WO2018161256A1 - Anti-counterfeit reflective sheet - Google Patents

Abstract

An anti-counterfeit reflective sheet. The sheet is a retroreflective element provided with an anti-counterfeit bonding layer. The anti-counterfeit bonding layer is a resin containing a pigment having persistent luminance or fluorescence. The anti-counterfeit reflective sheet facilitates identification of counterfeits, and enables accurate identification of a tampered certificate sticker or car plate having the anti-counterfeit reflective sheet attached thereon.

Description

 Anti-counterfeit reflector  Anti-counterfeit reflector

 Technical field

The present invention relates to a road marking, a road sign, a work sign, and the like, a vehicle, a motorcycle, a motorcycle, and the like, a safety material such as a clothing, a life jacket, and the like, a reflective film or a reflection of an advertising material such as a kanban or a vehicle. In detail, regarding the field of reflective films containing re-reflective elements or the field of reflective sheets, more specifically, an anti-counterfeit reflective film or an anti-counterfeit reflective sheet.

 Background technique

Conventionally, a retroreflective sheeting or a re-reflecting sheet which reflects incident light toward a light source has been known, and is widely used in the technical field or the use as described above by utilizing the excellent reproducibility of the re-reflecting sheet at night. In the field, for example, a road sign using a re-reflective reflection sheet, a sign of a work, etc. At night, a light source ray of a vehicle using a traveling vehicle or the like, and a re-reflection mark reflected toward the traveling vehicle can be driven. Provide excellent visibility and deliver clear messages.

 In particular, in recent years, the use of certification stickers and license plates for re-reflective reflection films has been increasing.

 Summary of the invention

The problem to be solved by the present invention or the technical problem is to overcome the shortcomings of the prior art, to provide an anti-counterfeit reflective film or an anti-counterfeit reflective sheet, and to provide the anti-counterfeit reflective film or the anti-counterfeit reflective sheet manufacturing method (the manufacturing method will be implemented) Provided in detail in the method).

The anti-counterfeit reflection sheet (or re-reflection sheet) of the present invention is provided with a security-proof layer on a re-reflective reflection element having a re-reflective reflection element, and the anti-counterfeit adhesion layer is a resin containing a light-storing or fluorescent pigment. That is, in the present invention, it is necessary to include an adhesive layer (or a glue layer) in which the constituent component is an adhesive resin containing a light-storing (also referred to as luminous) or ultraviolet fluorescent (also abbreviated as fluorescent) functional pigment.

 Returning to the reflective element, for example, a glass bead and/or a microprism type structure.

A part of the re-reflecting sheet is made of ultraviolet light (hereinafter abbreviated as UV light), and contains a phosphor (the above-mentioned ultraviolet fluorescent functional pigment may also be referred to as a phosphor, hereinafter abbreviated as a UV phosphor), and an adhesive layer UV of the resin composition. Luminous, visually recognized by the use of UV-emitting content can be identified as fake (like coins, subject to UV light

 After the shot, there will be red or green colors on the pattern).

Alternatively, a part of the re-reflecting sheet is illuminated by a layer of luminous light containing a light-storing functional pigment and a resin, and the viewer can recognize the forgery by using the luminous content of the night light (just like the escape sign of the corridor, when there is no electricity, the pattern Will shine by myself).

The present invention is an anti-counterfeit reflection sheet which can be used for various kinds of authentication stickers (also referred to as decals, English: stickers) and license plates, which have an anti-counterfeiting effect and a light-storing or ultraviolet fluorescent adhesive layer.

If the anti-counterfeiting of the light-storing or UV-fluorescent pigment is used, the light-storing or UV-phosphor is anti-counterfeiting on the surface or inside of the re-reflective element, which affects the retroreflective performance of the re-reflective element, as well as the light-storing or UV phosphor pigment. The weather resistance has an effect, resulting in a shortened service life and thus affecting the anti-counterfeiting performance and effect.

However, the present invention can use the light-storing or UV phosphor anti-counterfeiting method on the back side of the retroreflective element, such that it has substantially no effect on the retroreflective performance; second, such a structure is protected from direct sunlight, wind and rain, or other factors. Direct impact, which in turn can extend the life of anti-counterfeiting.

As is known to all, the existing re-reflective film on the market is very good at nighttime visibility. Therefore, this year, various vehicle license plates, decals, and the like have been greatly increased.

 However, the above-mentioned used authentication stickers and license plates are stripped and stolen.

 Or, the above-mentioned used authentication stickers and license plates are also copied, and all of these become major problems.

The re-reflective sheeting provided by the present invention is excellent in that it can clearly identify the authentication sticker and whether the license plate is forged or not, if the attached authentication sticker or the license plate is tampered with.

More specifically, the YVO4 laser marking machine is used to mark the re-reflection sheet to contain a light-storing or fluorescent dynamic pattern. As shown in FIG. 6, FIG. 6 is a laser-shielded or UV-fluorescent anti-counterfeit laser marking pattern (or characters, lines, marks) as one of the anti-counterfeiting schemes of the present invention, and the laser marking 'NCI' three letters. After that, the laser light is irradiated on the white reflective sheet by the UV ultraviolet light 61. The visual marker 60 can see ultraviolet light such as red or green at the 'NCI' three letters, and the other reflective sheet surface is not marked. Or after laser marking, after being irradiated by natural light or LED lamp 62 for 5 minutes or more, move to the dark place (the longer the time, the better the effect), and the viewer 60 can find the 'NCI' three letters. Green or other color light is emitted, and the surface of the reflector other than the three letters does not emit light.

