CN1175316A - Reflective sheet - Google Patents
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- CN1175316A CN1175316A CN 95197617 CN95197617A CN1175316A CN 1175316 A CN1175316 A CN 1175316A CN 95197617 CN95197617 CN 95197617 CN 95197617 A CN95197617 A CN 95197617A CN 1175316 A CN1175316 A CN 1175316A
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Abstract
A reflective sheet having a smooth surface layer where light is incident, which includes a fluoresin film having a total transmittance of 80% or greater on the surface layer. Even when this reflective sheet is used in a cold place, the surface thereof is substantially free from icing and the deposition of snow, and it can be easily cleaned if it has seribbles in paint and ink.
Description
Technical field
The present invention relates to reflective sheet, it can be used for sign such as road markings, engineering sign class, the number plate of vehicles such as automobile, autobike, safety equipment classes such as clothes, life preserver, sports goods such as ski stick, billboard etc. the equipment etc. of keeping the score; Especially, even when cold zone uses, also seldom on the retroreflecting thin sheet surface, freeze or accumulated snow, and, even when the retroreflecting thin sheet surface also need not with an organic solvent during by pollutions such as coating, printing ink, only just wipe away or wash and easily to remove pollution, thereby be to pollute the property removed excellence by sky.
Background technology
Can make light early is exactly well-known towards the reflective sheet of light source retroreflecting, utilizes its retroreflecting, and oneself is widely used in various as mentioned above fields this light sheet.
Yet, these have reflective sheet earlier, variety of problems especially when using, cold zone is arranged, for example, skiing is raised in the winter time, when temperature drops to when subzero, the retroreflecting performance is descended, in addition, when the Shi Xuehui that snows attached to retroreflecting plate surface on, under the significant situation of adhesion amount, as the sign Presentation Function can completely lose, therefore, cold zone take place repeatedly ice and snow etc. cause visibility to descend or the retroreflecting performance under the trouble of degradation.
About prevent to freeze at such cold zone, the trial of accumulated snow, existing people proposed several schemes, for example, U.S. Patent No. 5,087,508 instructionss disclose and be equipped with heat storage substance in signs, rely on that heat prevents to freeze, the method for accumulated snow.Yet this method exists in sign the trivial operations that is equipped with heat storage substance, and this outfit problem such as also can raise the cost, and its shortcoming is to make the extensive practicability very difficulty that becomes.
In addition, recently, especially road markings, engineering sign etc. identify the surface of class, and usually owing to mischief and by pollutions such as coating, printing ink, taking place becomes problem as degradation trouble under the Presentation Function of sign.The trial of the function that pollution on the sign class that is subjected to this type of pollution is removed and recover to be lost also once the someone carried out, for example, on the retroreflecting thin sheet surface, make the solution coat of acrylic compounds crosslinked resin etc., dry, form the strong superficial layer of solvent resistance, under situation about being polluted, implement with the organic solvent wiping except that the method for depolluting etc.Yet, in this method, in any case also need to be used for the solvent of dissolved contaminants matter when remove polluting, thereby have couple operating personnel to produce the harmful effect on the health or environment produced the such shortcoming of harmful effect.
And then, the also known reflective sheet that a kind of so-called inclosure eyeglass type is arranged, wherein at least a portion of retroreflecting thin plate is made of the fluorine-type resin film.For example, the spy opens and discloses a kind of super-weathering resistance reflective sheet in the clear 4-86701 communique, it is lamination glass of high refractive index pearl, a focus layer film successively in a superficial layer of being made up of the fluorine-type resin film, covers a metal level then and form on the focus layer film.
According to this patent gazette, also disclosing above-mentioned super-weathering resistance reflective sheet can make as follows: coating is the coating of major component with fluorine-type resin solution on suitable support film, make it the dry fluorine-type resin superficial layer that forms, a kind of adhesive layer film coating of coating on this superficial layer, after making it drying, beaded glass is imbedded in this adhesive layer film, and then be coated with a kind of focus layer film coating thereon, make it dry, on this focus layer film, form metallic reflector then, in addition, between superficial layer and adhesive layer, can also use the same method a middle layer is set.
