CN1436203A - Adherable fluorine-contg. sheet and adhering method and adhesion structure using same - Google Patents

Abstract

The present invention provides an adherable fluorine-containing material sheet, an adhesive fluorine-containing material sheet, an adhering method of a fluorine-containing material sheet, and an adhesion structure. In one aspect, on the surface of an electron beam non-degradable fluorine-containing material, an adherability-imparting layer is provided, between which a chemical bond is formed by electron beam irradiation.

Description

The adhesive bonding method and the glued construction of fluorine material plate that can be bonding, fusible fluorine material plate and fluorine material

Technical field

The present invention relates to a kind of fluorine material plate, a kind of fusible fluorine material plate, a kind of adhesive bonding method and glued construction of fluorine material plate that can be bonding.

Background technology

Fluorine material such as Dyneon ^TMTHV (terpolymer of tetrafluoroethylene, R 1216 and vinylidene fluoride, Dyneon company make) and PVDF (poly(vinylidene fluoride)) have the fabulous performance that the hydrocarbon system material can not have, so occupy very important position industrial.For example, fluorine material is suitable as the surfacecti proteon material of billboard, reverberator, solar cell etc., and is particularly suitable for outdoor use, because it has special performances, as good chemical stability, fabulous weathering resistance and higher thermostability.

Fluorine material can be by embedding or fixing and use as a part individually with screw etc., and, fluorine material is more expensive usually, and therefore, it is mainly by being used as the matrix material that improves function be used in combination (lamination or the covering) of other material.These matrix materials will be as for example, final coating for the protective membrane of getting film or billboard.

But the surface energy of fluorine material itself is lower, therefore, to dissimilar materials, the tack extreme difference of tackiness agent or pressure sensitive adhesive for example.In order to address this problem, studied the method for various raising bond propertiess up to now.

These method rough segmentations are 1) the insufficient fluorine material of bond properties is carried out modification, make it can be attached to the method on the existing hydrocarbon material (tackiness agent), 2) tackiness agent or pressure sensitive adhesive are carried out modification, make it can be bonded in method on the insufficient material of bond properties, and 3) a certain special binder layer is inserted in method between these heterospheres.More particularly, in situation 1) in, fluorocarbon material is carried out surface treatment, this surface treatment comprises dry-cure, as flame treating and Corona discharge Treatment (referring to U.S. Patent No. 3,133,854, embodiment 10), and wet treatment, combination as alkaline solution, liquefied ammonia and sodium, and the combination of sodium Metal 99.5-naphthalene/tetrahydrofuran complex solution (referring to U.S. Patent No. 3,133,854 and No.4,740,562 and Japanese Patent Application No.61-7337).Simultaneously, proposed a kind of fluoropolymer to be carried out bulk modified (for example, mixed with polymers or dehydrofluorination (referring to U.S. Patent No. 4,230,768)), to improve its method to the bond properties of dissimilar materials.In situation 2) in, people's such as Yagi Japanese Patent Application No.3-163182 discloses the validity of the IPN type tackiness agent that comprises acryloyl polymkeric substance and fluoropolymer, and it obtains by dissolving fluorochemical monomer and solidify this mixture in acryloyl monomer; People's such as Usami Japanese Patent Application No.61-31411 discloses by mixing the validity of the tackiness agent that acryloyl monomer or oligopolymer and fluoropolymer obtain, and the consistency between them is better; People's such as Kumar U.S. Patent No. 5,482,991 discloses the validity of the acrylic pressure-sensitive adhesive that contains fluorinated acrylamide acyl siloxanes.Aspect theory research, reported in that piece article of people such as Paciorek in J.Polym.Sci. the 45th phase 405-413 page or leaf (1960), fluoropolymer, poly(vinylidene fluoride) (PVDF) behind dehydrofluorination with the reaction of amine.People such as Schonhorn reported in the 4th phase of J.Adhesion Sci.Technol. the 277th page (1989), PVDF and the reaction that contains the Resins, epoxy of diamine curing agent.But, situation 3) be difficult to and situation 2) clearly distinguish, a kind of mixture of polymers of using two or more in order to the formation binder layer reported, to improve adherent method between the dissimilar materials.People's such as Kawashima European patent EP-0523644 has proposed by improving bond properties in conjunction with fluoropolymer and polyamide resin.An industrial examples of applications is the Denka DX film that is described in the Denka company of Japanese Patent Application No.2-28239.This film mainly is to produce by two different layers of melting-coextrusion ratio of mixture.For example, skin comprises the composition of PVDF/PMMA=80/20, and internal layer comprises the composition of PVDF/PMMA=20/80.Stage in the end, pressure sensitive adhesive is coated on has on the higher internal layer of relatively large PMMA (polymethylmethacrylate) component and polarity.

In the present invention, but the formation that the most important is a viscosity gives layer promptly, is specifically shone by electron beam and is formed undercoat.Here, the routine techniques as the formation undercoat of cruces of the present invention is described below.

As everyone knows, the electron beam irradiation has caused polymkeric substance such as poly crosslinked, has improved thermotolerance thus.For example, John Scheirs chief editor's Modern Fluoropolymers (modern fluoropolymers) (New York JohnWiley﹠amp; Sons company published in 1997) it is described.And people such as Maku-uchi have proposed in J.Poly.Sci.Poly.Chem.Ed. the 14th phase 617-625 page or leaf (1976), can produce free radical and form crosslinking structure with electron beam irradiation PVDF the time.

People's such as Sidney Japanese Patent Application No.2-209928 and they are at international conference (Proceedings of Rad Tech Asia ' 91, Osaka, Japan (-18 days on the 15th April in 1991)) proposes in the publication on, under electron beam irradiation, make polyfunctional acrylic ester such as vinylformic acid trimethylammonium propyl ester (TMPTA) and crosslinked fluororubber, and with the TMPTA polymer graft on the copolymer chain of vinylidene fluoride and R 1216.People's such as Hayami Japanese Patent Application No.8-245850 has described under electron beam irradiation by linking agent, improves the thermal characteristics of THV etc. as TMPTA or triallyl isocyanurate (TAIC).

On the other hand, known electronic bundle irradiation also can be used as the means of cross-linked binder or pressure sensitive adhesive of being used for.The U.S. Patent No. 2,956,904 of Hendriks has reported that shining cross-linked rubber by electron beam is pressure sensitive adhesive.

People's such as Yarusso U.S. Patent No. 5,266,400 discloses that to reduce the cross-linked rubber that is used for that is applied on paper (Mierocrystalline cellulose), polypropylene or the tetrafluoroethylene that is easy to be degraded by electron beam be the method for the acceleration voltage of pressure sensitive adhesive.But, if acceleration voltage is increased to the degree that electron beam works to substrate, substrate meeting degraded.

People's such as Babu U.S. Patent No. 5,209,971 discloses with electron beam shines the polyolefin pressure sensitive adhesive with crosslinked pressure sensitive adhesive, improves cohesive force and stable on heating method thus.

People's such as Bonk U.S. Patent No. 4,563,388 has reported that the acryloyl that is coated on the polyolefin mould material with the electron beam irradiation is a pressure sensitive adhesive, to improve the bond properties on the interface.Similarly, people's such as Mori Japanese Patent Application No.63-150330 reported, when being that monomer is laminated on the polyolefin film by acryloyl, when electron beam is radiated on this metal sheet, can improve bonding between polyolefine and the acryloyl material to metal sheet.The embodiment of people's such as Magat U.S. Patent No. 3,252,880 illustrates, when PTFE (tetrafluoroethylene) plate is immersed in the acryloyl monomer, and apply gamma-rays thereon after 3 days, on the surface of PTFE plate grafting acrylonitrile polymer, produce binding property thus from the teeth outwards.But the Tg of polyacrylonitrile itself is about 100 ℃, can not be effective as pressure sensitive adhesive.