That is, the YVO4 laser marking machine is used to mark the re-reflection sheet on the above-mentioned re-reflection sheet. The part marked by the laser can be text, pattern, line, and then irradiated with ultraviolet rays, or, by using light irradiation, returning to the reflection sheet, moving to In the dark place, it is possible to determine whether it is forgery. In addition to the laser marking method, it is also possible to not vaporize the specular reflection layer.

The type of the above laser marking machine is not limited as long as it is suitable for marking of the reflective sheet, and may be other than YVO4, such as CO2, optical fiber, etc. Laser marking can be currently in the field of anti-counterfeiting of reflective sheets. There have been more than ten years of marking methods, and can also refer to the utility model patent “a three-dimensional dynamic anti-counterfeiting product” applied by Enxi Ai (Hangzhou) Film Co., Ltd., and the application method is 201520794345.9.

In addition, the re-reflective reflection sheet is attached to a metal plate such as an aluminum plate, and then peeled off, and the metal plate substrate is irradiated with UV ultraviolet light or moved to a dark place, and it is possible to determine whether there is a history of sticking or uncovering to confirm whether or not there is Was forged.

Alternatively, the UV layer of the security layer may be directly irradiated, or light may be irradiated, and then moved to a dark place to determine whether there is a history of sticking or uncovering to confirm whether it has been forged.

In the anti-counterfeit sheet of the present invention, the re-reflective reflection element of the constituent elements in the re-reflective reflection field is not limited, and for example, a micro-spherical lens such as a glass bead and a vacuum-aluminum metal film light reflection constitute a lens-type re-reflection reflection. The formed elements, or microprism type reintroduction elements having an angle of about 90° with respect to each other, are all possible.

Further, the configuration of the re-reflecting element is not limited, for example, an open type re-reflective reflection structure, a capsule-type re-reflective reflection structure, a sealed type re-reflective reflection structure, a capsule-type microprism type reflection structure, and a metal-evaporated microprism type reflection. Construction and so on are all possible.

The open reflection structure is a sectional view as shown in FIG. 1, 11 is a support layer, 12 is a glass microbead ball, and the glass microbead ball has a filling ratio of 60 to 90% in the support layer; 13 is a specular reflection. The layer 14 is an anti-counterfeit adhesive layer containing a resin having a light-storing property or a phosphor pigment composition, and it is possible to confirm whether it is a counterfeit product by natural light or UV ultraviolet light from the L direction.

The open reflection structure includes a support layer (or a support layer) on the side of which light is placed on a side of the glass bead ball, and a side opposite to the light reflection is a reflective metal film or a specular reflection layer, and most of the reflection layer The glass bead ball is embedded in the support layer and the back layer is a security layer.

The capsule type re-reflective reflection structure is a sectional view as shown in FIG. 3, 31 is a light-permeable protective layer, and 36 is a support layer in which the lower microsphere of the glass microbead ball 34 is buried in the support layer 36. 32 is light The light-transmitting protective layer 31 and the support layer 36 are joined to form a support for supporting. Because of the support of the support, an air capsule 33 is formed. The lower hemisphere of the glass microbead ball 34 is a metal evaporation layer 35 as a reflective film. It can be reflected in the direction of the light source and then reflected back to the reflective element. 37 is a resin anti-counterfeit adhesive layer containing a light-storing or phosphor pigment composition, 38 is a rubber protective layer, which can be a paper or plastic film, which can be The release paper peeled off from the rubber protective layer can also be directly bonded to the adhesive and cannot be uncovered. It is confirmed by natural sunlight or UV ultraviolet light from the L direction whether it is a counterfeit product.

The capsule type re-reflective reflection structure is a sectional view as shown in FIG. 3, which includes a protective layer and a support layer. The protective layer is placed on the incident side of the light of the support layer, and a layer of glass micro is placed on the side of the support layer near the protective layer. Beads, and most of the glass bead balls are buried in the support layer, and the buried glass bead balls are covered with metal, which is also the main component of the lens type re-reflection, and the protective layer and the There is an air layer between the lens-type re-reflection element layers, and the air layer is formed by bonding the protective layer and the support layer to form a stent, and is formed into a sealed empty chamber by being formed by each of the brackets.

The enclosed refraction structure is a sectional view as shown in FIG. 2, 21 is a protective layer, 22 is a printed layer, 23 is a support layer, and a glass microbead ball 24 is supported in the support layer, and the glass microbead ball 24 is supported The filling rate in the layer is between 60 and 90%. 25 is the focus forming layer, 26 is the specular reflection layer, 27 is a resin anti-counterfeit adhesive layer containing a light-storing or phosphor pigment composition, and 28 is a rubber protective layer, which may be paper. For the class of plastic or plastic film, the protective layer of the adhesive may be a release paper which can be peeled off from the protective layer of the adhesive, or may be directly bonded to the adhesive (ie, the adhesive layer) and cannot be uncovered. Self-light or UV ultraviolet light is used from the L direction. Confirm if it is a counterfeit.

The enclosed re-reflective reflection structure is a cross-sectional view as shown in FIG. 2, and includes a light transmissive protective layer (abbreviated as a protective layer) and a light transmissive supporting layer (abbreviated as a supporting layer), and the light transmissive supporting layer On the opposite side of the incident side of the light, a layer of glass microbeads is placed, and half of the balls are buried in the support layer, and the side of the glass microbeads not embedded in the support layer is a layer of light focus forming layer. (or the focus forming layer), the side of the glass bead ball which is not in contact with the focus forming layer forms a specular reflection layer. Also in Fig. 2, if necessary, a light translucent layer may be applied to the light transmissive protective layer. Protective layer.