Yet, under the situation of the little resin of surface tension such as fluorine-type resin, majority is poorly soluble to organic solvent, when preparing the organic solvent solution of this resinoid, have the resin choice scope is narrowed down or in the selection of organic solvent problem such as very arduous, its present situation is to differ to obtain enough gratifying reflective sheet surely.
The objective of the invention is, shortcoming in view of these prior arts, a kind of improved reflective sheet is provided, make and just can give the retroreflecting thin plate with anti-icing property and anti-accumulated snow by simple operations, even and then sign class etc. the product surface that utilizes the retroreflecting thin plate also need not the use meeting human body or environment are produced dysgenic wiping solvent when being subjected to pollution such as coating, printing ink, just wipe away or wash and easily to remove pollution by means of sky.
Disclosure of the Invention
The present inventor is at improving at lip-deep icing property of the debatable reflective sheet of cold zone or accumulated snow, improve the method for the easiness of reflective sheet depollution simultaneously, various researchs have been carried out, found that, pass through on the light incident side surface of retroreflecting thin plate now via the so extremely shirtsleeve operation of the bonding layer of transparent fluorine-type resin of adhesive phase film, just can significantly improve anti-icing property, anti-accumulated snow and the depollution easiness of reflective sheet.
Therefore, according to the present invention, a kind of reflective sheet is provided, and it has at light incident side on this surface of retroreflecting thin plate of flat top layer and forms via the fluorine-type resin film of a kind of full light transmittance of adhesive phase lamination more than 80%.
Below illustrate in greater detail reflective sheet of the present invention.
Paste the retroreflecting thin plate of fluorine-type resin film according to the present invention, so long as have smooth surface (promptly having flat front face) at its light incident side, its type just is not particularly limited, for example, can use and enclose eyeglass type retroreflecting thin plate, capsule eyeglass type retroreflecting thin plate, reflective sheets such as capsule corner type retroreflecting thin plate, metallization corner type retroreflecting thin plate.These reflective sheets and manufacture method thereof are recorded in the patent documentation respectively, for example, enclose eyeglass type retroreflecting thin plate and be recorded in special public clear 56-2921 communique (U.S. Patent No. 4,025,674 instructionss), capsule eyeglass type retroreflecting thin plate is recorded in the spy and opens clear 60-194405 communique (U.S. Patent No. 4,653,854 instructionss), capsule corner type retroreflecting thin plate is recorded in U.S. Patent No. 3,417,959 instructionss, and metallization corner type retroreflecting thin plate is recorded in the spy and opens clear 49-106839 communique (U.S. Patent No. 3,712,706 instructionss) etc., take quoting of these documents to replace its specific descriptions here.
The invention is characterized in and on the level and smooth light incident side superficial layer of aforesaid reflective sheet, paste the fluorine-type resin film.
As the fluorine-type resin film that will paste, can use its full light transmittance is more than 80%, is preferably more than 85%, is the high clarity films more than 90% better.In this instructions, the full light transmittance of fluorine-type resin film is with the numerical value of " ヘ イ ズ メ one one TC-H III " (Tokyo electricity look corporate system) when measuring.
In addition, the thickness of above-mentioned fluorine-type resin film is not particularly limited, because of purposes of reflective sheet etc. different, can in wide scope, change, but generally can 1～100 μ m, more fortunately 5～80 μ m, better at 10～70 μ m, further better in 20～60 mu m ranges.
As the fluorine-type resin that can be used for this type of film preparation, can use such as tetrafluoroethene, a chlorotrifluoroethylene, trifluoro-ethylene, vinylidene fluoride, the homopolymer of the fluorochemical monomer beyond the fluoroolefins hydro carbons monomers such as fluoroolefins such as fluorothene, hexafluoropropylene hydro carbons monomer, perfluoroalkyl vinyl ether, the full fluoroalkane ester of (methyl) acrylic acid etc., these fluorochemical monomers each other or the polymkeric substance of these fluorochemical monomers and other copolymerisable monomer, and these equal potpourris of (being total to) polymers and other resin.