In addition to these, unified being described below adhered at the interface that forms with electron beam.Japanese Patent Application No.3-250034 has proposed " form the method for fluoropolymer layer on plastic-substrates, this method comprises: will be applied on the plastic-substrates by the masking liquid that adding oligopolymer or polymkeric substance in the monomer that contains the polyfluoro group obtain, also with electron beam it be shone " thereon.According to this method, the oligopolymer of 0.1-30wt% (dissolve or be dispersed in the monomer) added have in the electron beam polymerisable monomer of polyfluoride group, this monomer solution is coated on frosting, and the electron beam with 5-200kGy shines it then, and polymerization is also solidified this monomer.This invention is characterised in that, can form the polymeric film that comprises the polyfluoride group at frosting in the short period of time, and this film does not have the freonll-11 solvent and has excellent adhesion performance.

People's such as J.Kelber U.S. Patent No. 7,036,039 and 4,861,408 have proposed, and shine the binding property of improving substrate by under high vacuum low-energy electron beam being carried out on the polymeric film surface.More particularly, in high vacuum (10 ^-8Torr) (100-10 000eV) handles polymer surfaces, for example with low-energy electron beam in, very, remove fluorine with carbon-fluorine bond from substrate surface near the part (50-10,000 ) on PTFE surface, change this key into carbon-carbon bond or carbon-oxygen bond, improve binding property thus various materials.The film of this processing can use common adhesive to be combined on the surface of brass, copper or steel.

People's such as J.Evans U.S. Patent No. 4,533,566 has proposed, and carries out electron beam by the polyester film to the substrate used as the siloxanes release liner and shines and improve binding property.This patent relates to the manufacturing of release liner, and discloses the method that links the siloxanes thin layer on flexible polyester film.More particularly, when polyester film oxygen concentration less than 500ppm, be preferably less than in the atmosphere of 40ppm when mobile, polyester film be exposed at least 20kGy, preferably 20-200kGy, be more preferably under the electron beam of 50-100kGy, on the film surface, form silicon layer thus.

Toray has submitted the invention of a series of use fluororesin films as substrate to.Wherein, Japanese Patent Application No.10-58617 discloses a kind ofly has stain-proofing layer on a surface, and the reparation plate that comprises fluoro-resin of pressure sensitive adhesive layer is arranged on another surface.By to the surface treatment of fluororesin film or between fluororesin film and stain-proofing layer or pressure sensitive adhesive layer, prime, can quicken bonding between fluororesin film and stain-proofing layer or the pressure sensitive adhesive layer.When between fluororesin film and pressure sensitive adhesive layer, UV-absorbing layer being set, and when in UV-absorbing layer, adding linking agent, can get off to obtain crosslinked by being heated or being exposed to ultraviolet ray or electron beam.But, by surface treatment or prime, can quicken bonding between fluororesin film and the UV-absorbing layer.

Japanese Patent Application No.4-146129 has described, has the technology that the fluorine resin film that forms the printed layers of inkwood oil/fat composition in the metallic surface forms the metal that has been coated with resin by hot melt, wherein, the inkwood oil/fat composition comprises the resin that energy line is curable.In this technology, printed layers only is printed on a part of fluorine resin film, and fluorine resin film hot melt is on metallic membrane.And fluorine resin film hot melt does not still use tackiness agent to link with it on metal base.

Japanese Patent Application No.5-8353 has described a kind of pitch tube that is suitable for as the motor vehicle fuel pipe, and wherein, the pitch tube with polyamide resin skin and fluoro-resin internal layer is crosslinked to produce under being exposed to and shining, and introduces crosslinking structure thus.This is a kind of pair of extrusion resin product, and is different with adhesive plate of the present invention.

But the weakness of these technology is: the binding property between fluorine material and the tackiness agent is not high enough, and it is higher than complexity or cost to reach the adherent process.Therefore, need a kind of sufficiently high easier method of binding property that can make between fluorine material and the tackiness agent.

Under the situation of these routine techniquess, need a kind of make the fluorine material plate with sufficiently high binding property attached to the easier method on the adherend.

Summary of the invention

The present invention is used for addressing the above problem, and relate to without surface treatment or particular adhesive form can be bonding the fluorine material plate.The present invention also relates to the method for a kind of fusible fluorine material plate, bonding fluorine material plate, and the glued construction that uses the fluorine material plate that this can be bonding.

The present inventor before disclosed the pressure sensitive adhesive plate that comprises substrate, this substrate is the nondegradable fluorine material plate of electron beam, and the pressure sensitive adhesive layer that is with or without the middle layer betwixt that is positioned at outer surfaces of substrates, wherein, the fluorine material plate have with pressure sensitive adhesive layer or with the middle layer banded chemical bond that directly contacts with the fluorine material plate, this chemical bond is radiated at least by electron beam and forms (Japanese Patent Application No.11-189081) on the fluorine material plate.The present inventor further studies this, confirmed a kind of can be bonding the fluorine material plate (herein, but viscosity is given layer and is positioned on the surface of the nondegradable fluorine material plate of electron beam, at least but the irradiation of fluorine material plate is formed in fluorine material plate and viscosity by electron beam and to give chemical bond between the layer) to using other tackiness agent, comprise adherend bonding effective of Resins, epoxy, hot melts and acryloid cement.The present invention finishes on the basis of this discovery.

Fluorine material plate that can be bonding of the present invention is a kind of fluorine material plate that can be bonding basically, but it is by coating in fluorine-containing substrate or piles up viscosity and (for example give material, the hot melts of monomer, slurry, oligopolymer or polymkeric substance, perhaps polymerisate solution or aqueous dispersant), and shine it, but can use non-pressure sensitive adhesive adherent viscosity to give layer to obtain to form with electron beam.Irradiation by electron beam, but viscosity is given material component polymerization (crosslinked), and but viscosity gives the free radical reaction of the free radical and the substrate molecule of material molecule, thereby can form stronger Chemical bond effect between low-down two layers of script bond properties, makes that simultaneously substrate is crosslinked.But the viscosity on the fluorine material plate of gained is given layer and has been shown good and binding property common adhesive, and therefore, the fluorine material plate can successfully adhere on the adherend that uses common adhesive.

The structure of fluorine material plate that can be bonding of the present invention, its advantage is, form on the fluorine material plate though but viscosity is given layer, can remove the special surface that between two layers, uses binder layer or fluorine material required in the routine techniques fully from and handle.But viscosity is given the polymerization (crosslinked) of material and be important factors with the reaction of dissimilar materials on the interface, but, the crosslinked of substrate plate can form according to the intensity of electron beam, for example, substrate plate can be whole crosslinked, but perhaps only have and viscosity give the substrate of the contiguous part in interface between the material can be crosslinked, this moment, some materials were carried out the degraded of molecular linkage by electron beam, therefore careful the needs.

The invention provides the adhesive bonding method of fusible fluorine material plate and fluorine material plate, use be above-mentioned fluorine material plate that can be bonding, and the structure that forms.

(1) a kind of fluorine material plate that can be bonding, but it comprises the nondegradable fluorine material plate of electron beam that has viscosity to give layer in its surface, wherein, have chemical bond between the layer but give in fluorine material plate and viscosity, this chemical bond by at least on the fluorine material plate irradiating electron beam form.

(2) as describe in (1) can be bonding the fluorine material plate, wherein, the fluorine material plate contains the crosslinked polymkeric substance by the electron beam irradiation.

(3) as describe in (1) and (2) can be bonding the fluorine material plate, wherein, but viscosity give material and contain that but crosslinked viscosity is given layer by the electron beam irradiation.

(4) as describe in (1)-(3) can be bonding the fluorine material plate, wherein, the fluorine material plate contains the above fluorine of 10wt%.

(5) as describe in (1)-(4) can be bonding the fluorine material plate, it is transparent.

