TWI297305B - - Google Patents

Description

1297305 * A7 B7 V. INSTRUCTIONS (彳) AREAS: The invention is a reflective sheet suitable for: road markings, construction markings, etc.; vehicle, locomotive and other vehicle identification signs; clothing, life-saving appliances and other safety equipment; Sports equipment such as ski poles; and signage equipment such as kanban. Especially when used in cold areas, the surface is also less prone to icing and snow adhesion. When the surface is stained with paint or ink, it is not necessary to use organic solvents. It can be easily removed by wiping or washing. A highly reversible reflective sheet; and associated with a reflective sheet on which the printed layer is disposed. Prior Art: Reflective sheets that reflect light back to the source have been known in the past; utilizing their reflective properties, the sheet is widely used in each of the above items. However, these past reflective sheets, especially in cold regions, will cause various problems. For example, in winter, when the temperature is below zero, the water droplets attached to the surface of the reflective sheet will reduce the reflective performance due to icing; At that time, due to the adhesion of snow to the surface of the reflective sheet, the notice function of the important logo will be completely lost. Therefore, in cold regions, problems such as reduced visibility and reduced reflection performance caused by ice and snow are endless. Recently, especially on the surface of markings such as road signs and construction signs, paints, inks, and the like have been smeared by malicious means, which has also caused the signage of the logo to be reduced. In view of the above-mentioned shortcomings of the prior art, the present invention provides the following retroreflective sheeting (refer to International Publication No. WO97/22098 and U.S. Patent Application No. 0U0574) which is capable of imparting anti-icing properties by a simple method. Kiss and snow-proof U adhesion; marking and other surfaces using reflective sheet products, painted, oily ϋ Yin Guo National Standard (CNS) A-Grid (21〇X 297 公黄) -4 - 1297305 A7 B7 V. Invention Explanation (2) In the case of smudging such as ink, 'no need to use solvent removal that affects the human body and the environment. It is easy to remove dirt by wiping or washing. The reflective sheet is characterized in that it is formed on the surface layer of the retroreflective sheeting having a smooth surface layer on the light incident side, and is formed by laminating a fluorine-based resin film having a total light transmittance of 80% or more via an adhesive layer. . The above-mentioned retroreflective sheeting has improved the above-mentioned shortcomings of the prior art, but does not have a printing layer for notice, decoration, and the like. Further, when a printing layer is provided between the fluorine-based resin film of the above-mentioned retroreflective sheeting and the adhesive layer, the fluorine-based resin film generally has poor adhesion to the printing layer, so the fluorine-based resin film and the printing layer are not good. When the water or the solvent 4 is immersed and swelled, the fluorine-based resin film may be peeled off or the like. Brief Description of the Invention: Therefore, the reflective sheet provided by the present invention is intended to impart anti-icing property and anti-snow adhesion by a simple method; the surface of a reflective sheet product such as a logo, paint, ink, etc. In the case of smearing, it is not necessary to use solvent removal which affects the human body or the environment, and it is easy to remove the smear by wiping or washing with water; and it has a printing layer, and the mesangial layer has no problem of flaking. The present invention provides a retroreflective sheeting for achieving the above object, characterized in that it comprises: on the surface layer of the retroreflective sheeting having a smooth surface layer on the light incident side, the total light transmittance is 80% across the layer of the adhesive layer. In the above fluorine-based resin film, a printed layer in which a printing region is discontinuous is provided between the fluorine-based resin film and the adhesive layer. The reflective sheet having the printing layer of the present invention has a low surface tension due to its surface protection using a vaporized resin, and has good weather resistance and resistance to -5 - A ^, n > O q ^ mm 297 ^ 1297305 A7 ___ B7 V. INSTRUCTIONS (3) Solvent and mechanical strength, when used in cold areas, the surface of the reflective