As above-mentioned copolymerisable monomer, can enumerate such as ethene, alkenes monomers such as propylene, ethylene methacrylic ether, ethyl vinyl ether, the normal-butyl vinethene, the cyclohexyl vinethene, (ring) alkyl vinyl ether class monomers such as cyclopentyl vinethene, vinyl acetate, propionate, new vinyl acetate acid, Versatic vinyl acetate (trade name, Shell Co. Ltd's system), vinyl benzoate, the p-tert-butyl benzoic acid vinyl acetate, the cyclohexane-carboxylic acid vinyl acetate, generating vinyl carboxylate esters monomers such as methylvinyl acetate, vinyl chloride, vinyl halides class monomer beyond the fluorochemical monomers such as vinylidene chloride, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) acrylic ester monomers such as (methyl) lauryl acrylate, 2-hydroxyethyl vinethene, 3-hydroxypropyl vinethene, 4-hydroxybutyl vinethene, 2-hydroxyethyl allyl ether, hydroxyl monomers such as (methyl) acrylic acid 2-hydroxy methacrylate, acrylic acid, hydroxyl monomers such as methacrylic acid, (methyl) acrylic acid N, the N-dimethylamino ethyl ester, (methyl) acrylic acid-N, N-diethylamino ethyl ester, N, N-diethylamino ethyl vinyl ether etc. contains amino monomers, the glycidyl vinethene, (methyl) glycidyl acrylate etc. contains the epoxy radicals monomer, trimethoxyvinylsilane, triethoxy vinyl monosilane, 2-(trimethoxysilyl) ethyl vinyl ether, γ-(methacryloxypropyl) propyl trimethoxy monosilane etc. contains the hydrolysable silyl group monomer, 2-(trimethyl silyloxy) ethyl vinyl ether, 4-(trimethyl silyloxy) butyl vinyl ether etc. contains the silyloxy monomer, (methyl) acrylic acid trimethyl silyl ester, 5-(trimethyl silyloxy carbonyl) valeric acid vinyl acetate etc. contains silyloxy carbonyl monomer etc.
These copolymerisable monomers can use by a certain percentage, make from the surface tension of the film of formed fluorine analog copolymer manufacturing reach below 40 dynes per centimeter, more fortunately below 35 dynes per centimeter, better below 31 dynes per centimeter.Here, the surface tension of film is the numerical value during by following measure.
In surface tension is under the situation of the film more than 31 dynes per centimeter, the different multiple wetting test of surface tension is coated with into wire with wetting index titer [with the pure pharmaceutical worker's industry of light corporate system] on film surface under 23 ℃, the atmosphere of 65%RH (relative humidity), have or not adhesional wetting with the ocular estimate judgement after about 3 seconds, determine the surface tension of film surface according to the titer number that adhesional wetting is arranged.And be lower than in surface tension under the situation of film of 31 dynes per centimeter, use the methanol mixed liquor, measure contact angle with sessile drop method and determine surface tension.
As the fluorine-type resin that can be used for the present invention preferably, can exemplify such as teflon, tetrafluoroethylene/perfluoro alkyl vinyl ether multipolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/hexafluoropropylene/perfluoroalkyl vinyl ether multipolymer, tetrafluoroethylene/ethylene multipolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene/ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride etc.
In addition, the potpourri of equal (being total to) polymers of these fluorine classes and other resin also can use.As other resin that can mix, can enumerate such as polyacetals resin, polycarbonate resin, polyamide-based resin, polystyrene resins, acrylic compounds resin, vinyl acetate esters resin polyurethanes resin, phenol resin, polyimide resin.
The blending ratio of these other resins can be can make from the surface tension of the film of formed resin potpourri manufacturing to fall into ratio in the above-mentioned scope.
