CN107107556A - Multi-layer fluoropolymer films, its layered product and the method for forming layered product - Google Patents

Multi-layer fluoropolymer films, its layered product and the method for forming layered product Download PDF

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Publication number
CN107107556A
CN107107556A CN201580073310.9A CN201580073310A CN107107556A CN 107107556 A CN107107556 A CN 107107556A CN 201580073310 A CN201580073310 A CN 201580073310A CN 107107556 A CN107107556 A CN 107107556A
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China
Prior art keywords
layer
fluoropolymer
film
prime coat
mixture
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CN201580073310.9A
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Chinese (zh)
Inventor
H.黄
D.徐
F.乔
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Honeywell International Inc
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Honeywell International Inc
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Publication of CN107107556A publication Critical patent/CN107107556A/en
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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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/10—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products
    • E04C2/20—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products of plastics
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • 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
    • B32B2307/71—Resistive to light or to UV
    • 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
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • 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
    • B32B2419/00—Buildings or parts thereof
    • 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
    • B32B2607/00—Walls, panels

Abstract

Method the invention provides multilayer film, layered product and for forming multilayer laminated body.The multilayer film includes the color-printed layer (30) of fluoropolymer layer (10), prime coat (20) and the covering prime coat (20).The prime coat (20) includes acrylic polymer and optional UV absorbents and/or curing agent.The multi-layer fluoropolymer films can be used for building laminate structure.