(6) as describe in (1)-(5) can be bonding the fluorine material plate, it is a layer protecting film.

(7) a kind of fusible fluorine material plate, it comprise (1)-(6) but in describe can be bonding the fluorine material plate and be formed at viscosity and give non-pressure sensitive adhesive layer on the laminar surface.

(8) the fusible fluorine material plate as describing in (7), wherein, binder layer is a hot-melt adhesive.

(9) a kind of method of bonding fluorine material plate, it comprise by with adhesive application on the surface of fluorine material plate that can be bonding and/or adherend or between them, apply tackiness agent, make (1)-describe in (6) can be bonding the fluorine material plate be bonded on the adherend.

(10) adhesive bonding method as describing in (9), wherein, tackiness agent is a hot-melt adhesive.

(11) adhesive bonding method as describing in (9), wherein, tackiness agent is a crosslinking binder.

(12) a kind of glued construction of fluorine material plate, wherein, be described in (1)-(6) can be bonding the fluorine material plate be bonded on the adherend by tackiness agent.

(13) glued construction as describing in (12), wherein, tackiness agent is a hot-melt adhesive.

(14) glued construction as describing in (12), wherein, tackiness agent is a crosslinking binder.

Description of drawings

But Fig. 1 forms the example that viscosity is given the fluorine material substrate of layer on one face.

But Fig. 2 forms the example that viscosity is given the fluorine material substrate of layer on two face.

Fig. 3 is the example that has the fluorine material substrate of undercoat on substrate surface, forms the hot-melt adhesive layer on undercoat.

Fig. 4 is the example that has the fluorine material substrate of undercoat on substrate surface, forms elastic layer on undercoat.

Fig. 5 is a bonding example of giving the fluorine material plate of viscosity of the present invention on adherend.

Embodiment

Substrate/fluorine material plate

As the fluorine material (that is, fluorine material or fluorinated material) of the fluorine-containing plate of viscosity of the present invention can be, for example, the homopolymer of fluorocarbons or multipolymer, its mixture or with floride-free mixtures of material.

The example of useful fluorochemical monomer comprises: R 1216 (HFP), tetrafluoroethylene (TFE), vinylidene fluoride (VDF), vinyl fluoride (VF), trifluorochloroethylene (CTFE), 2-five fluorine propenyl chlorides, perfluoroalkyl vinyl ether such as CF ₃OCF=CF ₂And CF ₃CF ₂OCF=CF ₂, 1-hydrogen five fluorine propylene, 2-hydrogen five fluorine propylene, difluoro Ethylene Dichloride, trifluoro-ethylene, 1,1-fluorine Ethylene Dichloride, vinyl fluoride and perfluor-1,3-diox (referring to U.S. Patent No. 4,558,142).The example of useful fluorine-containing diene comprises perfluor diallyl ether and perfluor-1,3-butadiene.Can come the copolymerization fluorochemical monomer with the terminal unsaturation monoene of free-floride such as ethene or propylene.In polyblend, fluorochemical monomer preferably accounts for whole monomeric 50wt% at least.Can make the polymkeric substance of peroxide-curable with containing iodine or brominated curing position monomer comes the copolymerization fluorochemical monomer.The suitable monomeric example in curing position comprises the terminal unsaturation monoene with 2-4 carbon atom, as difluoro bromine ethene, trifluoro bromine ethene, trifluoro iodoethylene and 4-bromo-3,3,4,4-tetrafluoro butene-1.

Also can use the homopolymer of these fluorocarbonss or multipolymer or they and another kind of mixture of polymers or cross-linking products.

The example of spendable fluoropolymer comprises polymkeric substance and multipolymer, as poly(vinylidene fluoride) (PVDF), fluorinated ethylene propylene (PVF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethylene-ethylene-propylene copolymer, tetrafluoroethylene-ethene-perfluoroalkyl vinyl ether multipolymer, tetrafluoroethylene-ethene-seven fluorine pentene copolymer, tetrafluoroethylene-ethene-(perfluoro butyl) ethylene copolymer, tetrafluoroethylene-ethene-hexafluoropropylene copolymer, tetrafluoroethylene propylene copolymer, tetrafluoroethylene-propylene-vinylidene fluoride copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-perfluoroalkyl vinyl ether multipolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymer (THV), hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride-tetrafluoro iodine propoxy-trifluoro-ethylene copolymer, tetrafluoroethylene-vinylidene fluoride copolymer, chlorotrifluoroethylene-ethylene copolymer, trifluorochloroethylene-vinylidene fluoride copolymer, vinylidene difluoride-hexafluoropropylene copolymer and vinylidene fluoride-trifluoro-ethylene copolymer.And, also can use grafting, block or the mixed polymer of these polymkeric substance, their example comprises: by trifluorochloroethylene-vinylidene fluoride copolymer being grafted to the graftomer that obtains on the vinylidene fluoride copolymer and the block polymer of tetrafluoroethylene-ethylene copolymer and vinylidene difluoride-hexafluoropropylene copolymer.

These polymkeric substance have commercially available, and their example comprises following product.Halar - ( Allied ) KF Polymer ( Kureha Kagaku ) Teflon FEP - ( ) Aclon - ( Allied ) KynarFlex 2800 - ( Atochem ) THV 220G -- ( Dyneon ) THV 500G -- ( Dyneon ) Aflon COP - ( ) Cefral Soft ( Central Glass ) Daiel T-530 - ( ) HTE X1500 - ( Dyneon ) NeoflonEP-610 - ( ) Aflas 150E - ( ) Aflas 200 -- ( ) Teflon PFA - ( ) Tedlar ( ) TFM-1700

The fluorine material that constitutes fluorine material plate substrate that can be bonding of the present invention contains fluorine, and therefore, it has fabulous chemical resistant properties, thermotolerance, mechanical property and electrical property.For this purpose, fluorine-containing amount must be at least the 10wt% of material, preferably 30wt% above, be more preferably more than the 40wt%.Fluorine content even can be 76wt% to the maximum for more than the 50wt%.Fluorine material plate of the present invention substrate be preferably in can carry out under the electron beam irradiation crosslinked.Under the situation that substrate is degraded by electron beam, the acceleration voltage of controlling electron beam or linear density lower, make electron beam not only can not see through and damage the surf zone of irradiation, and can not see through and damage whole substrate, also to pay special attention to irradiation time.For example, tetrafluoroethylene is a degradable polymer under the electron beam irradiation, is not suitable for the present invention.But the modified Teflon that uses degradation property to improve is comparatively suitable.Simultaneously, the degradable material of electron beam can be nondegradable with electron beam or the electron beam crosslinkable material be used in combination because the film that this binding substances forms can be under the electron beam irradiation or is destroyed with this understanding.

The thickness of fluorine material plate substrate that can be bonding of the present invention has no particular limits.Under the situation that protecting sheet is made by polyvinyl chloride, can use the commercially available prod of thick 5mm or the product that is called " film " that those thickness is lower than the hundreds of micron.Usually, the thickness of substrate is about 50-1,000 μ m.The application of substrate can be plate, adhesive tape, graphic films, insulcrete etc. without limits.Optionally, can in fluorine-containing material, add various additives, as tinting material (pigment and dyestuff), filler, UV light absorber.

But viscosity is given layer

But the viscosity used of fluorine material plate that can be bonding of the present invention is given material and is had no particular limits, and can use under the electron beam irradiation any material that can form chemical bond, can be glue bound again simultaneously with the fluorine material plate.