Yet, as the fluorine-type resin that can be used for the present invention particularly well, can enumerate tetrafluoroethylene units content in 15～85% (weight), more fortunately 25～75% (weight), tetrafluoroethylene/ethylene multipolymer and the polyvinylidene fluoride in 35～65% (weight) scope better.These all (being total to) polymers from viewpoints such as processability, film permanance, its weight-average molecular weight generally more fortunately 5,000～400,000, especially 7,000～300, in 000 the scope.
In addition, the potpourri of above-mentioned all (being total to) polymers and above-mentioned other resin is also still operable.In this case, be benchmark with the weight of potpourri, the fluorine class all (being total to) polymers better can account at least 70% (weight), especially more than 80% (weight), more specifically in 90% (weight).
And, as commercially available equal (being total to) polymers that contains fluoro olefine unit that can be used among the present invention, can enumerate such as " Off Le オ Application (fluorine road father-in-law) ", " ア Off ロ Application (Ah's fluon) TEE ", " ア Off Le Application (Ah fluorine's human relations) COP " (more than be the Asahi Glass corporate system), " Port リ Off ロ Application (poly-fluon) TFE ", " ネ オ Off ロ Application (new fluon) FEP ", " ネ オ Off ロ Application (new fluon) PFA ", " ネ オ Off ロ Application (new fluon) ETFE " (more than be ダ イ キ Application (Da Jin) industrial group system)), " テ Off ロ Application (teflon) TFE ", " テ Off ロ Application (teflon) FEP ", " テ Off ロ Application (teflon) PFA " " テ Off ロ Application (teflon) EPE ", " ラ Off ゼ Le (special fluorine short cut) " (more than be Mitsui Du Pont fluorine chemistry corporate system) etc.
In the fluorine class resin that the present invention uses,, if necessary, also can contain thermal stabilizer, light stabilizer, crosslinking chemical, colorant etc. in that physical properties such as the full light transmittance of film, surface tension are not produced in the scope of substantial effect.
Above-described fluorine-type resin better is to use such as heat fusing methods of forming such as extrusion by melting, rolling processes to be processed into film.
According to the present invention, the fluorine-type resin film that obtains like this will be via adhesive phase, better be that the pressure sensitive adhesive layer lamination covers on the light incident side flat top layer of retroreflecting thin plate.When carrying out this lamination, bonding agent can be coated on the stickup face of fluorine-type resin film in advance, perhaps can be coated on this superficial layer of retroreflecting thin plate, perhaps can be coated on bonding agent on this superficial layer of the stickup face of then it being transferred to the fluorine-type resin film on the suitable release materials or retroreflecting thin plate.
The thickness of the adhesive phase of Xing Chenging like this, the changes such as thickness of the resin film that can maybe will paste according to the kind of bonding agent, but generally can 5～80 μ m, more fortunately 10～70 μ m better in the scope of 20～60 μ m.
As above-mentioned bonding agent, generally be preferably and contain glass temperature (Tg) at-100 ℃～+ 50 ℃, especially the resin of binding property in-80 ℃～-20 ℃ scopes is the pressure-sensitive adhesive that main body is formed.
As this resin of binding property, the resin that usually is used for pressure-sensitive adhesive can use equally, its kind is not particularly limited, for example, can use acrylic compounds, polyurethanes, vinyl-vinyl acetate copolymer class, synthetic resin such as polysiloxane-based, but acrylic resin preferably wherein.
As such acrylic resin, can enumerate such as acrylic acid C such as ethyl acrylate, acrylic acid n-propyl, n-butyl acrylate, isobutyl acrylate, acrylic acid n-pentyl ester, acrylic acid 2-methyl butyl ester, the just own ester of acrylic acid, 2-EHA, acrylic acid n-octyl, Isooctyl acrylate monomer, acrylic acid ester in the positive ninth of the ten Heavenly Stems, acrylic acid esters in the different ninth of the ten Heavenly Stems
2-C
12At least a in the alkane ester (monomer A), contain at least a in functional group's acrylic monomer (monomers B) with acrylic acid, methacrylic acid, acrylamide, N-(methylol) acrylamide, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate etc., the resin that obtains so that Tg can fall into the ratio copolymerization in the above-mentioned scope.The copolymerization ratio of above-mentioned monomer A and monomers B, the weight ratio that is preferably monomer A/monomers B are in 99.5/0.5～70/30, especially in 99/1～75/25 the scope.