The capsule type microprism type refraction reflection structure is a sectional view as shown in FIG. 4, and 41 is a light transmissive protective layer (abbreviated as a protective layer), and the incident side of the protective layer is a triangular pyramid shape of about 90° to the opposite side. The cube corner retroreflective element layers 44, 43 are connection brackets of a triangular pyramid type cube corner retroreflective element layer 44 and a support layer 45. These brackets 43 form an air capsule structure 42, 46 is a resin anti-counterfeiting composition containing a light-storing or phosphor pigment. Next, the layer 47 is a rubber protective layer, which may be a paper or a plastic film. The adhesive protective layer may be a release paper that can be peeled off from the adhesive protective layer, or may be directly bonded to the adhesive (ie, the adhesive layer). Open. Use natural light or UV light from the L direction to confirm whether it is a counterfeit.

The capsule type microprism type refraction reflection structure is a sectional view as shown in FIG. 4, and includes a light transmissive protective layer and a support layer, and a layer of the microprism type retroreflective element is formed on the opposite side of the light incident on the protective layer. (referred to as the retroreflective element layer), and between the layer of the microprism type reintroduction element and the support layer is an air layer (or air capsule structure), and the air layer is the microprism type reintroduction element The layer and the supporting layer are formed by sticking to form a bracket, and are formed by the brackets to form a sealed empty chamber. Also in FIG. 4, if necessary, a light-transparent protective layer may be further coated with a light-transparent layer. Protective layer.

The metal vaporized microprism type reflection structure is a sectional view as shown in FIG. 5, 51 is a light transmissive protective layer, and a triangular pyramid type having an opposite surface of about 90° between the protective layer 51 and the specular reflection layer 53 is provided. The solid angle retroreflective element layer 52, 54 is a resin anti-counterfeit adhesive layer containing a light-storing or phosphor pigment composition, and 55 is a rubber protective layer, which may be a paper or plastic film, and the adhesive protective layer may be a protective layer from the adhesive. The release paper that has been peeled off can also be directly attached to the glue (ie, the adhesive layer) and cannot be uncovered. It is confirmed by natural light or UV ultraviolet light from the L direction whether it is a counterfeit product.

The metal-steamed microprism-type reflection structure is a cross-sectional view as shown in FIG. 5, and includes a light-transmitting protective layer, and a layer of a microprism-type retroreflective element is formed on the opposite side of the light incident on the protective layer (referred to as a retroreflective element). Layer), the retroreflective element layer is followed by a specular reflection layer, a security layer and a glue protection layer. Also in Figure 5, if necessary, a light transmissive protection layer can be applied to the light transmissive protective layer. Floor.

In the present invention, the anti-counterfeit adhesive layer is a resin containing a light-storing or fluorescent functional pigment, and the resin may be contained in an amount of 0.01 to 95 parts by weight based on 100 parts by weight of the light-storing pigment or the fluorescent pigment, and the light-storing pigment or the fluorescent pigment can be used in the weight. The amount may be 1 to 20 parts by weight, and more preferably 2 to 15 parts by weight. The amount of the light-storing or fluorescent functional pigment added is not critical to the upper limit and the lower limit, and is suitable. It can be fully anti-counterfeit, has excellent visibility and recognition, and as long as there is no problem that the adhesive layer is too hard to cause brittleness, or poor adhesion, that is, if it is in the above range Therefore, as long as the previous conditions are met, no special limitation is made.

 In order to better highlight the anti-counterfeiting performance of the anti-counterfeit adhesive layer, the resin of the anti-counterfeit adhesive layer is colorless and optimal.

The fluorescent pigment is not particularly limited as long as it can satisfy the ultraviolet ray luminance of the above-mentioned anti-counterfeiting condition after the ultraviolet ray irradiation, and is generally preferably an organic fluorescer, for example, naphthalene. A phenol triazole system, a benzoxazole system, etc.; an inorganic phosphor which is generally opaque, and an inorganic metal chloride (inorganic metal lanthanide) or a halogen compound (ハロゲン) The compound system, the sulfide system, and the like; the above various phosphors can be arbitrarily selected.

As the organic phosphor, for example, diaminopurine (ジアミノスチルベンゼン), sodium fluorescein (ウラニン), thioflavin T (チオフラビンT), red (エオシン), rhodamine B (ローダミン B), acridine orange (アクリジンオレンジの他), diphenylmethane (lanthanide), triphenylmethane (lanthanide), xanthene (lanthanide), thiazide (lanthanide), thiazole (チアゾール) For the parent dye, it is possible to use one or a mixture of two or more.