Description

Multi-layer fluoropolymer films, its layered product and the method for forming layered product
Technical field
The technical field of the present invention is related to multilayer film, its layered product and the method for forming the layered product in general, more In particular to multi-layer fluoropolymer films, its layered product and the method for forming the laminate.
Background
In construction and building industry, window profile and aluminium-plastic panel are usually using polymethyl methacrylate/polyvinylidene fluoride (PMMA/PVDF) co-extruded films or PMMA film to be to protect the substrate of coloring to exempt from weathering, for example by ultraviolet (UV) light, humidity and Acid rain.In window profile, the PMMA film or the co-extruded films are visually transparent, and it usually contains UV absorbents, Hence in so that its part stops UV, and forced together with the substrate thermosphere of coloring or thermosphere is pressed in the substrate of coloring.It is described The substrate of coloring is typically based on the colored printing thing based on acrylic acid on polyvinyl chloride (PVC) or PMMA film.The film The PMMA resins that are modified by the PMMA copolymers or toughness of toughness reinforcing of PMMA parts be made, to avoid known PMMA fragility from asking Topic.
In aluminium-plastic panel, the PMMA/PVDF of the PMMA or coextrusion is visually transparent, and usually contains UV Absorbent, hence in so that its part stops UV, and by its colored printing and passes through adhesive and aluminium foil or other paper tinsel basalises Force together or be laminated in aluminium foil or other paper tinsel substrates.However, PMMA for film forming, printing and lamination for be insufficient to it is soft Tough, therefore cause operating difficulties using PMMA when for such application.When being exposed to solvent during cleaning PMMA is also easy to rupture.PMMA can shrink at a temperature of more than 80 DEG C and in about 100 DEG C of glass transition temperature In the case of tend to rupture at low temperature.In addition, PMMA is very hygroscopic, it can not be protected if substrate is to water and/or acid-sensitive Protect them.The UV absorbents being compounded in PMMA film are also easy to migrate to surface and lose its effectiveness over time.
Known fluoro-containing copolymer film has excellent weatherability and to UV light, acid rain and the chemical inertness of mould.Due to it Low surface tension, fluoropolymer is relatively dust-proof and substantially self-cleaning.These benefits cause fluoropolymer Thing film acts as outdoor film and layered product, the particularly good candidate as external protection film.
However, for the application that those require colored printing and aesthetic effect, such as colorful window profile and plastic-aluminum Composite material, fluoro-containing copolymer film is not used by due to its low-surface-energy.Fluoro-containing copolymer film or UV light are transparent, therefore The colored printing thing in lower substrates is not protected.U.S. Patent Publication No. 2013/0136910 and WO 2009/000566 are described There is the PVDF/PMMA films of improved weatherability and chemical resistance；But, do not disclose their colored printing adaptive.
Accordingly, it is desired to provide a kind of have good colored printing adaptive, good weatherability and effectively protect lower section The multilayer film that is damaged from UV of colored printing thing.Additionally, it is desirable to provide it is a kind of with good colored printing adaptive, it is good Weatherability and the multilayer laminated body for effectively protecting the colored printing thing of lower section to be damaged from UV.It is also expected to providing for forming this The method of the multilayer laminated body of sample.In addition, with reference to accompanying drawing and the background of the present invention, by subsequent detailed description of the invention and Appended claims, other desired features and characteristics of the invention will become clear and definite.
General introduction
Multilayer film, the multilayer laminated body formed by such multilayer film is provided herein and such multilayer laminated body is formed Method.In an exemplary embodiment, multilayer film is provided herein.The multilayer film include have first surface and The fluoropolymer layer of the second surface relative with the first surface；Cover the bottom of the first surface of the fluoropolymer layer Enamelled coating, the prime coat includes acrylic polymer and UV absorbents；With the printing layer for covering the prime coat.
Multilayer laminated body is provided herein.The multilayer laminated body include with first surface and with the first surface The fluoropolymer layer of relative second surface；Cover the prime coat of the first surface of the fluoropolymer layer, the priming paint Layer includes acrylic polymer；Cover the colored printing nitride layer of the prime coat；Cover the bonding of the colored printing nitride layer Oxidant layer；With the basalis of covering described adhesive layer.
The method for forming multilayer laminated body is provided herein.Methods described includes UV absorbents being dissolved in solvent In, to form solvent mixture；The solvent mixture is mixed with acrylic polymer, to form priming paint；By the bottom Paint is coated on fluoropolymer layer, to form the fluoropolymer layer of primer coating；The coating is printed using color inks The fluoropolymer layer of priming paint, to form the film of color inks printing；Substrate is pressed on by the film layer that the color inks print On.
The brief description of accompanying drawing
The present invention is described hereinafter in conjunction with following accompanying drawing, and wherein identical numeral represents identical element, and Wherein：
Fig. 1 is the diagram of the fluoro-containing copolymer film with primer coating according to an exemplary；
Fig. 2 is the diagram of the building laminate structure of the use fluoro-containing copolymer film according to an exemplary；With
Fig. 3 is the curve map for representing UV and transmission of visible light.
Describe in detail
What detailed description below was merely exemplary in itself, it is no intended to limitation various embodiments herein.This Outside, it is intended in the absence of by any theoretical constraint proposed in foregoing background or following detailed description.
The embodiment of present disclosure is related to multilayer film, the layered product of such multilayer film and for being formed in general The method of the layered product.Present disclosure is related to good colored printing adaptive, excellent intrinsic weatherability and lower section The film based on fluoropolymer of the UV protective effects of colored printing thing.In an exemplary embodiment, building is also formed Layered product.Term " building layered product " is used to describe all lamination knots including window profile, wallboard and roof herein Structure material.Term " section bar " is used to describe window frame herein.The window frame has certain section structure to provide intensity, peace Dress and assembling and heat-proof quality.