sheet is less icing and snow, and the surface of the reflective sheet is smeared with paint, ink, etc. When it is not necessary to use organic solvents, etc., it is easy to remove the stains by wiping or washing. Therefore, it is suitable for identification such as road signs and construction marks; vehicle identification signs such as automobiles and motorcycles; safety equipment such as clothes and life-saving appliances; Sports equipment such as ski poles; and signage equipment such as kanban. In the reflective sheet having the printing layer of the present invention, when the printing area is discontinuous, when it is applied outdoors or washed with a solvent, even if the interface between the fluorine resin film and the printing layer is immersed in water or solvent, the water is immersed. Or the immersion of the solvent or the like will be limited to the separate printing area and will not spread to the entire surface of the reflective sheet. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an enlarged cross-sectional view showing an example of a retroreflective sheeting of the present invention, which is laminated on a surface layer of a lens-sealed retroreflective sheeting, and is formed by laminating an adhesive layer, a printing layer, and a fluororesin film. Fig. 2 is an enlarged cross-sectional view showing an example of the retroreflective sheeting of the present invention, which is attached to the surface layer of the lens-interfering retroreflective sheeting layer, a layer of a carrier layer, a printed layer, and a gas-based resin film. Fig. 3 is an enlarged cross-sectional view showing an example of the retroreflective sheeting of the present invention, which is obtained by laminating an adhesive layer, a printing layer, and a fluorine-based resin film on the surface layer of the reticle type reflective sheet. Fig. 4 is an enlarged cross-sectional view showing an example of the retroreflective sheeting of the present invention, which is obtained by laminating an adhesive layer, a printing layer, and a fluorine-based resin film on the surface layer of the ruthenium reflective reflective sheet. r% ~ 6 - f ^ e-π ^ y J _ —— ---- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1297305 A7 B7 V. Invention description (4) —-- Fig. 5 is a general view showing an example of a printing pattern unit of a printing layer and an arrangement form thereof. Fig. 6 is a view showing a whole of a printing pattern unit of a printing layer and an arrangement form thereof. Figure 7 is an enlarged cross-sectional view of a retroreflective sheeting of the present invention attached to a surface of a sheet of reflective sheet as shown in Figure ι. Figure 8 is an enlarged cross-sectional view of a retroreflective sheeting of the present invention attached to a surface of a sheet of reflective sheet as shown in Figure 设置. Figure 9 is an enlarged cross-sectional view of a retroreflective sheeting of the present invention attached to a surface of a reflective sheet as shown in Figure 2 with a second printed layer. Figure 10 is an enlarged cross-sectional view of a retroreflective sheeting of the present invention attached to a second printed layer disposed beneath the surface layer of the sheet of reflective material as shown in Figure 2. Figure 11 is an enlarged cross-sectional view showing a retroreflective sheeting of the present invention, which is provided with a second printing layer disposed on the surface layer of the retroreflective sheeting as shown in Figure 3. Figure 12 is an enlarged cross-sectional view showing a retroreflective sheeting of the present invention, which is provided with a second printing layer disposed under the surface layer of the reflective sheet as shown in Figure 3. Figure 13 is an enlarged cross-sectional view showing a retroreflective sheeting of the present invention, which is provided with a second printing layer disposed on the surface layer of the retroreflective sheeting as shown in Figure 4. Figure 14 is an enlarged cross-sectional view showing a retroreflective sheeting of the present invention, which is provided with a second printing layer disposed under the surface layer of the reflective sheet as shown in Figure *. DETAILED DESCRIPTION OF THE INVENTION: The retroreflective sheeting of the present invention will be described in detail below. The retroreflective sheet to which the fluorine-based resin film of the present invention is attached is not particularly limited in that it has a smooth surface layer (i.e., has a smooth surface layer). For example, the lens-sealed retroreflective sheeting shown in Fig. 1;