Even as also being good especially acrylic resin in resin of binding property, can enumerate butyl acrylate (BA) and acrylic acid (AA) with the weight ratio of BA/AA in 99.1/0.9～70/30, especially carry out copolymerization in the scope of 99.5/0.5～80/20 and the multipolymer that obtains.
In addition, in above-mentioned resin of binding property, for the weatherability that improves himself with become the purpose of weatherability of the retroreflecting thin plate of lining, it is desirable to also contain ultraviolet light absorber, and if necessary, can also cooperate the photooxidation inhibitor.
As the ultraviolet light absorber that can adopt in the above-mentioned resin of binding property, generally be preferably very big absorbing wavelength at 340～353nm, the absorbing agent in 343～346nm scope especially, for example, can enumerate cyanoacrylate, ultraviolet light absorbers such as benzotriazole, benzophenone class, salicylic acid, hydroquinones.The compound of response type in the middle of these absorbing agents, perhaps can with formed polymer reaction, perhaps can introduce in the polymkeric substance by reacting earlier with foregoing monomer.
The concrete example of the ultraviolet light absorber that can use, as the benzotriazole ultraviolet absorber, can enumerate such as 2-(3,5-di-t-butyl-2-hydroxy phenyl) benzotriazole, 2-[2-hydroxyl-3,5-two (α, α-Er Jiajibianji) phenyl]-2H-benzotriazole, 2-(3,5-two tertiary pentyls-2-hydroxy phenyl) benzotriazole etc.; As benzophenone class ultraviolet absorber, can enumerate such as 2-hydroxyl-4-octyloxy benzophenone, 2,4-dihydroxy benzoyl benzene, 2-hydroxyl-4-methoxyl-2 '-the hydroxyl benzophenone etc.; As the salicylic acid ultraviolet light absorber, can enumerate such as phenyl salicytate, p-octylphenyl salicylate, resorcinol one benzoic ether, salicylic acid 4-tert-butyl group phenyl ester etc.; Then,, can enumerate 3-diphenyl-ethyl acrylate, 2-cyano group-3,3-diphenylacrylate 2-Octyl Nitrite etc. such as 2-cyano group-3 as the cyanoacrylate ultraviolet light absorber.
In the middle of these, especially good is the benzotriazole ultraviolet light absorber.
Above-mentioned ultraviolet light absorber is per 100 weight portions of resin of binding property (in solid content) normally, can 0.5～10 weight portion, more fortunately 0.6～9 weight portion, in the scope of 0.7～8 weight portion, use better.
In addition, in adhesive phase, except that above-mentioned ultraviolet light absorber, it is desirable to also contain the photooxidation inhibitor, as the photooxidation inhibitor that can cooperate with it, can enumerate such as photooxidation inhibitor such as hindered amines or Hinered phenols, wherein be preferably hindered amines photooxidation inhibitor.
As above-mentioned hindered amines photooxidation inhibitor, be not particularly limited, but in general,, can enumerate those high molecular, N substituted piperidine alcohol nuclear is arranged as better example.This hindered amines photooxidation inhibitor usually preferably its weight-average molecular weight 400～10,000, especially 500～5, in 000 the scope.Concrete example as such hindered amines photooxidation inhibitor, can enumerate the such macromolecule ester of ester of BTCA and N substituted piperidine alcohol, wherein example can be enumerated commercially available product MARK LA-63 (trade name preferably, ア デ カ ア one ガ ス corporate system), MARKLA-62 (trade name, ア デ カ ア one ガ ス corporate system), TINUVIN-622LD (trade name, Japanese チ バ ガ イ ギ-corporate system) etc.By using such high molecular hindered amines photooxidation inhibitor, can prevent to decompose and break, its result makes and can keep performance in long-time.