Further, as an inorganic pigment, for example, Zn ₂ GeO ₄ : Mn, ZnO: Zn, ZnS: Cu, ZnS: (Cu, Al), (Zn, Cd) S: (Cu, Al), ZnS: (Cu, Au, Al), Zn ₂ SiO ₄ : Mn, ZnS: (Cu, Ag), (Zn, Cd) S: Cu, Gd ₂ O ₂ S: Tb, La ₂ O ₂ S: Tb, Y ₂ SiO ₅ : _{(Ce, Tb), CeMgAl 11} O 19: Tb, ZnS: (Cu, Co), LaOBr: (Tb, Tm), La 2 O 2 S: Tb, BaMg 2 Al 16 O 27 (Eu, Mu) and other green Luminescent inorganic phosphor; Y ₂ O ₃ :Eu, Y(P,V)O ₄ :Eu, S:Eu, 0.5MgF ₂ ·3.5MgO·GeO ₂ :Mn, YVO ₄ :Eu, (Y,Gd) BO ₃ : red luminescent inorganic phosphor such as Eu; Sr ₅ (PO ₄ ) ₃ Cl: Eu, BaMg ₂ Al ₁₆ O ₂₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, ZnS: Ag, CaWO ₄ , Y ₂ SiO ₅ : Ce, ZnS: (Ag, Ga, Cl), Sr ₂ P ₂ O ₇ : Eu, CaS: Bi, CaSrS: Bi and other blue-emitting inorganic phosphors; may be exemplified. One type or two or more types may be used. Mixed use is also possible. Also, the inorganic system herein and the above-mentioned organic system may be used in combination.

 The inorganic phosphor is excellent in light resistance, heat resistance, solvent resistance, and the like as compared with a general organic phosphor.

Further, in the inorganic phosphor, it is preferable that the particle diameter contained in 80% by weight or more is 25 μm or less, and in the green light-emitting inorganic phosphor, the particle size distribution is 0.1 to 50 μm, and most preferably, the particle diameter is about 12 μm. In the blue-emitting inorganic phosphor, the particle size distribution is 0.1 to 12 μm, and most preferably about 8 μm.

 Further, as the inorganic phosphor, UV ultraviolet irradiation having a wavelength of usually 250 to 400 nm is preferred.

In the light-storing pigment used in the present invention, after the light disappears, the residual light may be used for 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer. However, if only the discriminating person can be clearly distinguished from the anti-counterfeiting, then There is no strict limit on the residual light time.

The above-mentioned light-storing pigment is not particularly limited as long as it can be stored in the dark by natural light or nighttime LED light, and can be used as an anti-counterfeiting method. Starting from the acid-based light-storing pigment, in particular, the general formula contains MAl ₂ O ₄ (wherein M means at least one alkaline earth metal), and the metal acid compound is used as a mother crystal, and the rare earth metal is combined as an activator. A light-storing pigment of an atom is most preferred.

The above alkaline earth metal is preferably selected from at least one metal selected from the group consisting of Ca, Ba and Sr. Further, the rare earth metal is Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy. It is possible to select at least one of Ho, Er, Tm, Yb and Lu. The light-storing pigment is at least one metal-bonded rare earth metal selected as the activator Mn, Sn and Bi, that is, the light-storing pigment contains an activator Mn. , a kind of rare earth metal and alkaline earth metal (M) in Sn and Bi.

As a light-storing pigment, for example, SrAl ₂ O ₄ :Eu, SrAl ₂ O ₄ :(Eu,Dy), SrAl ₂ O ₄ :(Eu,Nd), SrAl ₂ O ₄ :(Eu,Pr), SrAl ₂ O ₄ : (Eu, Sm), SrAl ₂ O ₄ : (Eu, Tb), SrAl ₂ O ₄ : (Eu, Ho), SrAl ₂ O ₄ : (Eu, Mn), SrAl ₂ O ₄ : (Eu, Sn), SrAl ₂ O ₄ : (Eu, Bi), CaAl ₂ O ₄ : (Eu, Nd), CaAl ₂ O ₄ : (Eu, Sm), CaAl ₂ O ₄ : (Eu, Tm), CaAl ₂ O ₄ : ( Eu, Nd, La), CaAl ₂ O ₄ : (Eu, Nd, La), CaAl ₂ O ₄ : (Eu, Nd, Ce), CaAl ₂ O ₄ : (Eu, Nd, Pr), CaAl ₂ O ₄ : (Eu, Nd, Sm), CaAl ₂ O ₄ : (Eu, Nd, Gd), CaAl ₂ O ₄ : (Eu, Nd, Tb), CaAl ₂ O ₄ : (Eu, Nd, Dy), CaAl ₂ O ₄ : (Eu, Nd, Ho), CaAl ₂ O ₄ : (Eu, Nd, Er), CaAl ₂ O ₄ : (Eu, Nd, Tm), CaAl ₂ O ₄ : (Eu, Nd, Yb), CaAl ₂ O ₄ : (Eu, Nd, Lu), CaAl ₂ O ₄ : (Eu, Nd, Mn), CaAl ₂ O ₄ : (Eu, Nd, Sn), CaAl ₂ O ₄ : (Eu, Nd, Bi ), Ca _0.9 Sr _0.1 Al ₂ O ₄ : (Eu, Nd, La), Ca _0.9 Sr _0.1 Al ₂ O ₄ : (Eu, Nd, Dy), Ca _0.7 Sr _0.3 Al ₂ O ₄ : (Eu, Nd, Dy), Ca _0.9 Sr _0.1 Al ₂ O ₄ : (Eu, Nd, Ho), Ca _0.7 Sr _0.3 Al ₂ O ₄ : (Eu, Nd, Ho), etc., one or a combination of two or more may be used herein. of.

The residual light characteristic of this light-storing pigment is not limited, and in view of visibility, generally 150 mcd/m2 is possible, preferably 200 mcd/m ² , and more preferably 250 mcd/m ² .

The type of the anti-fake adhesive of the present invention is not particularly limited as long as it is a resin used as a general binder resin, and for example, a cellulose resin or an acrylic resin can be used. Any polymer or mixture such as a silicone resin, a melamine resin, a rubber resin, or a phenol resin; among them, an acrylic resin or a silicone resin which is excellent in weather resistance and has good adhesion characteristics is preferable, and is required. Bridging agents, additives, etc.

