙烯酸甲酯的至少一种复合于所述中间层上， 是 在臭氧氛围中进行的。
19、 根据权利要求 18所述的方法， 其特征在于， 利用臭氧发生器实现所述臭氧氛 围， 所述臭氧发生器功率 800 W， 所述臭氧氛围中的臭氧浓度为 40%， 气体流量为 3. 5 SCXFMo
20、 一种双向拉伸聚酯亚光预涂膜， 其是由权利要求 1-19任一项所述的方法制备 的。
21、 一种双向拉伸聚酯亚光预涂膜， 其特征在于， 包括：
基材， 所述基材由亮光双向拉伸聚酯薄膜和亚光涂层构成， 其中所述亚光涂层是通 过在所述亮光双向拉伸聚酯薄膜的第一表面涂布亚光清漆形成的；
中间层，所述中间层是通过在所述亮光双向拉伸聚酯薄膜的第二表面涂布聚乙烯亚 胺水溶液形成的； 以及
热熔胶层， 所述热熔胶层是通过挤出复合工艺， 将选自乙烯-醋酸乙烯酯、 低密度 聚乙烯、 乙烯 -丙烯酸乙酯和乙烯 -丙烯酸甲酯的至少一种复合于所述中间层上形成的。
22、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述亚光清 漆包含：
65-90重量份的聚氨酯类物质；
1-10重量份的亚光助剂；
0-12重量份的交联固化剂；
1-2重量份的成膜助剂；
0. 2-0. 3重量份的消泡剂； 以及
0. 05-0. 1重量份的润湿剂。
23、 根据权利要求 22所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述聚氨酯 类物质为选自水性聚氨酯乳液和溶剂型聚氨酯分散体的至少一种。
24、 根据权利要求 23所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述聚氨酯 分散体为选自丙烯酸改性的聚氨酯、聚酯改性的聚氨酯、聚碳酸酯改性的聚氨酯和脂肪 族的聚氨酯的至少一种。
25、 根据权利要求 22所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述亚光助 剂为选自二氧化硅、 微粉化蜡和有机亚光助剂的至少一种。
26、 根据权利要求 22所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述交联固 化剂为选自多官能度氮丙啶、 HDI三聚体、 HDI-IPDI复合三聚体和聚碳化二亚胺的至少 一种。
27、 根据权利要求 22所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述成膜助 剂为选自 N-甲基吡咯垸酮、 十二醇酯、 乙二醇和二乙二醇单丁醚的至少一种。
28、 根据权利要求 22所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述润湿剂 为选自乙醇、 异丙醇、 聚硅氧垸和改性聚硅氧垸的至少一种。
29、 根据权利要求 22所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述消泡剂 为选自聚二甲基硅氧垸、 乙醇和聚氧丙烯甘油醚的至少一种。
30、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述基材的 厚度为 13-110微米， 优选 13-75微米。
31、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述亮光双 向拉伸聚酯薄膜的厚度为 10-100微米， 所述亚光涂层的厚度为 1〜10微米。
32、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述聚乙烯 亚胺水溶液的固含量为 0. 5-1. 5%。
33、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述聚乙烯 亚胺水溶液的涂布量为 0. 009-0. 011g/m2 , 所述中间层的厚度为 0. 01-0. 03微米， 优选地， 所述聚乙烯亚胺水溶液的涂布量为 0. 009-0. 010 g/m2， 所述中间层的厚 度为 0. 01-0. 02微米。
34、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述热熔胶 层的厚度为 25-100微米， 优选 15-75微米。
35、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 通过选自辊 涂和喷涂的至少一种方式涂布亚光清漆。
36、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 在涂布聚乙 烯亚胺水溶液之前， 进一步包括将所述亮光双向拉伸聚酯薄膜的第二表面进行电晕处 理。
37、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 在所述亮光 双向拉伸聚酯薄膜的第二表面涂布聚乙烯亚胺水溶液之后， 于 85-95 下进行烘干处 理， 以便形成所述中间层。
38、 根据权利要求 21所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 所述将选自 乙烯-醋酸乙烯酯、 低密度聚乙烯、 乙烯 -丙烯酸乙酯和乙烯 -丙烯酸甲酯的至少一种复 合于所述中间层上， 是在臭氧氛围中进行的。