Paper foot

-7-

1297305

It mainly depends on the material of the formed fluorine-based resin film. The fluorine-based resin film is subjected to a surface treatment on the surface adjacent to the printing layer, and the surface tension is changed to 31 dyne/cm or more, and 35 of them are preferred, and those of 40 dyne/cm or more are particularly excellent. An excellent product with a large print layer adhesion. The method of the above surface treatment may be carried out by a corona treatment method, a sandblasting treatment method, a chemical etching treatment method, a flame treatment method, or the like, and particularly, a corona treatment method can obtain an excellent appearance product. In the example of the corona treatment method, for example, a corona treatment apparatus equipped with a ceramic electrode manufactured by Kasuga Electric Co., Ltd. is used to discharge the fluorine-based resin film and the printing layer adjacent to each other under the conditions of 120 W/m 2 ·min. The method of the desired surface tension. In the case of the chemical etching treatment, for example, a chemical etching method using a metal sodium-naphthalene complex tetrahydrofuran solution (manufactured by Kasei Precision Chemical Co., Ltd.; SD-N); and a chromic acid mixed liquid treatment method (for example, immersion) Chromic acid: water: sulfuric acid weight ratio of 70:20:10 70 ° C chromic acid mixture for 15 minutes, washed with water) and so on. When the non-printing surface of the fluorine-based resin film (the surface not adjacent to the printing layer) is subjected to the above surface treatment, the effect of preventing the staining of the object of the present invention is lowered, so that it is not applied. The surface tension of the film layer in this case is as follows when measured. When the surface tension of the film is 31 dyne/cm or more, the weather mark index standard solution (made by Wako Pure Chemical Industries Co., Ltd.) is used at 23 °. C, 65% RH of air, applied to the surface of the film layer in a line. After about 3 seconds, visually determine the presence or absence of water. From no. ^ ri ;> ^ n -9 - This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1297305 A7 B7 V. Description of invention ( The water-repellent 彳 indicates the surface tension of the surface of the film. When the surface tension of the film is less than 3 1 dyne/cm, the contact angle is determined by the droplet method using a methanol/water mixture. The thickness of the fluorine-based resin film is not particularly limited, and may vary within a certain range depending on the use of the reflective sheet, etc. Generally, it is preferably in the range of hiOO #claws, where 5 to 80 μm is preferred. For the production of the fluorinated resin of the fluorine-based resin film, for example, tetrafluoroethylene, chlorotrifluoroethylene, and trisole can be used. Fluorinated hydrocarbon-based monomers such as vinyl fluoride, vinylidene fluoride, vinyl fluoride, and hexa-propylene; perfluorinated alkyl vinyl ethers, and perfluorinated alkyl (inter) acrylates a fluorine-containing monomer other than the body; the single polymer; the fluorine-containing monomer, or the a copolymer of a fluorine-containing monomer and another copolymerizable monomer; and a mixture of the (co)polymer and another resin. The above-mentioned copolymerizable monomer, for example, a paraffin hydrocarbon such as ethylene or a mother-in-law Monomer; (cyclo)alkyl vinyl ether monomer such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, and cyclopentyl vinyl ether; vinyl acetate Base ester, vinyl propionate, vinyl acetate vinegar, "barcelic acid vinyl ester" (trade name, manufactured by Shell), vinyl benzoate, m-butyl butyl benzoate a vinyl carboxylate monomer such as a carboxylate, a cyclohexanecarboxylic acid vinyl vinegar, or a isopropenyl acetate; a vinyl halide monomer other than a fluorine-containing monomer such as vinyl chloride or ethylene bromide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (m-) oxime 10- The paper size applies to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) 1297305 A7 B7 V. DESCRIPTION OF THE INVENTION (8) Acrylating acid S, second butyl (m-) acrylic acid S, 2-ethylhexyl (m-) acrylate, n-octyl acrylate, isooctane (meth) acrylate, n-decyl acrylate, isodecyl acrylate, and acrylate acrylate monomer; 2-hydroxyethyl vinyl ether a hydroxyl group-containing monomer such as 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl propenyl ether, and 2-hydroxyethyl (meth) acrylate; acrylic acid, and fluorenyl group a carboxyl group-containing monomer such as acrylic acid; N,N-dimethylaminoethyl (meth) acrylate, N,N-diethylaminoethyl (meth) acrylate, and n,N-diethylaminoethyl An amino group-containing monomer such as vinyl ether; an epoxy group-containing monomer such as a glycidyl vinyl ether or a glycidyl acrylate; a trimethoxyvinyl fluorene methane and a triethoxyvinyl hydrazine; Water-decomposable Shiqi methane such as methane, 2-trimethoxyindolyl ethyl vinyl ether, and r-methacryloxypropyltrimethoxymethane a monomer; a decyloxy group-containing monomer such as 2-trimethylsulfonyloxyethyl vinyl ether; and dimethyltrimethylamyloxybutyl vinyl ether; and a trimethylsulfonyl group A methacrylate-containing carboxy group containing a methacrylate or a vinyl-5-trimethyl fluorenyloxycarbonylpentenoate. A fluorinated resin suitable for use in the present invention, for example, polytetrafluoroethylene, tetrafluoroethylene/perfluorinated alkyl vinyl ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/hexafluoropropylene/ Perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene/ethylene copolymer, poly-monofluorotrifluoroethylene, chlorotrifluoroethylene/ethylene copolymer, polyvinylidene fluoride, and polyvinyl fluoride. A mixture of the fluorinated (co)polymer and another resin may be used, and other resins obtained by mixing, for example, a polyacetal resin, a polycarbonate resin, a polyamine resin, or a polystyrene system may be used. Resin, acrylic resin,

L (4) with China® Secret (10)) A4 size (21〇X 297 mm) 1297305 A7 B7 V. Description of invention (9) Vinyl acetate resin, polyurethane resin, phenol resin, and polyimine Resin or the like. Particularly suitable for use in the fluorinated resin of the present invention, wherein the tetrafluoroethylene unit content is in the range of 15 to 85% by weight, preferably 25 to 75% by weight, more preferably 35 to 65% by weight, such as tetrafluoroacetic acid/ Ethylene copolymer and polyvinylidene fluoride. The (co)polymers are generally considered to have a weight average molecular weight of from 5,000 to 400,000, and preferably from 7,000 to 300,000, from the viewpoints of workability and film durability. Mixtures of the above (co)polymers with the aforementioned other resins may also be used. In this case, the amount of the fluorinated (co)polymer to be used in an amount of 7% by weight or more based on the weight of the mixture is preferably 80% by weight or more, and particularly preferably 9% by weight or more. The commercially available fluorine-containing fossil hydrocarbon unit (co)polymers suitable for use in the present invention, such as "polytetrafluoroethylene", "Aflon TFE", and "Aflon COP" (above by Asahi Glass Co., Ltd.) , "p〇lyfl〇n TFE", "Neoflon FEP", "Neoflon PFA", "Neoflon ETFE" (above by Daikin Industries Co., Ltd.), "Teflon TFE", "Teflon" FEP", "Teflon pFA", "Teflon EPE", and "Tefzel" (above by Mitsui DuPont Chemical Co., Ltd.). The fluorinated resin used in the present invention may contain a thermal stabilizer, a light stabilizer, a bridging agent, and a coloring agent as long as it does not substantially affect the physical properties such as the total light transmittance and surface tension of the film layer. Wait. The fluorinated resin described above is preferably formed into a film by a hot melt molding method such as a melt extrusion method or a calendering method.