According to an exemplary, first two layers of the multilayer film such as covered herein about 280 to about 400nm UV Have not less than about 80% in optical range with the transmissivity less than about 30% and in about 400 to about 800nm visible-range Transmissivity.The multilayer film includes the fluoropolymer with first surface and the second surface relative with the first surface Layer, the fluoropolymer layer has not less than about 80% transmissivity in about 280 to about 800nm light belt wide scope.Priming paint The first surface of the layer covering fluoropolymer layer.The prime coat includes acrylic polymer.Colored printing nitride layer is covered Cover the prime coat.
Priming paint is coated to the fluoro-containing copolymer film by using the prime coat based on acrylic acid, adding surface can be simultaneously And the fluoro-containing copolymer film of primer coating can colored printing.As used herein, " cover (overlays) " and " be covered in (overlaying) " refer to multiple layers directly with one another and/or be physically contacted.As used herein, " colored printing thing " includes pigment With the mixture for the polymeric binder (carrier) for carrying pigment.The polymer support is included based on acrylic acid or based on amino Polymer, solvent, dispersant, curing agent and/or its mixture of formic acid esters.
In an exemplary embodiment, the fluoropolymer is selected from polytrifluorochloroethylene (PCTFE), polytetrafluoroethyl-ne Alkene (PTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), ethylene-chlorinated (ECTFE), ethylene fluoride-the third Alkene (FEP), perfluoroalkoxy (perfluoroalkoxy) (PFA), ethylene-tetrafluoroethylene (ETFE) and its mixture.
The acrylic polymer of the prime coat is included selected from hydroxyl, carboxyl, amine, glycidyl and its mixture Functional group.In an exemplary embodiment, the acrylic polymer is selected from acrylic acid, methacrylic acid, acrylic acid Ester, the ester of methacrylic acid and its polymer of mixture and copolymer.It is adapted to acrylic polymer used herein Example be the commercially available priming paint Cytec VIACRYL SC 200 based on acrylic acid, it is available from Cytec Industries Of Smyrna, Georgia and DuPont 68040, it is available from DuPont, Wilmington, Delaware.
In an exemplary embodiment, the prime coat based on acrylic acid contains curing agent, such as polyisocyanates.Institute Curing agent is stated in the range of about 3% to about 5% (based on the weight of the priming paint).The curing agent be used for improve priming paint hardness and Durability.The example of suitable curing agent is included available from Bayer Material Science of Pittsburgh, Pennsylvania Desmodur N3300.
In an exemplary embodiment, the prime coat based on acrylic acid contains UV absorbents.The UV absorbs Agent is in the range of by weight about 3% to about 15%.The UV absorbents are selected from BTA, hydroxy-benzophenones；Nanometer The inorganic filler of size, such as zinc oxide or titanium dioxide；And its mixture.Suitable for the bottom based on acrylic acid covered herein The example of UV absorbents in enamelled coating includes the Tinuvin available from BASF of Charlotte, North Carolina 234.BTA can be in advance first dissolved in the solvent of such as ethyl acetate, then be mixed with the priming paint.UV absorbents： The ratio of solvent is about 1:10 to about 4:In the range of 10.By adding UV absorbents in the priming coat, realize high UV stops, while also keeping the high-transmission rate of visible ray.
In another exemplary embodiment, absorption UV of the priming paint based on acrylic acid comprising grafting benzo three Oxazolyl group and hindered amine as light stabilizer group (HALS).The BTA group and HALS are such as 2,2,6,6- tetramethyl piperidines Derivative is grafted on acrylic polymer chain.The example of UV absorbents and the acrylic primer of HALS grafting is commercially available From Nippon Shokubai Company of Japan HALSHYBRID UV-G.Obtained prime coat have weatherability and Both UV shield effectivenesses.
In an exemplary embodiment, the fluoro-containing copolymer film surface is processed before being coated with priming paint Surface.Coated for the ease of priming paint, the fluoro-containing copolymer film can be by routine techniques by plasma or sided corona treatment To at least about 36 dynes, especially greater than about 44 dynes.Generally, sided corona treatment is related to mechanism electric discharge.This corona discharge can be led Cause the partial ionization of ambient atmosphere.When plastic components is placed in discharge path, the electron bombardment produced in electric discharge should The surface of plastic components is so that molecular scission on surface.
Generally, corona treatment is related to mechanism electric discharge, but bulk plasma density ratio is big using sided corona treatment Much, speed and degree on material surface are incorporated into which enhance ionized molecule.In the case of no surface treatment, surface Tension force is below about 34 dynes, and does not make primer coating smooth and wetting, and this causes priming paint to be sprawled well on the surface of the film.
The priming paint is coated on by conventional rotogravure application and solvent drying process not surface treated or through table On the fluoro-containing copolymer film of face processing.Rotogravure application is using the engraved roll on surface with intaglio unit., will when operating coating Engraving roller segment immersion is filled in the pallet of priming paint.As roller rotates, priming paint is pushed into the intaglio unit on surface by it, then The roller is scraped with scraper before roller is contacted with film, so as to remove unnecessary priming paint and proper amount of priming paint is retained in into unit In to control coat weight.Then pressure roller is pressed on the top of engraved roll, and uncoated film is passed through pressure roller and carving Carve the nip point of roller.Pressure roller with the addition of pressure so that the film and the engraved roll good contact and cause priming paint from Intaglio unit is transferred to film surface.After rotogravure application, coated film is advanced through the drier or passage of heating to steam Send out solvent and dry the film.During rotogravure application technique, by the coating of priming paint liquid on the surface of the film, and by about 80 Solvent is evaporated at a temperature of in the range of to about 100 DEG C by dry channel.Priming paint is by solidify afterwards and is bonded on film surface. Post cure condition be usually in the range of about 25 to about 50 DEG C at a temperature of about 3 to about 5 days.
Using the film of the further intaglio printing primer coating of commercially available color inks, the color inks for example available from Toyo Ink Company commercially available GC Ink series, the ink based on polyurethane；Available from KIIAN Group's ACRILUX series, the ink based on acrylic acid；And/or its mixture.Cohesive of the colored printing thing on film can be according to ASTM D3359 are measured and evaluated.This method, which is related to, applies and removes adhesive tape on the otch being made in coating ink.Can be with Using UV-VIS spectrophotometers (Cary 4000) measure primer coating film light transmission, with measure UV shielding properties and Visible transmission performance.
Fig. 1 is the example of the multilayer film 2 with the first fluoropolymer layer, the second prime coat and the 3rd colored printing nitride layer Property embodiment.The multilayer film includes fluorine-containing with first surface 12 and the second surface 14 relative with the first surface Polymeric layer 10.Prime coat 20 covers the first surface 12 of fluoropolymer layer 10.Colored printing nitride layer 30 covers prime coat 20.