For example, but constitute viscosity to give the component of material can be hydrocarbon system (for example, acrylic ester, polyurethane series) or rubber based compound.In addition, even polyolefin, viscosity siloxane-based and fluorochemicals are lower usually, also can use, because can use associated tackiness agent.Generally the acrylate as the hydrocarbon system compound of Shi Yonging is particularly useful,, the substrate that the present invention uses is the fluorine material with fabulous chemical resistant properties and good weathering resistance, therefore, but viscosity is given material and is preferably had identical performance under same case, for this purpose, use siloxane-based, fluorine-containing or the polyolefin compound.But also can give material, but but the polymerization formation viscosity of perhaps giving material monomer by independent viscosity is given material with linking agent, oligopolymer or mixed with polymers viscosity.Viscosity is given composition and is preferably formed by electron beam sensitive monomer, oligopolymer, polymkeric substance or linking agent, because shining by electron beam, combining between substrate and the pressure sensitive adhesive quicken, and, but viscosity is given the shearing holding force or the thermotolerance of material and has been improved.

But the viscosity that can be endowed the fluorine material plate of viscosity is given layer and can be made by various materials, for example, the undercoat that forms by the material that tackiness agent is had higher wettability, by giving elastic layer, the monochromatic solid layer that elastic urethane of fluorine material plate or acrylic rubber glue material form, the printed layers that literal and background color or image are arranged or at the backing layer of the thickness that reduces fluorine material with the operability that is used for guaranteeing film when reducing cost, but it has no particular limits.

Below, the purpose in these middle layers is used in summary.

Undercoat

For example, can be with the surface of the material primary coat fluorine material substrate that tackiness agent is had higher wettability.Priming paint is the acrylate and the vinyl compound of electron beam curable preferably.For example, preferably can use monofunctional acrylate, comprise vinylformic acid, ethyl propenoate, butyl acrylate, 2-EHA, Isooctyl acrylate monomer, vinylformic acid methoxyl group ethyl ester, vinylformic acid 2-ethoxy ethyl ester, vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, glycidyl acrylate, isobornyl acrylate, vinylformic acid methoxy poly (ethylene glycol) ester, vinylformic acid morpholine ester, phenoxyethyl acrylate, vinyl-acetic ester and N-vinyl pyrrolidone, and polyfunctional acrylic ester, comprise triallyl isocyanurate, the diacrylate butanediol ester, pentaerythritol triacrylate, diacrylate macrogol ester and acroleic acid polyurethane.These acrylate can use separately or two or more being used in combination.

The advantage of undercoat is that for example, extremely thin undercoat can be caused under higher linear velocity surface reaction taking place by electrocuring, thus the fluorine-containing plate of viscosity that made giving of desired thickness minimum.

In the present invention, the thickness of undercoat has no particular limits, and can be, for example is lower than 100 μ m, and is suitable to being lower than 50 μ m.But in order to use fluorine-containing plate effectively, undercoat is preferably thinner, and under this meaning, thickness is preferably lower than 30 μ m, be more preferably and be lower than 10 μ m.

Elastic layer

But can be used as by the elastic layer that polyurethane material, acrylic rubber glue material, silicone elastomer material, snappiness epoxy material or foaming material form and to reach following purpose viscosity and give layer.The thickness on fluorine material top layer that can reduce to have weather resistance to be reducing cost, and do not damage the operability of film.And, owing to there is elastic layer, can improve the consistence (on solidified surface apply performance) of the solidified surface of conduct pressure tunic, perhaps the stability of resisting temperature cataclysm or weather resistance.In addition, when below elastic layer is positioned at substrate, it is as protective membrane, prevention or reduce by cobble collision or the cut that produced with the hard material friction, and to reach the purpose of material protection, perhaps prevention or reduce fluorine material generation crack itself.

Printed layers

The example of printed layers comprises the monochromatic solid layer or comprises literal/image and the printed layers of background color.For example, when using common coating to be coated with again, be coated with again in surface finish or after with solvent cleaning, but, have under the situation of printed layers and painted thereon or printing at the fluoropolymer membrane that has than high weather resistance, this process not necessarily perhaps can shorten this process.Even this layer is not used for coating and as protective layer, needs painted sometimes yet.Simultaneously, painted different according to situation, for example, need perhaps type sign or Babcock and Wilcox can be printed on the protective membrane in order to prevent observing the painted or translucent painted of background color (shielding).

Backing layer

The thickness on fluorine material top layer that no matter whether reduces to have weather resistance, be arranged on backing layer between fluorine material top layer and the binder layer in order to reach the purpose of the operability of guaranteeing film with the reduction expense.Its suitable example comprises acryloyl layer, layer of polyurethane and soft pvdf layer.

Optionally, but viscosity give material and can also comprise a spot of various additive, as pigment, dyestuff, softening agent, filler, stablizer, UV light absorber, antioxidant, smoothing agent, tensio-active agent and process oil.

It can be no-solvent type material (for example, the hot melts of slurry, oligopolymer or polymkeric substance), organic solvent type material and aqueous dispersion type material (for example, milk sap, suspension) that but the viscosity of using among the present invention is given material.

But these viscosity are given the quantity of layer and are not limit, and for example, can use such structure, as fluorine material substrate/undercoat, fluorine material substrate/undercoat/elastic layer or fluorine material substrate/undercoat/pigmented layer (printed layers).The invention is characterized in:, give on the layer but will make the fluorine material substrate that directly contacts with them be attached at viscosity by the electron beam irradiation with chemical process because the fluorine material substrate is lower to the binding property of adherend.

But giving material with the viscosity that the present invention uses is coated on fluorine-containing suprabasil method and has no particular limits.Can use solvent-borne type coating process or no-solvent type coating process at coating after drying solvent.The solvent that coating is used as solvent-borne type (normally polymers soln) generally uses ethyl acetate, methyl ethyl ketone or their mixed solvent.

In no-solvent type coating, but can not use solvent and directly coating viscosity give material (monomer, slurry, oligopolymer, polymkeric substance or their mixture), perhaps by coating such as spraying grade.Particularly under the situation of polymkeric substance, also can use the hot melts coating.

But be easy to wetting fluorine material substrate in order to make viscosity give material, can with fluorochemical surfactant, coupling agent, have a functional group such as hydroxyl, carboxyl or an ether fluorocarbon (for example, PFPE glycol (Dynamar FC-2202,3M company produces) adds viscosity and gives in the composition.And, but wettability also can by to form viscosity give add in the monomer of material photoinitiator, will to mixture be exposed to that the control that molecular weight or viscosity are increased is limited in pulpous state and in substrate painting slurry improve.

The object lesson of spendable coating process comprises: rod is coated with, winds the line that rod is coated with, four roller coat cloth, gravure coating, spraying, notch bar is coated with and moulded rod is coated with.

The fluorine material plate of having given viscosity of the present invention is characterised in that: by electron beam irradiation, form chemical bond between the layer but give in fluorine material substrate and viscosity.In the fluorine-containing plate of routine, when fluorine material is used as substrate, the bonding force deficiency between substrate and the binder layer, substrate does not have binding property because tackiness agent is to fluorine material.Therefore, in order to increase the bonding force between substrate and the binder layer, proposition is carried out special processing (for example, sodium Metal 99.5 is handled, alkaline purification) to substrate surface or insert special middle close binder (by fluorine material and tackiness agent are had the layer that fusible material forms) between them.But performance (for example, bond strength, transparency) and availability are difficult to obtain simultaneously.On the other hand, according to the present invention, find as long as shine by electron beam, but just can give and form chemical bond between the layer in fluorine material substrate and viscosity, strengthen the bonding force between them thus significantly, the result has obtained comprising the viscosity of practical fluorine material substrate and has given plate, and wherein, but viscosity is given layer and fully, firmly is attached in the fluorine material substrate.On the surface of the fluorine material substrate of shining with electron beam, the bond rupture of polymkeric substance is with the generation free radical, but the avtive spot that makes viscosity give material links thereon.Under the electron beam irradiation, also can produce free radical because but viscosity is given material, but promote substrate and viscosity to give the effect of mutually combining between the material.But can not produce about the viscosity that forms like this and give fusible problem between layer and the binder layer.