The molecular weight of the resin forming the anti-counterfeit adhesive layer is not limited, and it is preferable if the high molecular weight can be maintained, and the average molecular weight (hereinafter referred to as Mw as abbreviation) is 500,000 or more of the resin, preferably 5 to 1,000,000, preferably 60 to 100. Million, where the functional group Mw is More than 500,000 resins, bridging agent bridging reaction resins using isocyanate bridging agents are excellent.

The thickness of the security underlayer is preferably 5 μm to 200 μm, preferably 15 μm to 120 μm, and more preferably 30 μm to 60 μm.

 DRAWINGS

 Fig. 1 is an explanatory sectional view showing an open type re-reflective reflection sheet.

 Fig. 2 is an illustration of a closed type refraction reflection segment.

 Fig. 3 is a cross-sectional explanatory view of a capsule type re-reflective sheeting.

 Fig. 4 is a cross-sectional view showing the capsule prism type re-reflective reflection sheet.

 Fig. 5 is a cross-sectional view showing the metal evaporated microprism type reintroduction sheet.

 Fig. 6 is an explanatory diagram of anti-counterfeiting with a light-storing or UV-fluorescent anti-counterfeit laser marking pattern.

 detailed description

 The following is further illustrated by the examples.

 Example 1

 A transparent polyethylene terephthalate film having a thickness of 75 μ using Teijin Co., Ltd. (trade name: Tetoron Film) S-75, Teijin Co., Ltd.) as a substrate;

On this, 100 parts by weight of an acrylic resin solution (trade name: RS-1200) made by Enxi (Hangzhou) Film Co., Ltd., and 14 parts by weight of methylated melamine resin solution (trade name: NIKALAC) MS-11, SANWA CHEMICAL CO., LTD.), 4 parts by weight of a cellulose derivative (trade name: CAB, TOKUSHIKI Co., Ltd.), 1.5 Parts by weight of UV absorber (trade name: Seesorb 103, SHIPRO KASEIKAISHA CO., LTD.), 0.05 parts by weight of leveling agent (trade name) :BYK-300, BYK-Chemie Japan KK), 0.12 parts by weight of catalyst (trade name: BECKAMINE P-198 (DIC Co., Ltd.) and 16.7 parts by weight of a solvent (MIBK/toluene = 8/2) were stirred and mixed to prepare a resin compounding liquid for forming a surface protective layer, and the resin compounding liquid was applied to an engineering substrate. The film is dried to form a surface protective layer having a thickness of about 36 μ;

 100 parts by weight of acrylic resin (trade name) :RS-3000, Enxi Ai (Hangzhou) Film Co., Ltd.), 22 parts by weight of chromogenic precursor (trade name: AR-6300, TOKUSHIKI Co., Ltd.), 13.6 Parts by weight of isocyanate-based crosslinking agent (trade name: Sumijoule N-75, Sumika Bayer Urethane Co., Ltd.) and 20 as a solvent Parts by weight of toluene and 10 The parts by weight of MIBK were mixed and stirred to prepare a resin compounding liquid for forming a holding layer, and then the resin compounding liquid was applied onto the surface protective layer, followed by drying at 100 ° C for 5 minutes to form a thickness of about 13 μm, a transmittance of 10% of the focus forms the support layer on the opposite side of the layer;

A tiny glass ball (trade name: NB-23S, Enxi (Hangzhou) Film Co., Ltd.) was attached to the above support layer, and heat-treated at 145 ° C for 3 minutes and 30 seconds to make the tiny glass ball exposed from the support layer. The glass ball is immersed in the support layer, and the diameter of the tiny glass sphere is maintained in the support layer. 75%.

 In addition, the thickness and transmittance of various protective layers were as follows using a transparent polyethylene terephthalate film having a thickness of 75 μm from Teijin Co., Ltd. (trade name: Tetoron Film After coating and drying on S-75, Teijin Co., Ltd., the total thickness was reduced by 75 μm. The transmittance was measured by a protective layer together with a transparent polyethylene terephthalate film, and then multiplied by a coefficient of 0.93 to obtain a result.

 100 parts by weight of an acrylic resin solution (trade name: RS-5000, Enxiai (Hangzhou) Film Co., Ltd.), 5.5 parts by weight of methylated melamine resin solution (trade name: NIKALAC MS-11, SANWA CHEMICAL CO., LTD.) And 39.3 parts by weight of a solvent (MIBK/toluene=4/6) was mixed and stirred to prepare a resin compounding liquid for a focus forming layer, and the resin compounding liquid was applied onto a holding layer and a micro glass ball and dried. Thereby, a focus forming layer having an average thickness of about 23 μm was formed.

 Next, aluminum was vacuum-deposited on the focus forming layer to obtain a specular reflection layer.

 Will be 100 5% by weight of butyl acrylate BA/acrylic acid AA (weight ratio: BA/AA = 90/10) ethyl acetate copolymer solution (ethyl acetate / toluene = 1 / 1), 5 parts by weight of the fundamental special chemical ) making green phosphors ( Product name: MB-760), 0.5 parts by weight of isocyanate crosslinker (trade name: CoronateL, NipponPolyurethane Industry Co., Ltd.) and 16.1 parts by weight of ethyl acetate as a solvent were stirred and mixed to prepare a resin compounding liquid for forming a pressure-sensitive adhesive layer, and the resin compounding liquid was applied to a release film ( Trade name: E2P-H (P), LINTEC Corporation) and dried to form an adhesive layer (i.e., an adhesive layer) having a thickness of about 41 μm.