The use level of photooxidation inhibitor does not have strict restriction, can be according to changes such as its kinds, but in general, for per 100 weight portions of resin of binding property (in solid content), this inhibitor can be at 0.5～5 weight portion, more fortunately 0.6～4 weight portion, better in the scope of 0.7～3 weight portion.
Be in the major component adhesive composition that form, that be used to form adhesive phase with above-mentioned resin of binding property, except that above-mentioned ultraviolet light absorber and photooxidation inhibitor, can also suitably allocate universaling component into, for example ethyl acetate, ethyl acetoacetate equal solvent, colorants such as various pigment and dyestuff, crosslinking chemical, crosslinking accelerator etc.As crosslinking chemical, can enumerate such as isocyanates, epoxies, melamine class, aluminium chelate compound class etc., and, can enumerate such as dibutyl tin laurate etc. as crosslinking accelerator.
Above-described adhesive composition can be applied on the stickup face of described fluorine-type resin film or on the light incident side surface of retroreflecting thin plate, but in practicality, be preferably on the stickup face that is applied to the fluorine-type resin film in advance, with covering adhesive phases such as processing release papers, when needs processing release paper etc. is peeled off, pressure level is pressed onto on the light incident side surface of retroreflecting thin plate.
Above-described retroreflecting thin plate of the present invention; owing to utilize the low and weatherability of surface tension; solvent resistance; the fluorine-type resin film of excellences such as physical strength is protected its surface; even thereby such as when cold zone uses, also seldom on the retroreflecting thin sheet surface, freezing or accumulated snow; even on the surface of retroreflecting thin plate, be subjected to coating; also need not during pollutions such as printing ink with an organic solvent to wait; only just wipe away or wash and easily to remove pollution with sky; therefore; can be advantageously used in such as road markings; sign such as engineering sign class; automobile; number plate of vehicles such as autobike; clothes; safety equipment classes such as life-saving appliances; sports goods such as ski stick, billboard etc. the equipment etc. of keeping the score.
Embodiment
Below be described more specifically the present invention with embodiment and comparative example.The method and the evaluation method thereof that are noted that the anti-icing property test of retroreflecting thin plate in embodiment and the comparative example, anti-accumulated snow test, retroreflecting performance test, flexibility test and soil release characteristics test are as follows.
(1) anti-icing property test
The retroreflecting thin plate pastes on the whole surface of aluminium sheet of 7.5 * 15cm, makes test piece.This test piece stands vertically in-30 ℃ atmosphere, with spray-on process water droplet is sprayed on whole of this retroreflecting thin sheet surface, observes the icing state of 24 hours rear surfaces, by following benchmark evaluation:
5 freeze partly accounts for below 5% of the total area;
4 parts of freezing account for more than 5% of the total area～below 10%;
3 parts of freezing account for more than 10% of the total area～below 20%;
2 parts of freezing account for more than 20% of the total area～below 30%;
1 freezes partly accounts for more than 30% of the total area.
(2) anti-accumulated snow test
The retroreflecting thin plate pastes on the whole surface of aluminium sheet of 1 * 1.5m, makes test piece.When snowing this test piece is upright in outside the room, observes the surperficial accumulated snow situation after 24 hours, press following benchmark evaluation:
5 accumulated snow partly account for below 5% of the total area;
4 accumulated snow partly account for more than 5% of the total area～below 10%;
3 accumulated snow partly account for more than 10% of the total area～below 20%;
2 accumulated snow partly account for more than 20% of the total area～below 30%;
1 accumulated snow partly accounts for more than 30% of the total area.
(3) retroreflecting performance
Retroreflecting performance measurement method according to JIS Z-9117 regulation is measured.Be noted that the angle condition when measuring is 0.2 ° of view angle, 5 ° of incident angles.