In the present invention, but electron beam must be radiated at fluorine material substrate and viscosity at least gives on the interface between the layer.But the viscosity that electron beam not only preferably had been radiated in the fluorine material substrate but also irradiation forms is thereon given on the layer, because simple like this and bonding force is bigger.When electron beam is radiated in the fluorine material substrate, crosslinking structure can be introduced in the polymkeric substance of fluorine material substrate.

But give under the situation that forms covalent linkage between the layer in be radiated at fluorine material substrate and viscosity by electron beam, this bonding with by other method, as the structure difference that sodium Metal 99.5 is handled or alkaline purification obtains when forming chemical bond.Fluorine-containing substrate of having given viscosity of the present invention is to be feature to have the structure that obtains from electron beam irradiation.

As another feature of having given the fluorine-containing plate of viscosity of the present invention, but be radiated at fluorine material substrate and viscosity by electron beam are given when forming chemical bond between the layer, surface treatment is not carried out on the surface of fluorine material substrate, handles or corona discharge as sodium Metal 99.5.On the surface of the fluorine material substrate of having carried out the processing of surface treatment such as sodium Metal 99.5, have the vestige that surface treatment such as sodium Metal 99.5 are handled, still, the present invention does not have such vestige.For example, in sodium Metal 99.5 was handled, the surface discolouration of fluorine material substrate became brown or black.When the substrate variable color, the fluorine material plate can not be transparent.

According to the present invention, but give on the surface that material is coated on the fluorine material substrate when viscosity, and when linking thereon, but can carry out polymerization that viscosity gives material or crosslinked simultaneously by irradiation by the electron beam irradiation.Therefore, compare with routine techniques and the invention has the advantages that: but do not need additionally to be increased in the special procedure that fluorine material substrate and viscosity are given Cheng Jian between the layer.And, because fluorine-containing substrate also can be next crosslinked by the irradiation of electron beam, can further improve the chemical resistant properties and the thermotolerance of substrate.

But electron beam can be given layer one side or substrate one side from viscosity and shine.

But if produce free radical giving on the substrate surface that directly contacts of layer with viscosity, then the electron beam condition of shining is very abundant.But these conditions are given the kind of material and thickness and different according to fluorine material substrate or viscosity, and still, suitable is more than the 10keV.Be more preferably 50-200keV, 30-1,000kGy.

According to the present invention, find by electron beam the irradiation of substrate on the surface of substrate, producing free radical, but immediately on substrate surface coating viscosity give layer, form Chemical bond between the layer but also can give in fluorine material and viscosity.But, but give layer with on substrate surface, forming viscosity, then with the electron beam irradiation situation compare, the intensity of the chemical bond of formation has decline slightly.But give and keep vacuum between the layer though be preferably in electron beam irradiation substrate surface and coating viscosity in theory, to prevent free radical and the oxygen free radical reaction on the substrate surface, even but by irradiation EB, and then in common atmosphere (oxygen concentration: about 20%) the acrylate slurry is coated with thereon, also uses ultraviolet curing, also can be met the intensity of enough interfacial adhesion agent of practical application.

But can be by giving of gained the bounding force/stripping test of fusible fluorine material plate estimate the intensity that fluorine material substrate of the present invention and viscosity are given the chemical bond that forms between the layer.Concrete method will be described among the embodiment afterwards.

According to the present invention, confirmed from the result of the bounding force/stripping test of fluorine material plate that can be bonding (herein, but give form chemical bond between the layer in fluorine material substrate and viscosity): formed strong chemical bond between the layer but give in fluorine material substrate and viscosity.

Adhesive bonding method

On the fluorine material plate of having given viscosity of the present invention, but viscosity is given the surface that layer is formed at the relatively poor fluorine material substrate of binding property, therefore, with not using special methods with the same mode of the adhesive bonding method that uses common non-pressure sensitive adhesive, the fluorine material plate just is easy to be bonded on the surface of adherend.

Promptly, but give adhesive application on one or two surface and the surface of adherend of layer in the viscosity of the fluorine material plate of having given viscosity, but the viscosity of perhaps having given the fluorine material plate of viscosity is given between layer and the adherend, exert pressure then and make the fluorine material plate contact tightly or engage with adherend, therefore, the fluorine material plate can be bonded on the adherend.

The example of non-pressure sensitive adhesive that is used for this method is as follows.

Hot-melt adhesive

Hot-melt adhesive is meant that mainly comprising thermoplastic resin, solid content is 100% tackiness agent, and it at room temperature is a solid.Hot-melt adhesive usually in being called the coating machine of applicator hot melt separate, and under the melting state, be coated on the adherend.After under pressure, adhering to, when the melting resin cools off, bonding finishing.Under the situation of fluorine material plate that can be bonding of the present invention, but hot-melt adhesive can give laminar surface and adhere to provisionally by fusing or be coated on viscosity in advance, preparation is used for the fluorine material plate that adherent can be bonding.

The not moisture or solvent of hot-melt adhesive can save drying plant and time of drying, thereby finishes bonding by adhere to one short period under pressure having applied behind the tackiness agent.And unlike the pressure sensitive adhesive plate, hot-melt adhesive did not show bond properties before hot melt is separated, and therefore, its storage is simple, and storage stability is fabulous.

About constituting the composition of hot-melt adhesive, can use thermoplastic resin, tackifier or wax, optionally, can mix antioxidant, filler etc.The representational example of thermoplastic resin (base material polymer) comprising: vinyl-vinyl acetate copolymer (EVA), polyethylene, Atactic Polypropelene (APP), ethylene-ethyl acrylate copolymer (EEA), polymeric amide and polyester.The example of spendable tackifier comprises: rosin, rosin derivative, send alkene type resin and hydrocarbon resin (petroleum resin).Wax is used for reducing the melt viscosity or the control physical properties of tackiness agent, as open hour, softening temperature, hardness, thermal viscosity and caking.

The method of application of hot-melt adhesive (using method) is mainly according to its shape, promptly between block hot melts and membranaceous hot melts, and variant slightly.Under the situation of block hot melts; to become spherolite or bar-shaped hot-melt adhesive in having the applicator of different size, to heat, liquefy; and with point or linearly be coated on that the material (adherend) that will adhere to is gone up or with the spraying of spider net form, and before hot melt adhesive cools is solidified, another adherend is stacked thereon.Hot-melt adhesive solidifies at the several minutes internal cooling usually, and therefore, can obtain sufficiently high intensity this moment.Under the situation of membranaceous hot-melt adhesive, not to separate by hot melt to reach bonding, but the hot-melt adhesive that will be pre-formed film places and wants between two adherends of adherent (or two blocks of adherend plates), make these adherends by thermocompressor or hot-rolling, hot melts between the liquefaction adherend, bonding thus finishing.Want under the adherent situation on the whole surface of wanting the adherent material to be membranaceous or adherend, this method is effective.In the method, itself is heated adherend, and therefore, the relation between the thermotolerance that must be by considering adherend and the liquefaction temperature of hot melts is used this method.Specifically, for the lower adherend of thermotolerance or cause the situation of the use of dimensional change for the restricted passage heating, the tackiness agent that can liquefy at low temperatures, (production of 3M company) is effective as low melt series.Hot-melt adhesive comprises that also rubber is hot melts and its main component, usually use the polystyrene elastomerics in many cases, as SIS (styrene-isoprene-styrene copolymer-), SBS (styrene-butadiene-styrene multipolymer) and SEBS (styrene-ethylene-butylene-styrene multipolymer), perhaps ethylene series elastomerics.Simultaneously, be to mix tackifier or wax in the hot melts at rubber.In addition, hot-melt adhesive can be moisture curing hot melts (mainly being the polyurethane series hot melts).The difference of this and ordinary hot hot melt adhesive is that bond strength passs in time and increases, that is, curing reaction just carries out because of moist, but its using method is identical with the ordinary hot hot melt adhesive basically.