1297305 A7 ___ ____B7 V. Inventive Note (10) According to the invention, the fluorine-based resin film obtained above is formed on the surface of the fluorine-based resin film by a gravure printing method or the like; Preferably, the pressure-sensitive adhesive layer is laminated and coated on the smooth surface layer of the light incident surface of the reflective sheet. The printing layer provided between the fluorine-based resin film and the adhesive layer described above must have a discontinuous printing area. For example, the printing area 16 formed by the printing pattern unit shown in Figs. 5 and 6 is arranged in the form of a separate area. Since the printing sheet of the present invention is discontinuous, the reflective sheet of the present invention is smeared when it is applied outdoors, or the reflective sheet of the present invention is smeared, and when the surface is cleaned with a solvent, even at the interface between the fluororesin film and the printing layer, Infiltration of water or solvent occurs, and the infiltration of water or solvent is limited to a separate printing area and does not spread over the entire surface of the reflective sheet. The above-mentioned printing pattern unit is not particularly limited, and may be a pattern such as a circle, an ellipse, a square, or a rectangle, and a geometric figure composed of a straight line and a curved line may be used. In addition, a combination of words and symbols or a combination of two or more printed pattern units may be used. The pattern (pattern, line, curve, text, and δ, etc.) formed by the printed pattern units has a maximum printing width of 1 mm or less, preferably 5 mm or less, and 2 mm or less. When the maximum printing width exceeds 1 〇111111, it is likely to cause immersion in water, a solvent, or the like, causing swelling between the fluororesin film and the printing layer, and peeling of the fluororesin film. The arrangement of the above-mentioned printing embossing unit, such as the printing pattern unit used, is arranged in mutually independent regions, and the spacing between them can be arbitrarily arranged, but the arrangement of the non-printing portions between the printing pattern units is at least equal to imm. ^ A 〇r? 〇- _ This paper scale applies to China National Standard (CNS) A4 specification (2i〇x297 public love·)-------- 1297305 A7 Γ-—~一—___ Β7 V. Invention description (") is preferably 5 mm or more, and more preferably l〇mm or more. When the minimum interval is less than 1 mm, immersion due to water or solvent is likely to occur, and expansion occurs between the fluorine resin film and the printed layer. And a phenomenon in which the fluorine-based resin film is peeled off, etc. The printing layer formed as described above has a total printing area of 80% or less of the surface area of the reflective sheet, and 40% or less of them are preferable, and 2% or less is preferable. When the total printing area of the printing layer exceeds 8 〇 0 / 〇, the immersion of water or a heart agent or the like is likely to occur, and the fluorine-based resin film and the printing layer are swelled, and the fluorine-based resin film is peeled off. The layer consists of fluororesin, acrylic In the group of the resin, the polyester resin, the urethane resin, and the chlorinated vinyl resin, one or more of the resin for forming the printing ink is selected. The fluorinated resin layer of the formed printed layer is laminated with an adhesive layer. - When the coating layer is coated on the smooth surface layer of the light incident surface of the reflective sheet, the adhesive layer is formed by applying an adhesive to the adhesive surface of the fluorine resin film in advance; and applying the adhesive to the reflective sheet. The surface layer of the material is formed by molding; or after applying the adhesive to a suitable release material, it is transferred onto the adhesive surface of the fluorine-based resin film or the surface layer of the reflective sheet to be formed. The thickness of the adhesive layer formed as described above may vary depending on the type of the adhesive and the thickness of the resin film to be bonded, and is generally in the range of 5 to 80/zm, of which 10 to 70/zm is preferred, 20 to 60. The adhesive of the above-mentioned forming adhesive layer is generally suitable for the pressure-sensitive adhesive of the main component adhesive resin, and the secondary transition temperature (Tg) is 100 ° C to + 50 °. Within the range of c, one of which is 80 ° C ~ + 20 ° c is better For the adhesive resin, the pressure-sensitive adhesive used in the past can also be used. -14-^0303 This paper size is applicable to the Chinese national standard (CNS> A4 specification (210 X 2.97 mm) 1297305 A7 _______ B7 V. Invention description (12 There is no particular limitation on the type thereof. For example, an acrylic resin, a urethane vinegar system, a vinyl acetoacetate copolymer system, and a synthetic resin such as Shishi may be used. Among them, an acrylic resin is suitable. Resins, for example: ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-mercaptobutyl acrylate, n-hexyl acrylate, 2 _Ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-decyl propyl phthalate, and isodecyl acrylate, etc., one of the C2 to C12 alkyl acrylates Monomer A), with acrylic acid, methacrylic acid, acrylamide, N-pyridyl acrylamide, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate, etc., functional group containing propylene At least one of acid monomers ( Body B), the other of the available copolymerized in a proportion within the above range based on the Tg's. The copolymerization ratio of the above monomer a to the above monomer B is such that the weight ratio of the monomer A/monomer B is in the range of 99.5/0.5 to 70/30, and preferably 99/1 to 75/25. A suitable acrylic resin in the adhesive resin is a copolymer obtained by copolymerizing butyl acrylate (BA) and acrylic acid (AA), and the weight ratio of BA/AA is in the range of 99.1/0.9 to 70/30. Among them, 99.5/0.5~80/20 is preferred. The adhesive for forming the above-mentioned adhesive layer is preferably added to the ultraviolet absorber in addition to the above-mentioned adhesive resin for the purpose of improving the weather resistance of the substrate and the base reflective sheet, and a light stabilizer may be added as needed. The ultraviolet absorber suitable for the above adhesive resin generally has a maximum absorption wavelength in the range of 340 to 353 nm, and among them, 343 to 346 nm is preferable, for example, a cyanoacrylate type, a benzotriazole type, and a benzophenone type. , Salicylic acid, & UV absorbers such as stupid phenols. Among the reactive types, the A 4 A 〇 ^ "-Ci. j 篆 -15- & ruler applies to the Chinese National Standard (CNS) A4 specification (21〇 X 297 mm) 1297305