(4) flexibility test
The retroreflecting thin plate cuts into 10 * 10cm, under 5 ℃ condition, by means of sticking on Corvic tubulation of the about 5cm of diameter at the contact adhesive that is provided with on the retroreflecting thin plate back side, fixes for 10 seconds.Remove then and fix, observe sticking state, press following benchmark evaluation:
3 do not have to float, to peel off etc. and paste different shape;
2 float, peel off etc. paste different shape from end 10mm with interior scope;
1 floats, peels off etc. and pastes different shape and surpass from end 10mm.
(5) soil release characteristics test
The topical oil felt pen of retroreflecting thin plate is black defiles, and after dry 5 minutes, presses following benchmark evaluation soil release characteristics:
The simple wiping of 5 usefulness cloth just can be removed, and leaves no trace fully;
4 usefulness cloth can be removed during wiping energetically, leave no trace fully;
3 promptly use cloth energetically wiping can not remove fully, but on cloth, dip in water or ethanol wiping again
In time, can be removed and left no trace fully;
2 dip in water or ethanol on cloth can remove during wiping but leave vestige;
1 on cloth, dip in water or ethanol again wiping can not remove.
Embodiment 1
The about 40 μ m of thickness, full light transmittance 92%, the tetrafluoroethylene/ethylene multipolymer fluorine-type resin film of surface tension 23 dynes per centimeter [" ア Off ロ Application COP ", the Asahi Glass corporate system] and on processing release paper, be coated with a kind of mixed liquor, the pressure sensitive adhesive layer of the about 50 μ m of dry back thickness is fitted, be manufactured with the fluorine-type resin film of contact adhesive, described mixed liquor comprises butyl acrylate (BA)/acrylic acid (AA) multipolymer (weight ratio: ethyl acetate/toluene BA/AA=90/10) (4/6) solution (solid content=34%) 294 weight portions, benzotriazole ultraviolet light absorber [" TINUVIN328 ", チ バ ガ イ ギ one corporate system] 1.4 weight portions, hindered amines photooxidation inhibitor [" TINUVIN622LD ", チ バ ガ イ ギ one corporate system] 0.7 weight portion, and as acetate 1-methoxyl propyl ester-2/ dimethylbenzene (1/1) solution (solid content=75%) 0.3 weight portion of the hexamethylene diisocyanate class crosslinking chemical of crosslinking chemical.
Then, peel off the processing release paper on the fluorine class film of contact adhesive, paste, be laminated to commercially available capsule eyeglass type retroreflecting thin plate [" ニ Star カ ラ イ ト ULS512 ", ニ Star カ Port リ マ corporate system] the light incident side surface on, obtained having the retroreflecting thin plate of fluorine-type resin film lining superficial layer.
Resulting retroreflecting thin plate carries out various tests according to the afore-mentioned test method.Test result is listed in the following table 1.
Embodiment 2
Except that the vinylidene fluoride based resin film (PVdF) [" DX Off イ Le system 14S0050 " of the tetrafluoroethylene-ethylene copolymer film among the embodiment 1 with the about 50 μ m of thickness, full light transmittance 92%, surface tension 25 dynes per centimeter, Denki Kagaku Kogyo kabushiki's system] replace outside, equally carry out with embodiment 1, obtain the retroreflecting thin plate.Resulting retroreflecting thin plate carries out various tests according to the afore-mentioned test method.Test result is listed in the following table 1.
Comparative example 1
Commercially available capsule eyeglass type retroreflecting thin plate for using among the embodiment 1 carries out various tests according to the afore-mentioned test method.Test result is listed in the following table 1.
Comparative example 2
Except that the polyethylene terephthalate based resin film (PET) [" テ イ ジ Application テ ト ロ Application S-38 " of the tetrafluoroethylene-ethylene copolymer film among the embodiment 1 with the about 38 μ m of thickness, full light transmittance 93%, surface tension 41 dynes per centimeter, Supreme Being people's corporate system] replace outside, equally carry out with embodiment 1, obtain the retroreflecting thin plate.Resulting retroreflecting thin plate carries out various tests according to the afore-mentioned test method.Test result is listed in the following table 1.