These hot-melt adhesives are applicable to the didirtresistance that will improve the surface, improve chemical resistant properties, improve weathering resistance or reduce the application of frictional coefficient.

Curable adhesive

Curable adhesive comprises thermosetting adhesive, room-temperature-curable tackiness agent and ultraviolet curable tackiness agent.

(1) epoxy resin binder

Generally the curable adhesive of Shi Yonging is the epoxide resin type tackiness agent.But the rough segmentation of epoxide resin type tackiness agent is thermosetting adhesive and room-temperature-curable tackiness agent.Thermosetting adhesive is in down thermofixation of high temperature (common more than 80 ℃), and therefore, crosslinking structure is easy to densification, and cured product has high strength, superior thermotolerance and fabulous chemical resistant properties usually.The room-temperature-curable tackiness agent is by with epoxy owner agent and solidified reagents, mixes as amine or mercaptan, then the tackiness agent that at room temperature its curing is obtained.Its advantage is, does not need heating installation, and solidifies and can carry out out of doors.Even under the situation of room-temperature-curable tackiness agent, when it was heating and curing, curing can be finished at short notice or can quicken curing reaction.

(2) other curable resin tackiness agent

When using the curable tackiness agent of ultraviolet rays, use visible light or electron beam, can finish curing in the short period of time, in several seconds.Main component is acryloyl class, type siloxane or epoxy type adhesive normally.Specifically, except photocurable type, but the rough segmentation of acryloyl tackiness agent is: the anaerobic polymerization type that begins to react under the condition of secluding air, priming paint type, biliquid mixed type and microcapsule-type, these also can use.

Rubber is tackiness agent

Rubber is that tackiness agent comprises Hotmelt Adhesive (above-mentioned) and aerosol-type tackiness agent (following).In general, use the tackiness agent that obtains by dissolving rubber in solvent in many cases.The example of rubber comprises various rubber, is synthetic rubber, acrylic rubber, urethanes and silicon rubber as natural rubber, SBR (styrene butadiene rubbers), NBR (paracril), neoprene, isoprene-isobutylene rubber, poly-sulphur.In addition, can use derivative (for example, chlorinated rubber, vulcanized rubber, toxilic acid rubber) and graft copolymer or block copolymer rubber.Rubber uses extensively, because it can stick on many materials usually preferably, and its initial adhesion strength is bigger.In many cases, rubber is dissolved in the organic solvent, and the rubber solutions of gained is coated with or is sprayed on the adherend.Sometimes as aqueous dispersion type latex, this will be described below rubber.Usually be to add tackifier, vulcanizing agent and antioxidant in the tackiness agent to rubber.

Aqueous binder

Aqueous binder is the aqueous dispersion type tackiness agent in the present invention, comprises that previous known natural rubber is a latex.In recent years, using synthetic rubber in many cases is latex.The example that the main synthetic rubber that uses is a latex comprises: SBR (styrene butadiene rubbers), NBR (paracril), CR (neoprene), IR (synthetic polyisoprene) and acrylic rubber.Aqueous binder is that advantage is: because do not contain organic solvent, can improve Working environment (danger of no fire or poisoning); Because medium is a water, do not contain organic solvent, manufacturing procedure is simple; And compare with Solvent Adhesive, tackiness agent can use under higher concentration, because this is a dispersed adhesive.In many cases, in this aqueous binder, add linking agent, crosslinked accelerator, tackifier and intensifier usually.

The aerosol tackiness agent

The aerosol tackiness agent is a tackiness agent by dissolving or dispersion rubber usually, i.e. rubber is packed in the injector in solution and together with propelling agent and prepares.In some cases, tackiness agent does not use propelling agent to spray with spray form by hand pump.The composition itself of tackiness agent is identical with the composition of Solvent Adhesive or aqueous binder.

Other tackiness agent

It also is very suitable using instantaneous adhesive (cyanoacrylate system).

(fusible fluorine material plate)

In the adhesive bonding method that uses fluorine material plate that can be bonding of the present invention, as mentioned above, use tackiness agent, as hot-melt adhesive the fluorine material plate is bonded on the adherend, this not only can be undertaken by the method that at first applies tackiness agent to the fluorine material plate in bonding, but and can be by giving on the laminar surface interim bonding binder layer such as hot-melt adhesive to prepare fusible fluorine material plate by fusion in advance or with the viscosity that hot-melt adhesive is coated on fluorine material plate that can be bonding of the present invention, apply the fusible fluorine material plate that makes and their heating are carried out to finish the adherent method to adherend in the suitable stage.

Similarly, but the present invention also comprises the fusible fluorine material plate that obtains of surface of giving layer by the viscosity that provisionally tackiness agent is bonded in fluorine material plate that can be bonding.

Be suitable as the example of the tackiness agent of fusible fluorine material plate, except hot-melt adhesive, also comprise: acrylic-type adhesive binder, rubber are tackiness agent, latex build tackiness agent and instantaneous adhesive.

But the present invention does not comprise disclosed pressure sensitive adhesive among the Japanese Patent Application No.11-189081.

The example of useful tackiness agent comprises above-mentioned those tackiness agents relevant with adhesive bonding method, but can by consider the viscosity that forms on the fluorine material plate give between layer and the tackiness agent binding property, tackiness agent and adherend (for example, metal, glass, organic materials) between bond property, the final application in required character (for example, chemical resistant properties, weather, didirtresistance) and working conditions select suitable binder.

Below, describe structure example of the present invention, adhesive bonding method with reference to the accompanying drawings and given the fluorine material plate of viscosity and the glued construction of fusible fluorine material plate.

But Fig. 1 shows and form the example that viscosity is given layer 2 in fluorine material substrate 1.

But Fig. 2 shows and form the example that viscosity is given layer 2 and 3 on two surface of fluorine material substrate 1.In the fluorine material plate of having given viscosity of the present invention, but viscosity is given layer and can be positioned on two surfaces of fluorine material substrate.

But Fig. 3 shows and form the undercoat 4 of giving layer as viscosity on the surface of fluorine material substrate 1, and hot-melt adhesive layer 5 adheres to thereon the example of (example of fusible fluorine material plate) provisionally.

Fig. 4 show fluorine material substrate 1 and layer 6 as elastic layer on formation undercoat 4, and form the example of printed layers or backing layer thereon.In the example of Fig. 4, printed layers or backing layer 6 can directly form in fluorine material substrate 1, and need not form undercoat 4.

In these examples, the fluorine material plate of having given viscosity of the present invention is characterised in that: the bonding between the layer of fluorine material substrate 1 and direct contact with it is the Chemical bond that the electron beam irradiation is caused.Other each layer also can shine bonding by electron beam.

Fig. 5 shows the fluorine material plate of having given viscosity of the present invention is bonded in example on the adherend.The example of adherend 6 is glass or the plastic plates that should avoid surface contamination.When hot-melt adhesive 8 is in the melting state, be bonded on the adherend adding the fluorine material plate of depressing thereon with applicator (not shown) coated heat hot melt adhesive 87 of having given viscosity, then, in seconds with hot-melt adhesive 8 coolings, bonding thus finishing.

Embodiment

Below, with reference to embodiment the present invention is described, still, in any case the present invention is not limited to them.

Basilar membrane

The fluorocarbons basilar membrane that uses in embodiment and the comparative example is shown in following table 1.