Anyone who reacts with the formed polymer (adhesive resin) or who has previously reacted with the aforementioned military body may be added to the polymer. Specific UV and line absorbents are applicable. <Column: Benzotriazole. Sitting UV absorbers, for example: 2-(3,5-di-t-butylhydroxyphenyl)benzotriazole, 2-[2_hydroxy-3,5-di(α,α.dimethyldiphenyl) Amidoxime) phenyl]_2H- benzotriazole, and 2-(3,5-di-p-pentyl-2-hydroxyphenyl)benzotriazole; etc.; dimercaptoketone-based ultraviolet absorber, for example: 2-hydroxy-4-octyloxybenzophenone-, 2, bis-dihydroxydiphenyl-, and 2-hydroxy-4-methoxy-2, carboxydiphenyl fluorenone, etc.; Line absorbers, for example, p-phenyl sulphate, p-octylphenyl sulphate, resorcinol monobenzoate, and 't-butylphenyl sulphate; and cyanoacrylate It is a UV absorber, for example, ethyl cyano-3-3 3-diphenyl acrylate vinegar, and 2-ethylhexyl 2-cyano_3,3-diphenyl propyl tyanate. Among these, the stupid triazole-based ultraviolet absorber is most suitable. The above ultraviolet absorber is usually used under the weight of the adhesive resin of 1 〇〇 (solid portion), and the weight is in the range of 0.5 to 10, wherein the weight 〇 6 to 9 is preferred, and the weight is 0.7 to 8 Very good. The adhesive for forming the above-mentioned adhesive layer is preferably a light stabilizer added to the above-mentioned ultraviolet absorber. Suitable light stabilizers, for example, light stabilizers such as barrier amines or barrier phenols, among which barrier amine light stabilizers are suitable. The barrier amine light stabilizer is not particularly limited, and those having a high molecular weight are preferably those having a N-substituted piperidinyl group. The barrier amine light stabilizer generally has a weight average molecular weight of 4 〇〇 1 〇 〇, and 〇 (9), wherein 500 to 5,000 is preferred. The barrier amine light stabilizer, for example, butyl tetracarboxylic acid and N-substituted 1-piperidinyl polymer ester; commercially available sales - 16-010305 paper size standards apply to China National Standard (CNS) A4 specifications ( 210X 297 mm) 1297305