 Next, after bonding the specular reflection layer and the pressure-sensitive adhesive layer, the engineering substrate is peeled off, thereby obtaining an anti-counterfeit reflection sheet having an adhesive layer.

 Example 2

 In the present embodiment, in addition to 5 parts by weight of a green phosphor (hereinafter referred to as a special special chemical company) The product name: MB-760) was the same as that of Example 1 except that it was replaced by 5 parts by weight of N-Night Luminescent Co., Ltd. (trade name: G-300M).

 Example 3

On the engineering paper, a temporary support layer was formed by heating the adhesive at a softening temperature of about 105 ° C at 105 ° C, and a glass microsphere ball having an average particle diameter of about 65 μm and a tortuosity of about 1.91 was uniformly and closely placed thereon. Roller pressurization, 3/1 of the diameter of the tiny glass sphere is embedded in the resin.

Thereafter, aluminum is vacuum-plated on the bare side of the temporary support layer glass microbead ball, so that a metal evaporated film having a thickness of about 0.1 μm is formed on the glass microbead ball. Then, on the side of the temporary support layer on which the metal film is plated, A silane coupling agent liquid (manufactured by Toray Dow Corning Co., Ltd., trade name: SZ6030) having a viscosity of about 2 cP at 23 ° C was applied to form a film containing a coupling agent having a thickness of about 0.3 μm.

Next, 100 parts by weight of an acrylic resin solution having a solid content of about 50% by weight (manufactured by Nippon Co., Ltd., trade name ST-700), and 14.2 parts by weight of HMDI (4, 4'- Dicyclohexylmethane diisocyanate) The bridging agent was mixed with a synthetic resin solution, and the resin compounding liquid was applied onto a peeling-treated transparent polyethylene terephthalate film having a thickness of 20 μm, and the solvent was removed by drying to form a film having a thickness of about 30 μm. Then, 167 parts by weight of an acrylic resin solution (manufactured by Nippon Denshi Kogyo Co., Ltd., trade name KP-1864A) having a solid content of about 30% by weight, and an acrylic resin solution of 125 parts by weight and a solid content of about 40% by weight ( 10 parts by weight of CAB (cellulose acetate butyrate), 50 parts by weight of titanium dioxide, and MIBK (methyl isobutyl ketone), 30 parts by weight, and a mixture of 30 parts by weight of a resin solution, manufactured by Nippon Denshi Kogyo Co., Ltd., trade name: KP-1703A) The resin compounding liquid was applied onto the above-mentioned 30 μm film, and the solvent was removed by drying to form a support layer film having a total thickness of about 110 μm.

The support layer film and the previously prepared temporary support layer are glass-beaded by metal and coated with a coupling agent film, and when laminated, heated at 70 ° C and pressurized at 900 kg/m, glass beads One third of the diameter of the ball is buried in the support layer film.

The pressure-bonded film is made up of a paper tube having an inner diameter of about 75 mm and an outer diameter of about 95 mm, and the take-up tension is 40 kg/m, which is taken up for 500 m, and then left at room temperature for 20 hours, and the support film is completely bridged and then re-rolled. The engineering paper with polyethylene on the temporary support layer was peeled off, and the glass microbead balls were transferred to the support layer.

Next, a support layer film with glass bead balls and an unstretched acrylic film having a thickness of 75 μm and a total light transmittance of about 93%, and the glass microbeads and the acrylic film are relatively bonded while passing through the raised wire diameter. Between about 0.3 mm mesh shape, a surface temperature of about 190 ° C metal shaft and a rubber shaft having a surface temperature of about 60 ° C, the acrylic film side is in contact with the rubber shaft and passed, and the treated transparent polyethylene terephthalate is peeled off. The ester film side is pressurized and thermally deformed by the convex mesh metal shaft.

The peeled and treated transparent polyethylene terephthalate film was peeled off from the hot melt-deformed product, and then 100 parts by weight (manufactured by Nippon Denshi Kogyo Co., Ltd., trade name KP-997), and 5 parts by weight of the fundamental Special chemical company's green phosphor ( Trade name: MB-760) Stir-mixed and coated on a silicon-treated transparent polyethylene terephthalate release film having a thickness of about 75 μm to form a pressure-sensitive adhesive having a thickness of about 41 μm (ie, The layer is bonded to the support layer film to form a UV-emitting re-entry anti-counterfeit sheet having a capsule structure.

 Example 4

 In the present embodiment, in addition to 5 parts by weight of a green phosphor (hereinafter referred to as a special special chemical company) Product name: MB-760) Replaced with 5 parts by weight of N-Night Glue (made by Nippon Special Chemical Co., Ltd.) The product name was the same as in Example 3 except that the product name was G-300M. The luminescent luminous re-reflection sheet of the capsule structure was obtained.

 Example 5

 Reconstruction of reflective element 1

 Diamond turning with a front end angle of 68.53 degrees and 71.52 degrees, A method of cutting a metal surface into a brass plate master from three directions into a 60.62 degree cross section and a V-shaped groove in a cross-sectional shape, and forming a plurality of mountain-shaped triangular pyramids having a height of 100 μm on the brass plate master. Shaped solid angle.

 A metal mold made of nickel steel is formed on the surface of the master mold by an electric boring method.