Table 1: basilar membrane

Be called for short	Trade(brand)name or composition	Thickness (μ m)	Retailer
				????THV?500	The TFE-HFP-VDF terpolymer	????200	?Dyneon?LLC
????PVDF	??Kynar?740	????260	?Atochem
				????ETFE	ET 6235J ethene-TFE multipolymer	????120	?Dyneon?LLC
????m-PTFE	TFM-1700, modified ptfe	????100	?Dyneon?LLC

In table 1, THV is TFE-HFP-VDF terpolymer (TFE is that tetrafluoroethylene, HFP are that R 1216, VDF are vinylidene fluorides), and PVDF is a poly(vinylidene fluoride), and ETFE is ethene-TFE multipolymer, and m-PTFE is a modified Teflon;

By the heat pressurization PVDF and E-TFE plastic film are made film, PTFE is a commercial membrane, and m-PTFE is carried out the plunger tpe plastic film, the film of section system then;

The preparation of THV 500 usefulness T-plastic film forcing machines;

The electron beam irradiation

In following examples, under the condition of acceleration voltage 150-250kV, dosage 50-200kGy and linear velocity 2-5m/min, electron beam is irradiated into nitrogen atmosphere (oxygen concentration: about 50ppm) from anti-haftplatte one side at normal temperatures.The equipment that uses is the System 7824 that Energy Science company makes.

But the fluorine material plate is given the bonding of layer with viscosity

In following examples, be bonded on the fluorine film (THV film or pvdf membrane) but give layer by the electron beam irradiation viscosity that former intrinsic viscosity is lower.For example, viscosity is given isobornyl acrylate or butyl acrylate and acrylic acid mixture or coated material or the China ink that the material layer is resilient material such as urethane and acrylate elastomerics, polymerization formation undercoat or anchoring layer.In some cases, painted to each layer (resilient material, undercoat or coated material), therefore, can check this possibility at this.Simultaneously, but as can be known when viscosity is given layer and formed, it is bonding to use tackiness agent finally to finish, and this in conjunction with in, with aftermentioned method test bond strength.

Adherend (fluorine material plate)

About 200 μ m) or pvdf membrane (commercial membrane, thickness: about 260 μ m) the THV500 film (uses T-plastic film forcing machine to make thickness:.

But the viscosity that forms on the fluorine material plate is given layer

(a) undercoat

Use three kinds of materials, promptly, isobornyl acrylate (IBA, IB-XA, the production of oil chemistry Co., Ltd. of common prosperity society), tert-butyl acrylate (TBA, Osaka organic chemistry Co., Ltd. produces) and the mixture (ratio of mixture: BA/AA=30/70) of butyl acrylate (BA, Wako Pure Chemical Industries, Ltd. produces) and vinylformic acid (AA, Wako Pure Chemical Industries, Ltd. produces).Under any circumstance, (Darocur 1173 for the photoinitiator of adding 0.01% (for the embodiment of electrocuring) or 0.5% (for the comparative example of ultraviolet curing), the extraordinary product of Chiba KCC produces), after having increased viscosity, be coated with each material by uviolizing.Control coating thickness is about 30 μ m.After the coating,, use electron beam (embodiment) or ultraviolet ray (comparative example) to be cured then by transparent silicone release liner protection surface.Composition is shown in table 2.

(b) resilient material

As the polyurethane series material, vinylformic acid 2-methoxyl group ethyl ester (Wako Pure Chemical Industries, Ltd.'s production) is as acrylic rubber section bar material to use acroleic acid polyurethane (M-1310, synthetic chemistry Co., Ltd. in East Asia produces, cross-linking type is because this is two functional).Because vinylformic acid 2-methoxyl group ethyl ester is a simple function, under certain conditions, also will be to wherein adding linking agent.

At about 80 ℃ the higher hot melting of acroleic acid polyurethane of viscosity at room temperature is coated on the fluorine film, makes the thickness of film be about 200 μ m.Can add solvent diluent or tensio-active agent.By adding a small amount of (0.01% or 0.5%) photoinitiator, irradiation ultraviolet radiation then is increased to the viscosity of the vinylformic acid methoxyl group ethyl ester that at room temperature viscosity is lower and guarantees coating degree preferably.Optionally, can add tensio-active agent.Subsequently, in certain embodiments, add linking agent (KAYARAD HDDA, Nippon Kayaku K. K produces).Control coating thickness is about 200 μ m.After the coating,, use electron beam (embodiment) or ultraviolet ray (comparative example) irradiation then to solidify layers of material by transparent silicone release liner protection surface.Composition is shown in table 2.

(c) coated material or China ink

Use the China ink (UV FIL China ink No.190, kingdom's printing ink is made Co., Ltd. and produced) of ultraviolet curing, mark the line of wide about 300 μ m, and be cured by electron beam (embodiment) or ultraviolet ray (comparative example).

Electron beam or ultraviolet irradiation condition

Under the condition of acceleration voltage 250kV and linear density 200kGy, carry out the electron beam irradiation.Uviolizing is at irradiation dose 1,500mJ/cm ²Carry out.

Table 2: the collocation of composition and fluorine film

	Composition	The fluorine film
			Embodiment 1	The IBA+0.01% photoinitiator	????THV
Comparative example 1	The IBA+0.5% photoinitiator	????THV
			Embodiment 2	The IBA+0.01% photoinitiator	????PVDF
Comparative example 2	The IBA+0.5% photoinitiator	????PVDF
			Embodiment 3	The TBA+0.01% photoinitiator	????THV
Comparative example 3	The TBA+0.5% photoinitiator	????THV
			Embodiment 4	The TBA+0.01% photoinitiator	????PVDF
Comparative example 4	The TBA+0.5% photoinitiator	????PVDF
			Embodiment 5	The BA/AA=30/70+0.01% photoinitiator	????THV
Comparative example 5	The BA/AA=30/70+0.5% photoinitiator	????THV
			Embodiment 6	The BA/AA=30/70+0.01% photoinitiator	????PVDF
Comparative example 6	The BA/AA=30/70+0.5% photoinitiator	????PVDF
			Embodiment 7	????M-1310	????THV
Comparative example 7	The M-1310+0.5% photoinitiator	????THV
			Embodiment 8	????M-1310	????PVDF
Comparative example 8	The M-1310+0.5% photoinitiator	????PVDF
			Embodiment 9	The MEA+0.01% photoinitiator	????THV
Comparative example 9	The MEA+0.5% photoinitiator	????THV
			Embodiment 10	The MEA+0.01% photoinitiator	????PVDF
Comparative example 10	The MEA+0.5% photoinitiator	????PVDF
			Embodiment 11	MEA+0.01% photoinitiator+0.5% linking agent	????THV
Comparative example 11	MEA+0.5% photoinitiator+0.5% linking agent	????THV
			Embodiment 12	MEA+0.01% photoinitiator+0.5% linking agent	????PVDF
Comparative example 12	MEA+0.5% photoinitiator+0.5% linking agent	????PVDF
			Embodiment 13	MEA+0.01% photoinitiator+1% linking agent	????THV
Comparative example 13	MEA+0.5% photoinitiator+1% linking agent	????THV
			Embodiment 14	MEA+0.01% photoinitiator+1% linking agent	????PVDF
Comparative example 14	MEA+0.5% photoinitiator+1% linking agent	????PVDF
			Embodiment 15	????UV?FIL?190	????THV
Comparative example 15	????UV?FIL?190	????THV
			Embodiment 16	????UV?FIL?190	????PVDF
Comparative example 16	????UV?FIL?190	????PVDF

Conclusion

By after electron beam or the ultraviolet curing, remove protective lining (except embodiment 15 and 16 and comparative example 15 and 16).Subsequently, at room temperature all sample was immersed in the methyl ethyl ketone 24 hours, check binding property and solvent resistance between each layer then.In the sample of embodiment 1-16, between fluorine film and elastic layer, undercoat or coated material layer, do not produce and peel off, each layer do not dissolve or disappears in the solvent, do not observe special variation like this.On the other hand, in comparative example, taken place each interlayer peel off or solvent in dissolving.Gained the results are shown in following table 3.