For example, MARK H63 (trade name, Asahi Denki Kogyo Co., Ltd. MARK-LA62) (trade name, Asahi Denki Co., Ltd.), and TINUVIN-622LD (trade name, Japan Ciba-Geigy shares)艮A 司衣) and so on. The addition of the above-mentioned high molecular weight barrier amine light stabilizer prevents the occurrence of resin outflow, so that the performance can be maintained for a long period of time. The amount of the light stabilizer added is not strictly limited and may be changed depending on the type thereof, and is generally used under the weight of the adhesive resin of 100 (solid portion), and the weight is in the range of 0.5 to 5, wherein Weight 〇 6 ~ 4 is better, weight 〇 · 7 ~ 3 is particularly good. Forming the adhesive of the above adhesive layer, in addition to adding the above ultraviolet absorber and light stabilizer, other commonly added components, such as: ethyl acetate and ethyl acetate, such as ethyl acetate; various pigments and dyes; and bridging Agents, bridging promoters, etc., may be added as appropriate. The bridging agent is, for example, an isocyanate, an epoxy, a melamine, or a bismuth aluminum; the bridging accelerator such as dibutylzinc laurate. The above-mentioned adhesive agent can be applied to the adhesive layer of the fluorine-based resin film or the surface layer of the light-incident surface of the reflective sheet, but is applied to the adhesive surface of the fluorine-based resin film in advance, and the adhesive is coated with a release paper. The layer is removed from the release paper when necessary, and is laminated on the surface layer of the light incident surface of the reflective sheet. As shown in FIG. 7 to FIG. 14, the reflective sheet of the present invention is applied to a base reflective sheet (the above-mentioned lens-sealed reflective sheet, lens-cylinder type reflective sheet, and cockroach-type reflective sheet, The second printed layer 21 or 22 is provided on the surface layer 4 or below the surface layer 4, and the reflective layer or the like. 1297305 V. DESCRIPTION OF THE INVENTION (15) The second printing layers 2 1 and 22 can employ continuous printing areas without the need for the printing layer 2 to be a discontinuous printing area. Further, the second printing layers 2 1 and 22 have no particular limitation on the printing width of the printing region, the arrangement thereof, and the total printing area. The printing inks for forming the above-mentioned printing layers 21 and 22 are, for example, an evaporative drying type, an acid curing type, a heat curing type, a two-liquid curing type, an ultraviolet curing type, a thermal transfer ink, and a sublimation transfer ink. Evaporative drying type, acid curing type, heat curing type, two-liquid curing type, ultraviolet curing type, for example, ethylene acid type, acrylic type, polyester type, polyamido type, alkyd type, amine type, epoxy A system, a urethane type, a cellulose type, a rubber type, and a photocurable resin. For thermal transfer inks and sublimation transfer inks, for example, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-isobutylene copolymer, polyamine, polyester, poly Ethyl alcoholic butyric acid 1t carbazate, polyglycol g, etc. For the forming methods of the printing layers 21 and 22, for example, printing methods such as screen printing, ink jet printing, and gravure printing can be used, and the printing inks and printing methods are not particularly limited. Hereinafter, the present invention will be specifically described using examples and comparative examples. The anti-icing property of the antireflective sheet of the examples and the comparative examples, the anti-icing property test, the anti-slip adhesion test, the retroreflective property test, the softness test, the soil removal test, and the method of the printed layer adhesion test, and the like The evaluation methods are as follows. (1) Anti-icing property test A test sheet was obtained by laminating a pressure-sensitive adhesive and a reflective sheet of a printed fluorine-based resin film on a whole surface of an aluminum plate of 7·5 χ 15 cm. The test sheet is vertically erected in -30 C air, and sprayed to spray the water droplets on the reflective B-size. Applicable t _ home standard (CNS) A4 specification (1Τ;·)Χ 297 dongdong) 18 1297305 A7 B7 V. INSTRUCTIONS (16) The entire surface of the sheet was observed for the icing state of the surface after 24 hours, and was evaluated on the basis of the following. 5... The icing portion is less than 5% of the total area. 4... The icing portion accounts for more than 5% of the total area, and 1% is not full. 3... The icing portion accounts for more than 1% of the total area, and 2% is not full. 2... The icing portion accounts for more than 2% of the total area, and 3〇% is not full. 1... The icing portion accounts for more than 3% of the total area. (2) Snow adhesion test The test sheet was obtained by laminating a pressure sensitive adhesive and a reflective sheet of a printed fluorine resin film on a 1×1.5 m aluminum plate. The test piece was placed perpendicular to the S: outdoor snowfall, and the snow adhesion state of the surface after 24 hours was observed and evaluated on the basis of the following. 5... The snow-attached portion is less than 5% of the total area. 4... The snow-attached part accounts for more than 5% of the total area, and 10% is not full. 3... The snow-attached part accounts for more than 1% of the total area, and 2% is not full. 2... The snow-attached part accounts for more than 20% of the total area, and 30% is not full. 1... The snow-attached portion accounts for more than 3% of the total area. (3) Reverse performance test The reflective sheet, which has been laminated with a pressure sensitive adhesive and a fluorine-based resin film, is measured for its light-reflecting performance by the measurement of the light-reflecting property specified in J1SZ-9117. The angular condition at the time of measurement is the observation angle 〇·2. , · and the incident angle of 5. . (4) Flexibility test reflective sheet, which has been laminated with pressure-sensitive adhesive and printed fluorine-based resin film, 'cut 10×10 cm at 5 ° C to reflect the pressure on the back side of the reflective sheet 010308 -19 - This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ' - 1297305 A7 Γ--------- --- Β7___ V. Description of invention (17) Adhesive is attached to The 5 cm (/) gas ethylene resin water pipe was fixed for 10 seconds, and the bonded state was observed after the fixing was taken, and evaluated on the following basis. 3···No roll-up, peeling, etc. 2···Rolling, peeling and other bonding irregularities, within the range of 1 〇mrn from the edge. 1 ··· Roll up, peel off and other adhesive irregularities, exceeding the edge 1 〇 mm. (5) Dirty removal test sheet, which was laminated with a pressure-sensitive adhesive and a printed fluorine-based resin film, was smeared with an oil-based black pen. After drying for 5 minutes, the soil was removed by the following criteria. Sex. 5··· Wipe with a dry cloth can be easily removed, and there is no trace at all. 4 ··· Wipe with a dry cloth to remove it, and there is no trace at all. 3... It cannot be completely removed by strong wiping with a dry cloth; however, it can be removed by wiping with water or ethyl acetate, and there is no trace at all. 2... It can be removed with a cloth dampened with water or ethyl alcohol, but leaves traces. 1... It cannot be removed with a cloth dampened with water or ethyl alcohol. (6) Printed layer adhesion test The reflective sheet of a 50 mm square and 1 mm thick aluminum plate was laminated with a pressure sensitive adhesive and a fluorine-based resin film. The WS type solar carbon specified in JIS A1415-1977 was used. In the arc lamp type, the weathering resistance tester was carried out, and after the light-water deterioration promotion test (weather resistance test) for one hour, the printed fluorine-based resin film of the pressure-sensitive adhesive I was peeled off, and the evaluation was performed on the following basis. Its printed layer is adhesive. 5... 100% of the printed area is peeled off from the interface between the adhesive layer and the surface of the reflective sheet I. 1297305