In an exemplary embodiment, the method to form multilayer laminated body is disclosed.UV absorbents are dissolved first In a solvent, to form solvent mixture.The solvent mixture is mixed with acrylic polymer, to form priming paint.So The priming paint is coated on fluoropolymer layer afterwards, to form the fluoropolymer layer of primer coating.The prime coat and institute Fluoropolymer layer is stated directly to contact.Then the fluoropolymer layer of the primer coating, color inks are printed with color inks The layer of printing is directly contacted with the prime coat, to form the film of color inks printing.Then the color inks are printed Film and substrate are laminated together or are laminated in substrate.
In an exemplary embodiment, the film that adhesive can be used to print above-mentioned primer coating and color inks Forced together or laminated thereon with building layered product such as polyvinyl chloride (PVC) or aluminium foil or transition metal layers of foil, to provide family Outer weatherability.Described adhesive is selected from ethane-acetic acid ethyenyl ester, polyurethane, acrylate and its mixture.
Fig. 2 is the exemplary of the building layered product 4 using fluoro-containing copolymer film as shown in Figure 1.Construction level Laminate 4 includes the fluoropolymer layer 10 with first surface 12 and the second surface 14 relative with the first surface.Priming paint Layer 20 covers the first surface 12 of fluoropolymer layer 10.Colored printing nitride layer 30 covers prime coat 20.Adhesive phase 40 is covered Colored printing nitride layer 30 and the covering adhesive phase 40 of basalis 50.In an exemplary embodiment, basalis 50 is gold Belong to paper tinsel or PVC.
The following examples include representational fluoro-containing copolymer film.These embodiments be not construed as it is restricted, because For according to the method and appended claims covered herein, other equivalent embodiments will become clear and definite.
Embodiment 1
Test sample, which is prepared, using Honeywell Hydroblock PCTFE films is used as fluoropolymer.Typical 50 microns Hydroblock PCTFE films have the characteristic as listed in table 1 below：
Table 1
Preparation test sample as described in the following table 2.
Table 2
Primer coating weight is measured by the amount in the hard resin dried and be retained in after evaporation solvent on film.It is based on Dry primer weight calculates the percentage by weight of UV absorbents.All percentages are by weight.Using commercially available Huang The film of chromatic ink intaglio printing primer coating.
UV transmissivities and transmission of visible light are shown in Figure 3.Measured and applied using UV-VIS spectrophotometers (Cary 4000) The light transmission of the film of priming paint is covered, to measure UV shielding properties and visible transmission performance.
In figure 3, X-axis 60 represents that the ultraviolet of the measurement in terms of nm to the optical wavelength of visible ray, and Y-axis 70 represents to pass through The light transmission measured by transmittance percentage of multi-layer fluoropolymer films.5 (80) of primer coating, it is containing acrylic acid Using the UV absorbents of grafting in the prime coat of resin, best UV shieldings are shown under effective load.Tester 1 And the result of tester 2 (130) shows 280-400nm (UV light) and 400-800nm (visible ray) light transmission all (140) Greater than about 92%, this shows that the film is visually transparent and without UV blocking effects.1 (120) of primer coating show The transmissivity for showing 280-400nm UV light is about 60%, it means that the priming paint of the film stops the UV light of a part.400- The transmissivity of 800nm light is still higher than about 92%, and this shows that the priming paint does not stop visible ray and the film is visually Transparent.2 (110) of primer coating show that 20% UV light passes through coated film.2 (110) of primer coating also do not stop Visible ray.3 (100) of primer coating show that 10% UV light passes through coated film.The 3 of primer coating do not stop visible yet Light.4 (90) of primer coating and 5 (80) of primer coating show that the transmissivity of 280-400nm UV light is below about 10%, spy The transmissivity for not being 280-380nm UV light is almost about 0%, and this produces the best UV blocking effects of test sample, simultaneously 400-800nm visible ray is passed through and coated film is still visually transparent.
Measured by ASTM D3359 and evaluate cohesive of the colored printing thing on film.Printability test result is shown in In table 3 below.
Table 3
Test sample Dyne level (dynes per centimeter) Printability ASTM grades
Tester 1 34 (untreated films) 0B
Tester 2 52 3B
The 4 of primer coating Priming paint 4B
Table 3 is shown, in the case of the priming paint covered herein, and the adhesiveness of color inks has desired effect, The ink wherein peeled off is considerably less.For printability test, prepared and cut using 6 1mm apart parallel blade Cutter.Select the grid region in ink layer and cutter is placed in grid region.Cutter is depressed and gently pulled, So that the first otch about 20mm length.Second otch is made at 90 DEG C and centered on original otch, to be formed in ink layer Comb mesh pattern.Use brush clean cut region.The adhesive tapes of 3M 610 are placed on the center of comb mesh pattern, to ensure and ink Layer contact.Rubbed adhesive tape securely with erasing rubber.After 90 seconds, by catching movable end and with the angle as close possible to 180 ° Itself is quickly withdrawn into remove adhesive tape.Check grid region and the grade of cohesive is determined according to following yardstick.
The edge of 5B- otch is that do not have grid separation in complete smooth and grid.
The flakelet of 4B- coatings is separated and the region disconnecting less than 5% in infall.
Edge of the flakelet of 3B- coatings along otch and in infall separation.The net that impacted region is about 5% to 15% Lattice.
Coating described in 2B- has thin slice along edge and on the grid of part.The net that impacted region is about 15% to 35% Lattice.
Edge of the coating described in 1B- along otch has the thin slice of big print ribbon form and all grids are separated.By shadow Loud region is the grid of about 35% to about 65%.
Edge of the coating described in 0B- along otch has the thin slice of big print ribbon form and all grids are separated.By shadow Loud region is greater than about 65%.
4 (90) of primer coating show the best cohesive for the test sample that grade is 4B.Above-mentioned primer coating and The film of color inks printing can use adhesive to be forced together with PVC profile or metal foil layer, to provide outdoor weathe resistance.
, should although showing at least one exemplary in detailed description of the invention above Also there is substantial amounts of variant in understanding.It should also be understood that one or more exemplaries are only examples, it is no intended to appoint Where formula limits the scope of the present invention, applicability or configuration.On the contrary, detailed description above will carry for those skilled in the art For the easily route map of the exemplary for realizing the present invention.It should be appreciated that not departing from appended claims In the case of the scope of the present invention of middle elaboration, the function of the element described in an exemplary embodiment and configuration can be made Go out various changes.