40 parts by weight of acrylic resin, dimercaptodiphenyl sulfide dimethyl methacrylate (ビス(メタクリロイルチオフェニル)スルフォイド), 2,4 dibromophenyl acrylate (2,4-ジブロモフェニル(メタ)アクリレート) 58 Parts by weight, photo-curing catalyst "Darocur 2 parts by weight (manufactured by Seiko Co., Ltd.), a surface protective layer having a refractive index of n = 1.63 and an acrylic ultraviolet curable resin solution for a re-reflective element layer, and the resin was applied to a metal mold. Then, a 50 μm acrylic resin film (manufactured by Kaneka Chemical Industry Co., Ltd., 014NST), which is a surface protective layer, is bonded to the ultraviolet curable resin.

 Next, the acrylic resin film surface is irradiated with ultraviolet rays to cure the ultraviolet curable resin. Finally, the cured resin is peeled off from the metal mold.

 Support layer and connection bracket formation

 The polyester fiber resin composition was coated on the surface of a smooth PET film having a thickness of 38 μm to form a support layer and a connecting bracket.

 Recombination of the composition of the reflection sheet

Then, the surface protective layer and the re-reflective reflection element layer and the support layer and the bonding layer are convexly engraved with a mesh surface temperature of 0.3 mm in line width between 190 ° C metal shaft and rubber shaft, wherein the re-reflective element It is pressed and brought into contact with the rubber shaft, and is sealed and sealed into a reflection sheet by a hot melt method.

100 parts by weight (manufactured by Nippon Denshi Kogyo Co., Ltd., trade name: KP-997), and 5 parts by weight of a green phosphor (manufactured by Basic Special Chemicals Co., Ltd.) were obtained from the hot-melt-deformed product ( Trade name: MB-760) Stir-mixed and coated on a silicon-treated transparent polyethylene terephthalate release film having a thickness of about 75 μm to form a pressure-sensitive adhesive having a thickness of about 40 μm. The support layer film is bonded to form a UV illuminating re-reflection sheet of a capsule microprism type structure.

 Example 6

 In the present embodiment, in addition to 5 parts by weight of a green phosphor (hereinafter referred to as a special special chemical company) Product name: MB-760) Replaced with 5 parts by weight of N-Night Glue (made by Nippon Special Chemical Co., Ltd.) Except for the trade name: G-300M), the rest were the same as in Example 5. A luminous-type re-entry anti-counterfeit sheet having a capsule structure was obtained.

 Comparative example 1

In the comparative example, except that 5 parts by weight of N-Night (product name, G-300M) manufactured by Kokusai Special Chemical Co., Ltd. was not added, the same procedure as in Example 1 was carried out, and a sealed re-reflective sheet was obtained.

 Comparative example 2

 In this comparative example, except for 5 parts by weight of a green phosphor (manufactured by Basic Special Chemical Co., Ltd.) The product name: MB-760) was the same as in Example 2 except that it was not added. An enclosed re-reflective sheet was obtained.

 Comparative example 3

In the present comparative example, except that 5 parts by weight of N-Night Light (trade name, G-300M) manufactured by Kokusai Special Chemical Co., Ltd. was not added, the same procedure as in Example 3 was carried out, and a capsule-type re-reflective sheet was obtained.

 Comparative example 4

 In this comparative example, except for 5 parts by weight of a green phosphor (manufactured by Basic Special Chemical Co., Ltd.) Trade name: MB-760) The same as in Example 4 except that it was not added. A capsule-type re-reflective sheet was obtained.

 Comparative Example 5

In the present comparative example, except that 5 parts by weight of N-Night (product name, G-300M) manufactured by Kokusai Special Chemical Co., Ltd. was not added, the same procedure as in Example 5 was carried out, and a microprism type re-reflective sheet was obtained.

 Comparative Example 6

 In this comparative example, except for 5 parts by weight of a green phosphor (manufactured by Basic Special Chemical Co., Ltd.) The trade name: MB-760) was the same as in Example 6 except that it was not added. A micro-angular type re-reflective sheet was obtained.

 The anti-counterfeiting performance of the above Examples 1 to 6 and Comparative Examples 1 to 6 was compared.

 Test method 1: Using ultraviolet light, directly observe whether the anti-counterfeit rubber layer will produce ultraviolet light, which is referred to as method one.

Test method 2: Under natural light or under the illumination, the protective paper on the anti-counterfeit rubber layer is directly stripped (if it is transparent PET, CPP and the like can be removed without peeling), direct for 10 minutes, take the dark to observe whether the anti-counterfeit rubber layer is It will emit luminous light, referred to as method two.

Test method 3: The front side of the film is taken on the laser marking machine, and certain patterns and processing conditions are set. Laser marking on the film can be seen at a certain angle or at any angle. See, but can not completely destroy the security layer. Then, The ultraviolet light is irradiated on the mark, and it is observed whether the ultraviolet light is generated at the laser-proof marking, which is referred to as method three.

Test method 4: The front side of the film is taken on the laser marking machine, and certain patterns and processing conditions are set. Laser marking on the film can be seen at a certain angle or at any angle. See, but can not completely destroy the anti-counterfeit rubber layer. Then, the marked part is under natural light or under the illumination, direct for 10 minutes, get to the dark to see if the laser marking will emit night light, referred to as method four.

Test method 5: The film is laminated on an aluminum plate polished with 280 sand skin, and after 7 days of curing at 23 ° C, the film is removed, and the ultraviolet light is used to directly observe whether the residual glue at the stripped aluminum plate generates ultraviolet rays. Light, referred to as method five.