Table 3: the variation after immersing in the solvent

Embodiment 1	There is not special variation
		Comparative example 1	Acrylate layer is dissolved in the solvent
Embodiment 2	There is not special variation
		Comparative example 2	Acrylate layer is dissolved in the solvent
Embodiment 3	There is not special variation
		Comparative example 3	Acrylate layer is dissolved in the solvent
Embodiment 4	There is not special variation
		Comparative example 4	Acrylate layer is dissolved in the solvent
Embodiment 5	There is not special variation
		Comparative example 5	Acrylate layer is dissolved in the solvent
Embodiment 6	There is not special variation
		Comparative example 6	Acrylate layer is dissolved in the solvent
Embodiment 7	There is not special variation
		Comparative example 7	Layer of polyurethane peels off and is suspended in the solvent
Embodiment 8	There is not special variation
		Comparative example 8	Layer of polyurethane peels off and is suspended in the solvent
Embodiment 9	There is not special variation
		Comparative example 9	The acrylic rubber glue-line is dissolved in the solvent
Embodiment 10	There is not special variation
		Comparative example 10	The acrylic rubber glue-line is dissolved in the solvent
Embodiment 11	There is not special variation
		Comparative example 11	The acrylic rubber glue-line peels off and is suspended in the solvent
Embodiment 12	There is not special variation
		Comparative example 12	The acrylic rubber glue-line peels off and is suspended in the solvent
Embodiment 13	There is not special variation
		Comparative example 13	The acrylic rubber glue-line peels off and is suspended in the solvent
Embodiment 14	There is not special variation
		Comparative example 14	The acrylic rubber glue-line peels off and is suspended in the solvent
Embodiment 15	There is not special variation
		Comparative example 15	Coated material is dissolved in the solvent
Embodiment 16	There is not special variation
		Comparative example 16	Coated material is dissolved in the solvent

The formation of multilayered structure

But known when above-mentioned viscosity give that layer forms and attached to fluorine material on the time, but viscosity is given layer itself and finally can be come bonding by tackiness agent.Therefore, show here and use the poor especially fluorine material film TFM-1700 (modified Teflon) of viscosity and as the result of the bond test of the ETFE (ethylene/tetrafluoroethylene/vinylidene fluoride copolymer) of the exemplary of fluorine material and PVDF (poly(vinylidene fluoride)).The structure of test board is a four-layer structure: fluorine material film/electron beam curable material (undercoat)/tackiness agent/adherend.The tackiness agent that uses is epoxy resin binder, UV curable adhesives and hot-melt adhesive.In all cases, the present invention can both significantly improve the binding property of fluorine material film.

(1) but give layer with the prepolymer slurries of different BA that form and AA as viscosity and be coated with the thickness difference of coating.Electron beam with different dose irradiation, with the polymerization undercoat, makes undercoat and substrate combination from a side of undercoat.

Use epoxy resin binder (Scotch-Weld DP-100 Plus clear, 3M company makes) to be bonded on the sheet glass separately plate of handling like this and the untreated plate that is used for comparison.The thickness of tackiness agent is about 30 μ m.

After the viscosity, measure 180 ° of stripping strengths of fluorine material plate, wherein, peeling rate is 30mm/min.

The results are shown in table 4.

Table 4: the result who uses the bond test of epoxy resin binder

		Dosage (kGy)	Form	Priming paint thickness (μ m)	Stripping strength (N/25mm)
						Embodiment 17	???ETFE	????100	?BA/AA(90/10)	?????5	????14.5
Comparative example 17	???ETFE	Do not have	?-	?????-	????0.4
						Embodiment 18	???PVDF	????100	?BA/AA(90/10)	?????5	????28
Comparative example 18	???PVDF	Do not have	?-	?????-	????5-25
						Embodiment 19	???TFM-1700	????100	?BA/AA(75/25)	?????70	????14.5
Embodiment 20	???TFM-1700	????100	?BA/AA(75/25)	?????5	????10.5
						Embodiment 21	???TFM-1700	????150	?BA/AA(75/25)	?????5	????9.0
Embodiment 22	???TFM-1700	????150	?BA/AA(75/25)	?????5	????8.2
						Comparative example 19	???TFM-1700	Do not have	?-	?????-	????3.2

(2) carry out bondingly with above-mentioned same method, substitute beyond the epoxy resin binder, the stripping strength mensuration that uses the same method except using ultraviolet curable tackiness agent (Scotch-Grip LC-2101,3M company makes).The thickness of tackiness agent is about 30 μ m.The thickness that consists of IOA/AA (90/10), coating of undercoat is about 5 μ m, electron beam intensity is 100kGy.

The result is summarized in table 5.

Table 5: the result who uses the bond test of ultraviolet curable tackiness agent

		Dosage (kGy)	Form	Priming paint thickness (μ m)	Stripping strength (N/25mm)
						Embodiment 23	????ETFE	????100	?BA/AA(90/10)	????5	????2.3
Comparative example 20	????ETFE	Do not have	?-	????-	????0.1
						Embodiment 24	????TFM-1700	????100	?BA/AA(90/10)	????5	????9.1
Comparative example 21	????TFM-1700	Do not have	?-	????-	????0.35

(3) repeat said process, substitute beyond the epoxy resin binder except using hot-melt adhesive (triple bond film 668,3M company makes).Pressurizeed for 10 seconds at 160 ℃ of tabular tackiness agents that thickness is about 100 μ m, make its thickness be about 90 μ m behind the pressurized.

The result of stripping strength is summarised in the table 6.

Table 6: the result who uses the bond test of hot-melt adhesive

		Dosage (kGy)	Form	Priming paint thickness (μ m)	Stripping strength (N/25mm)
						Embodiment 25	????TFM-1700	????100	???BA/AA ??(75/25)	????5	????9.5
Comparative example 22	????TFM-1700	Do not have	??-	????-	????1.5

Claims (14)

1. One kind can be bonding the fluorine material plate, but it comprises having the nondegradable fluorine material plate of electron beam that viscosity is given layer in its surface, it is characterized in that: have chemical bond between the layer but give in fluorine material plate and viscosity, described chemical bond by at least on the fluorine material plate irradiating electron beam form.
2. 2. according to the described fluorine material plate that can be bonding of claim 1, it is characterized in that: described fluorine material plate contains the crosslinked polymkeric substance by the electron beam irradiation.
3. 3. according to claim 1 or 2 described fluorine material plates that can be bonding, it is characterized in that: but crosslinked viscosity is given material but described viscosity gives that layer contains by electron beam irradiation.
4. 4. according to claim 1,2 or 3 described fluorine material plates that can be bonding, it is characterized in that: described fluorine material plate contains the above fluorine of 10wt%.
5. 5. according to each described fluorine material plate that can be bonding among the claim 1-4, it is transparent.
6. 6. according to each described fluorine material plate that can be bonding among the claim 1-5, it is a layer protecting film.
7. 7. fusible fluorine material plate, but it comprise among the claim 1-7 each described can be bonding the fluorine material plate and be formed at described viscosity and give non-pressure sensitive adhesive layer on the laminar surface.
8. 8. according to the described fusible fluorine material plate of claim 7, it is characterized in that: described binder layer is a hot-melt adhesive.
9. 9. the method for a bonding fluorine material plate, it comprise by with adhesive application described can be bonding the fluorine material plate and/or the surface of adherend on or between them, apply tackiness agent, make that each described fluorine material plate that can be bonding is bonded on the adherend among the claim 1-6.
10. 10. according to the described adhesive bonding method of claim 9, it is characterized in that: described tackiness agent is a hot-melt adhesive.
11. 11. according to the described adhesive bonding method of claim 9, it is characterized in that: described tackiness agent is a crosslinking binder.
12. 12. the glued construction of a fluorine material plate is characterized in that: each described fluorine material plate that can be bonding is bonded on the adherend by tackiness agent among the claim 1-6.
13. 13. according to the described glued construction of claim 12, it is characterized in that: described tackiness agent is a hot-melt adhesive.
14. 14. according to the described glued construction of claim 12, it is characterized in that: described tackiness agent is a crosslinking binder.

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