39、 根据权利要求 38所述的双向拉伸聚酯亚光预涂膜， 其特征在于， 利用臭氧发 生器实现所述臭氧氛围，所述臭氧发生器功率 800 W，所述臭氧氛围中的臭氧浓度为 40%， 气体流量为 3. 5 SCXFM。
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CN107020783A (zh) * 2017-04-15 2017-08-08 温州市金田塑业有限公司 一种低光泽度消光雾度分布可控bopp薄膜以及制备方法
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CN109291697B (zh) * 2018-09-26 2021-02-02 苏州泛普科技股份有限公司 书写板
CN109203787B (zh) * 2018-09-30 2020-12-25 苏州泛普科技股份有限公司 智能黑板
CN111748296A (zh) * 2020-07-16 2020-10-09 惠州艺都文化用品有限公司 一种用于基材表面的热覆合膜
CN112111238A (zh) * 2020-08-12 2020-12-22 安徽国风塑业股份有限公司 一种触感型无底涂bopet哑光预涂膜及其制备方法
CN112143010A (zh) * 2020-09-25 2020-12-29 苏州市贝特利高分子材料股份有限公司 耐划伤哑光复材及其制备方法
CN114889283B (zh) * 2022-04-13 2023-08-29 安徽国风新材料股份有限公司 一种高粘结强度免底涂预涂膜用bopet薄膜及其制备方法
CN115011268B (zh) * 2022-07-18 2023-06-09 惠州艺都文化用品有限公司 家具膜及其制备方法
CN115505155B (zh) * 2022-09-27 2023-03-10 惠州艺都文化用品有限公司 一种板材膜及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101402269A (zh) * 2008-10-22 2009-04-08 北京康得新复合材料股份有限公司 一种双向拉伸增黏预涂膜
CN201702995U (zh) * 2010-05-24 2011-01-12 张家港保税区康得菲尔实业有限公司 双向拉伸聚丙烯抗划伤亚光预涂膜
CN102533151A (zh) * 2012-01-04 2012-07-04 北京康得新复合材料股份有限公司 一种可生物降解的预涂膜
CN102604523A (zh) * 2012-03-20 2012-07-25 北京康得新复合材料股份有限公司 用于bopp薄膜的水性亚光抗划痕涂料及其制备方法
CN102690591A (zh) * 2011-03-25 2012-09-26 上海文澜源印务有限公司 热转印用全漫反射哑光涂层材料及其用途和使用方法
CN102732174A (zh) * 2012-06-26 2012-10-17 北京康得新复合材料股份有限公司 预涂膜及该预涂膜的制备方法
CN102757740A (zh) * 2012-07-04 2012-10-31 北京康得新复合材料股份有限公司 双向拉伸数码预涂膜及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101402269A (zh) * 2008-10-22 2009-04-08 北京康得新复合材料股份有限公司 一种双向拉伸增黏预涂膜
CN201702995U (zh) * 2010-05-24 2011-01-12 张家港保税区康得菲尔实业有限公司 双向拉伸聚丙烯抗划伤亚光预涂膜
CN102690591A (zh) * 2011-03-25 2012-09-26 上海文澜源印务有限公司 热转印用全漫反射哑光涂层材料及其用途和使用方法
CN102533151A (zh) * 2012-01-04 2012-07-04 北京康得新复合材料股份有限公司 一种可生物降解的预涂膜
CN102604523A (zh) * 2012-03-20 2012-07-25 北京康得新复合材料股份有限公司 用于bopp薄膜的水性亚光抗划痕涂料及其制备方法
CN102732174A (zh) * 2012-06-26 2012-10-17 北京康得新复合材料股份有限公司 预涂膜及该预涂膜的制备方法
CN102757740A (zh) * 2012-07-04 2012-10-31 北京康得新复合材料股份有限公司 双向拉伸数码预涂膜及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10619020B2 (en) 2015-06-30 2020-04-14 Dow Global Technologies Llc Polyethylene films with matte surface
CN114456422A (zh) * 2022-03-10 2022-05-10 山东胜通光学材料科技有限公司 一种高附着性厚型增亮聚酯基膜的制备方法
CN114456422B (zh) * 2022-03-10 2023-08-29 山东胜通光学材料科技有限公司 一种高附着性厚型增亮聚酯基膜的制备方法

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