4.··More than 76% of the printed area, 1%% is not full and the interface of the surface layer of the reflective sheet is peeled off. 3···Printing part of the area is more than 33%, 76% is not full and the interface of the surface layer of the reflective sheet is peeled off. The interface is peeled off by the adhesive layer 2 by printing the partial area of 1 〇 〇 % from the adhesive layer 2 . After the weather resistance test of the adhesive layer and the fluorine-based resin film, the fluorine-based resin film was peeled off. Example 1 : a tetrafluoroethylene/ethylene copolymer fluorine-based resin film c〇p having a thickness of about 40 #m, a surface tension of 23 dyne/cm, and a total light transmittance of 92% or more, manufactured by Asahi Glass Co., Ltd.) The surface to be printed was subjected to a corona processing machine (manufactured by Chungao Electric Co., Ltd.) to have a surface tension of 42 dyne/cm. Then, on the corona-treated surface of the fluorine-based resin film, it is printed by gravure printing method, which is a black opaque ink using the following composition; and the printing system is as shown in FIG. 5, and the minimum printing width is lmni2 text and a circle. The printing pattern unit formed by the pattern has a grid-like arrangement in which the longitudinal pitch Ριη and the lateral pitch Pw of the sheet are 150 mm. Ink component, polyester resin ink binder, 9.5 wt%, stone sputum, 1% by weight, ethylene glycol monoethyl acetate, 69.4% by weight, C9 petroleum fraction, 21.0% by weight, "made after printing" Printed surface of resin film, affixed with: butyl acrylate (BA) / acrylic (AA) copolymer (weight ratio:

-twenty one -

Order

Line paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1297305 A7 _____Β7_ _ V. Invention description (19) BA/AA two 90/10) ethyl acetate/toluene (4/6) The solution (solid part = 34%) accounted for 294 'stumped and reset three. The UV absorber (r Tinuvin 328, manufactured by Ciba-Geigy Co., Ltd.) has a weight of 1 > 4, the barrier amine light stabilizer (r Tinuvin 622LP), manufactured by Ciba-Geigy Co., Ltd., 0.7, and the bridging agent. a cyclohexane diisocyanate bridging agent 1 - methoxyacetic acid propyl ester-2 / diphenylbenzene (1/1) solution (solid portion = 75%), accounting for 0.3% by weight; After being applied to a release paper, it was dried to form a pressure-sensitive adhesive layer having a thickness of about 50 / / m to form a printed fluorine-based resin film having a pressure-sensitive adhesive. Next, a printed fluorine-based resin film having a pressure-sensitive adhesive is removed from the release paper and attached to a commercially available white lens-cylinder type reflective sheet (NC Light SEG 15012, Japan Carbide Polymer Co., Ltd. The light incident surface layer 'of the light incident surface layer' has a reflective sheet having a surface layer coated with a fluorine-based resin film. The obtained retroreflective sheeting was subjected to various experiments in accordance with the above experimental method, and the experimental results are shown in Table 1 which will be described later. Example 2: A printed fluorine-based resin film having a pressure-sensitive adhesive prepared in Example 1 was attached to a commercially available white enamel type reflective sheet (NC Light crystal grade 92802, Japan Carbide Industry) A light-incident surface layer of a light-incident surface of a company made by Co., Ltd. can obtain a retroreflective sheeting having a surface layer coated with a fluorine-based resin film. The obtained retroreflective sheeting was subjected to various experiments in accordance with the above experimental method, and the experimental results are shown in Table 1 which will be described later. Example 3:

In Example 1, a vinylidene fluoride resin film (PVdF) having a thickness of about 50 // m, a total light transmittance of 92%, and a surface tension of 25 dyne/cm (DX C: A: ii -22- paper) was used. The scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 1297305 V. Invention description (2〇) film 14S0050, manufactured by Electric Chemical Industry Co., Ltd.), replacing the fluorine system of tetrafluoroethylene/ethylene copolymer Resin film. A reflective sheet having a surface layer coated with a fluorine-based resin film was obtained in the same manner as in Example 1 except that the surface of the printing surface was subjected to corona treatment to a surface tension of 43 dyne/cm. The resulting retroreflective sheeting was subjected to various experiments according to the above experimental method, and the experimental results are shown in the following table. [Embodiment 4] In Embodiment 1, as shown in Fig. 6, a printing pattern unit composed of a character and a circular pattern is used in the form of a cross-shaped reverse pattern of a minimum printing width of imm. In addition to the corona-treated surface of the fluorine-based resin film, in the gravure printing method, a translucent gray ink having the following composition is used, and in the same manner as in the first embodiment, a surface layer coated with a fluorine-based resin film can be obtained. Reflective sheet in gray appearance. In the above-described printing pattern unit, the longitudinal pitch Pm and the lateral pitch pw of the sheet are arranged in a bird shape of 2 mm, and the minimum interval between the non-printed portions of the printed pattern unit is 2 mm. The obtained retroreflective sheeting was subjected to various experiments in accordance with the above experimental method, and the experimental results are shown in Table 1 which will be described later. Ink component Polyester resin ink binder 9.59 wt% 0.01 wt% 6 9.4 wt% 21.0 wt% Carbon black ethyl alcohol monoethyl acetate g C9 petroleum fraction Comparative Example 1: In Example 1, a thickness of about 38 was used. # m, a polyethylene terephthalate resin film (PET) having a total light transmittance of 93 〇 / 〇 and a surface tension of 41 dyne / cm (Teijin Te Duolong s-38, manufactured by Teijin Co., Ltd.), Replacing the four-gas paper sheet χ; 297; ^ 1297305 A7 B7 V. Invention (21) The fluorine-based resin film of the ethylene/ethylene copolymer is the same as that of the first embodiment, and the reflector having the surface layer of the printed fluorine-based resin film is obtained. material. The obtained retroreflective sheeting was subjected to various experiments in accordance with the above experimental method, and the experimental results are shown in Table 1 which will be described later. Comparative Example 2: In Example 1, except for the corona-treated surface of the fluorine-based resin film, the entire surface printing was performed by gravure printing, and the printing pattern unit combined with the character and the circular pattern was the same as Example 1, A reflective sheet having a surface layer of a printed fluorine-based resin film and a gray appearance can be obtained. The obtained retroreflective sheeting was subjected to various experiments in accordance with the above experimental methods, and the experimental results are shown in Table 1 which will be described later. Disk_1: Example Comparative Example 1 2 3 4 1 2 Anti-icing performance experiment 5 5 4 5 1 5 Snow adhesion test 5 5 4 5 1 5 Reflective performance experiment 320 820 304 120 294 65 Softness experiment 5 3 4 5 3 5 Dust removal test 5 5 4 5 1 5 Printing adhesion test 4 4 5 4 5 2 -24- -V.; 1, This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 A) | Year 7 B7

12 9 No. 02922 Patent Application Replacement Page (January 96) V. Invention Description (22) [Simple description of component symbols] 1. Fluororesin film 9. Air layer 2. Printed layer 10. Adhesive Layer 3. Adhesive layer 11. Auxiliary layer 4. Surface layer 12. Prism layer 5. Bead adhesion layer 13. Substrate followed by material layer 6. Glass beads 14. Peeled material layer 7. 'Focus layer 15. Incident light 8. Light reflection layer 21~22· Second printing layer-25 This paper size is applicable to Chinese national standard (Cf^S) A4 specification (210 X 297 mm)

Claims (1)

129^^^502922 Patent Application b8s Chinese Patent Application Substitution (January 1996) g VI. Application for Patent Fanyuan~~-1 For a reflective sheet, it is characterized in that it is attached to the light incident side. On the surface layer of the smoothing sheet of the smooth surface layer, a fluorine-based resin film having a total light transmittance of 80% or more is laminated on the surface layer of the reflective sheet, wherein the gas-based resin film and the adhesive layer are provided. a printing layer in which a printing area is discontinuously formed, wherein the printing layer is formed by forming a pattern in which the printing area formed by the printing pattern unit is formed as a separate area, and the pattern of the printing pattern unit is formed, and the maximum printing width is丨〇mm or less, the non-printing portion between the adjacent printing pattern units, and the minimum interval is 1 mm or more. 2. The retroreflective sheeting of claim 1, wherein the printing layer is composed of a resin selected from the group consisting of a fluorine resin, an acrylic resin, a polyg resin, a urethane resin, and a vinyl chloride resin. One or more of the group is formed by printing an ink bonding resin. 3. The reflective sheet of claim 1, wherein the entire printed area of the printed layer accounts for less than 8 % of the surface layer area of the reflective sheet. 4. The retroreflective sheeting of the ninth aspect of the invention, wherein the fluororesin film is surface-treated so that the surface tension of the surface bonded to the printing layer is 31 dyne/cm or more. 5. The retroreflective sheeting of claim 4, wherein the surface treatment is carried out by a corona discharge treatment. 6. The reflective sheet of claim 1, wherein the fluorine-based resin film has a total light transmittance of 85% or more. 7. The retroreflective sheeting of claim 1, wherein the fluorine-based resin film comprises a tetrafluoroethylene/ethylene copolymer or a polyvinylidene fluoride. 76659-960123.doc This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1297305 έβ8 C8 D8 VI. Patent application scope 8. For the reflective sheet of claim 7 of the patent scope, the above PTFE The ethylene/ethylene copolymer has a tetrafluoroethylene unit content of 15 to 85% by weight. 9. The retroreflective sheeting of claim 1, wherein the adhesive layer is formed by a pressure sensitive adhesive. 10. The retroreflective sheeting of claim 1, wherein the second printed layer is disposed above or below the surface layer. 76659-960123.doc This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)