Test Method 6: The film is attached to an aluminum plate polished with 280 grit sand, and after 7 days of curing at 23 ° C, the film is removed, and the stripped aluminum plate is exposed to direct light for 10 minutes under natural light or under illumination. Observe whether there will be night light in the dark, referred to as Method 6.

 The test results are shown in Table 1.

 Table 1

	method one	Method Two	Method three	Method four	Method five	Method six
Example 1	no	Have	no	Have	no	Have
Example 2	Have	no	Have	no	Have	no
Example 3	no	Have	no	Have	no	Have
Example 4	Have	no	Have	no	Have	no
Example 5	no	Have	no	Have	no	Have
Example 6	Have	no	Have	no	Have	no
Comparative example 1	no	no	no	no	no	no
Comparative example 2	no	no	no	no	no	no
Comparative example 3	no	no	no	no	no	no
Comparative example 4	no	no	no	no	no	no
Comparative Example 5	no	no	no	no	no	no
Comparative Example 6	no	no	no	no	no	no

In the above embodiments 5 and 6, since there is no metal specular reflection layer, it can be directly irradiated with ultraviolet rays or placed under natural light or under the illumination lamp to confirm whether there is UV or luminescent anti-counterfeiting function. Also, the back protective paper is PET, CPP or other similar transparent or translucent, can confirm whether there is UV or luminous anti-counterfeiting function directly from the protective paper.

As described above, the present invention can provide an excellent anti-counterfeit retroreflective sheeting which cannot be copied, and can be applied to traffic signs, engineering marks, commercial signs, automobile license plates, retroreflective labels, and retroreflective RFID (radio wave identification) labels.

Claims (15)

1. An anti-counterfeit reflection sheet characterized in that an anti-retroreflective layer is provided on a re-reflective reflection element having a re-reflective reflection element, and the anti-counterfeit adhesion layer is a resin containing a light-storing or fluorescent pigment.
2. The anti-counterfeit reflection sheet according to claim 1, wherein the anti-counterfeit adhesive layer is provided on a back surface of the re-reflective reflection element.
3. The anti-counterfeit reflection sheet according to claim 1, wherein the re-reflective reflection element includes a light-storing or fluorescent dynamic pattern.
4. The anti-counterfeit reflection sheet according to claim 1, wherein the re-reflective reflection element has an open re-reflective reflection structure, a capsule-type re-reflective reflection structure, a sealed-type re-conversion reflection structure, and a capsule-type microprism type reflection structure. Or metal vaporized microprism type reflection structure.
5. The anti-counterfeit sheet according to claim 1, which comprises 0.01 to 95 parts by weight of a light-storing or fluorescent pigment per 100 parts by weight of the resin.
6. The anti-counterfeit sheet according to claim 1, wherein the resin is colorless or colored.
7. The anti-counterfeit reflection sheet according to claim 1, wherein the fluorescent pigment is an organic phosphor and/or an inorganic phosphor; and the organic phosphor includes a naphthol triazole or benzoxazole system. Or the organic phosphor is diaminopurine, sodium fluorescein, thioflavin T, erythromycin, rhodamine B, acridine orange, diphenylmethane, triphenylmethane, xanthene, thiazide Or one or a mixture of two or more of thiazoles; the inorganic phosphor includes an inorganic metal chloride, a halide or a sulfide; or the inorganic phosphor is a green light-emitting inorganic phosphor, a red light-emitting inorganic A phosphor or a blue-emitting inorganic phosphor.
8. The anti-counterfeit sheet according to claim 7, wherein the inorganic phosphor contains 80% by weight or more of a particle diameter of 25 μm or less.
9. The anti-counterfeit reflection sheet according to claim 1, wherein the light-storing pigment is an acid-based light-storing pigment, and the component of the acid-based light-storing pigment is a metal acid compound in combination with a rare earth metal atom, and a general formula of the metal acid compound is MAl2O4, wherein M means at least one alkaline earth metal.
10. The anti-counterfeit reflection sheet according to claim 9, wherein the alkaline earth metal is at least one selected from the group consisting of Ca, Ba and Sr; and the rare earth metal is Sc, Y, La, Ce, Pr, Nd, Sm, Eu At least one of Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu is selected.
11. The anti-counterfeit reflection sheet according to claim 9, wherein at least one metal-bonded rare earth metal is selected from Mn, Sn and Bi.
12. The anti-counterfeit sheet according to claim 1, wherein the resin is any one of a cellulose resin, an acrylic resin, a silicone resin, a melamine resin, a rubber resin, and a phenol resin.
13. The anti-counterfeit sheet according to claim 1, wherein the resin has an average molecular weight of 500,000 or more.
14. The anti-counterfeit reflection sheet according to claim 1, wherein the anti-counterfeit adhesion layer has a thickness of 5 μm to 200 μm.
15. The method for identifying an anti-counterfeit reflector according to any one of claims 1 to 14, characterized in that

    First, after the laser marking, the anti-counterfeit reflection sheet is irradiated to the dark place by natural light or LED light for 5 minutes, and then the viewer can find that the laser marking mark emits green, red or other color light, and the laser marking The surface of the reflector outside the place does not emit light;

    Or sticking the anti-counterfeit reflection sheet on a metal plate such as an aluminum plate, and then peeling off, using UV light to the metal plate substrate or moving to a dark place, and then judging whether there is a history of sticking or uncovering to confirm whether it is forged;

    Or, directly irradiate the anti-counterfeit layer with UV-UV light, or light, and then move to a dark place, and then judge whether there is a history of sticking or uncovering to confirm whether it is forged.