Embodiment 3
Remove the capsule eyeglass type retroreflecting thin plate that is used as the retroreflecting thin plate among the embodiment 1 with commercially available inclosure eyeglass type retroreflecting thin plate [" ニ Star カ ラ イ ト SEG15012 ", ニ Star カ Port リ マ corporate system] replace outside, equally carry out with embodiment 1, obtain the retroreflecting thin plate.Resulting retroreflecting thin plate carries out various tests according to the afore-mentioned test method.Test result is listed in the following table 1.
Comparative example 3
Commercially available inclosure eyeglass type retroreflecting thin plate for using among the embodiment 3 carries out various tests according to the afore-mentioned test method.Test result is listed in the following table 1.
Table 1
Claims (15)
1. retroreflecting thin plate, this thin plate have at light incident side on this superficial layer of retroreflecting thin plate of flat top layer and form via the fluorine-type resin film of the full light transmittance of adhesive phase lamination more than 80%.
2. the described retroreflecting thin plate of claim 1, wherein the fluorine-type resin film has the full light transmittance more than 85%.
3. the described retroreflecting thin plate of claim 1, wherein the fluorine-type resin film is tetrafluoroethylene/ethylene multipolymer or polyvinylidene fluoride.
4. the described retroreflecting thin plate of claim 3, wherein the tetrafluoroethylene/ethylene multipolymer contains the tetrafluoroethylene units of 15～85% (weight).
5. the described retroreflecting thin plate of claim 1, wherein the fluorine-type resin film is by the melt-shaping manufactured.
6. the described retroreflecting thin plate of claim 1, wherein the thickness of fluorine-type resin film is 1～100 μ m.
7. the described retroreflecting thin plate of claim 6, wherein the thickness of fluorine-type resin film is 5～80 μ m.
8. the described retroreflecting thin plate of claim 1, wherein adhesive phase is made up of pressure-sensitive adhesive.
9. the described retroreflecting thin plate of claim 8, wherein pressure-sensitive adhesive mainly is made up of acrylic resin.
10. the described retroreflecting thin plate of claim 1, wherein adhesive phase contains ultraviolet light absorber.
11. the described retroreflecting thin plate of claim 10, wherein ultraviolet light absorber is the benzotriazole ultraviolet light absorber.
12. the described retroreflecting thin plate of claim 10, wherein adhesive phase further contains the photooxidation inhibitor.
13. the described retroreflecting thin plate of claim 12, wherein the photooxidation inhibitor is the hindered amines photooxidation inhibitor of high molecular.
14. the described retroreflecting thin plate of claim 1, wherein the thickness of adhesive phase is 5～80 μ m.
15. the described retroreflecting thin plate of claim 14, wherein the thickness of adhesive phase is 10～70 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB951976176A CN1140888C (en) | 1995-12-12 | 1995-12-12 | Reflective sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB951976176A CN1140888C (en) | 1995-12-12 | 1995-12-12 | Reflective sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175316A true CN1175316A (en) | 1998-03-04 |
| CN1140888C CN1140888C (en) | 2004-03-03 |
Family
ID=5083304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB951976176A Expired - Lifetime CN1140888C (en) | 1995-12-12 | 1995-12-12 | Reflective sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1140888C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023039743A1 (en) * | 2021-09-15 | 2023-03-23 | 3M Innovative Properties Company | Retroreflective sheeting for digital cutting |
-
1995
- 1995-12-12 CN CNB951976176A patent/CN1140888C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023039743A1 (en) * | 2021-09-15 | 2023-03-23 | 3M Innovative Properties Company | Retroreflective sheeting for digital cutting |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1140888C (en) | 2004-03-03 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 19980304 Assignee: Nippon Carbide Industries (Hangzhou) Co., Ltd. Assignor: Tokyo Contract record no.: 2010990000164 Denomination of invention: Reflective sheet Granted publication date: 20040303 License type: Exclusive License Record date: 20100401 |
|
| CX01 | Expiry of patent term |
Granted publication date: 20040303 |
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| EXPY | Termination of patent right or utility model |