Claims (10)

1. multilayer film, it includes：
With first surface and the second surface relative with the first surface fluoropolymer layer, the fluoropolymer layer There is not less than about 80% transmissivity in about 280 to about 800nm light belt wide scope；With
The prime coat of the first surface of the fluoropolymer layer is covered, the prime coat is inhaled comprising acrylic polymer and UV Receive agent；With
Cover the colored printing nitride layer of the prime coat.
2. the multilayer film of claim 1, wherein the fluoropolymer be selected from PCTFE, PVF, ETFE, PVDF, ECTFE, FEP, PFA and its mixture.
3. the multilayer film of claim 1, wherein the colored printing nitride layer includes color inks, the color inks are selected from and are based on The ink of acrylic acid, ink and its mixture based on polyurethane.
4. the multilayer film of claim 1, wherein the UV absorbents include BTA.
5. the multilayer film of claim 1, wherein the acrylic polymer is selected from acrylic acid, methacrylic acid, acrylic acid The polymer and copolymer of ester, the ester of methacrylic acid and its mixture.
6. multilayer laminated body, it includes：
With first surface and the second surface relative with the first surface fluoropolymer layer, the fluoropolymer layer There is not less than about 80% transmissivity in about 280 to about 800nm light belt wide scope；
The prime coat of the first surface of the fluoropolymer layer is covered, the prime coat includes acrylic polymer；
Cover the colored printing nitride layer of the prime coat；
Cover the adhesive phase of the colored printing nitride layer；With
Cover the basalis of described adhesive layer.
7. the multilayer laminated body of claim 6, wherein the fluoropolymer be selected from PCTFE, PVF, ETFE, PVDF, ECTFE, FEP, PFA and its mixture.
8. the multilayer laminated body of claim 6, wherein the substrate is selected from PVC, aluminium, transition metal and its mixture.
9. forming the method for multilayer laminated body, it the described method comprises the following steps：
By the dissolving of UV absorbents in a solvent, to form solvent mixture；
The solvent mixture is mixed with acrylic polymer and UV absorbents, to form priming paint；
The priming paint is coated on fluoropolymer layer, to form the fluoropolymer layer of primer coating；
The fluoropolymer layer of the primer coating is printed using color inks, to form the film of color inks printing；With
The film layer that the color inks print is pressed in substrate.
10. the method for claim 9, wherein the fluoropolymer is PCTFE.
CN201580073310.9A 2015-01-13 2015-01-13 Multi-layer fluoropolymer films, its layered product and the method for forming layered product Pending CN107107556A (en)

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PCT/CN2015/070608 WO2016112494A1 (en) 2015-01-13 2015-01-13 Multilayer fluoropolymer films, laminates thereof, and methods of forming the laminates

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Citations (5)

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Publication number Priority date Publication date Assignee Title
CN1473111A (en) * 2000-10-30 2004-02-04 ��Ļ���Ű˾ Process for making protected printed images
CN101198463A (en) * 2005-02-23 2008-06-11 埃克阿泰克有限责任公司 Plastic panels with uniform weathering characteristics
CN101730717A (en) * 2007-06-22 2010-06-09 赢创罗姆有限责任公司 Pmma/pvdf film with particularly high weathering stability and high uv protective action
EP2363427A1 (en) * 2008-07-10 2011-09-07 Avery Dennison Corporation Film comprising a strengthening layer and an ink receptive layer, and laminate thereof
CN203974180U (en) * 2014-05-27 2014-12-03 广州宏信塑胶工业有限公司 High-weatherability is electroplated printing PVC adhesive plaster

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Publication number Priority date Publication date Assignee Title
JP3618292B2 (en) * 2000-11-10 2005-02-09 日本カーバイド工業株式会社 Retroreflective sheet with printed layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1473111A (en) * 2000-10-30 2004-02-04 ��Ļ���Ű˾ Process for making protected printed images
CN101198463A (en) * 2005-02-23 2008-06-11 埃克阿泰克有限责任公司 Plastic panels with uniform weathering characteristics
CN101730717A (en) * 2007-06-22 2010-06-09 赢创罗姆有限责任公司 Pmma/pvdf film with particularly high weathering stability and high uv protective action
EP2363427A1 (en) * 2008-07-10 2011-09-07 Avery Dennison Corporation Film comprising a strengthening layer and an ink receptive layer, and laminate thereof
CN203974180U (en) * 2014-05-27 2014-12-03 广州宏信塑胶工业有限公司 High-weatherability is electroplated printing PVC adhesive plaster

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