WO2005022211A1 - 破壊層の設置された再帰反射シート - Google Patents
破壊層の設置された再帰反射シート Download PDFInfo
- Publication number
- WO2005022211A1 WO2005022211A1 PCT/JP2004/012872 JP2004012872W WO2005022211A1 WO 2005022211 A1 WO2005022211 A1 WO 2005022211A1 JP 2004012872 W JP2004012872 W JP 2004012872W WO 2005022211 A1 WO2005022211 A1 WO 2005022211A1
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- WO
- WIPO (PCT)
- Prior art keywords
- layer
- sheet
- resin
- retroreflective sheet
- retroreflective
- Prior art date
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/12—Reflex reflectors
- G02B5/126—Reflex reflectors including curved refracting surface
- G02B5/128—Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
Definitions
- the present invention relates to a retroreflective sheet having a novel structure, and more particularly, to a retroreflective sheet characterized in that a rupture layer is provided on a part of the retroreflective sheet.
- a retroreflective sheet comprising at least a surface layer, a retroreflective element layer, and an adhesive layer
- at least one destructive layer is provided between layers constituting the retroreflective sheet.
- the resin constituting the destructive layer is an alicyclic polyolefin resin or an alicyclic acrylic resin
- the retroreflective sheet is adhered to the substrate and then peeled off from the substrate.
- the present invention also relates to a retroreflective sheet provided with a destruction layer, which is separated at an interface between the destruction layer and a layer that is in close contact with the destruction layer, or is delaminated by destruction of the destruction layer.
- the present invention relates to a retroreflective sheet provided with a useful destruction layer in a reflector of an infrared light reflection type sensor.
- a retroreflective sheet used for various kinds of authentication stickers, etc. when the retroreflective sheet once adhered is torn off and used for another purpose, one of the retroreflective sheets is used. Destruction layer is provided in the part The purpose is to make it impossible for the retroreflective sheet to be destroyed and diverted. (Hereinafter, this is also referred to as a tampering prevention effect or a re-peeling prevention effect.)
- a retroreflective sheet with a destruction layer that can be used for a tamper-proof sticker that can withstand long-term use at high temperatures and maintain a stable tamper-proof effect. Aim.
- an encapsulated lens type retroreflective sheet using a small glass sphere provided with a specular reflection layer and a capsule lens type retroreflective sheet are well known.
- WO WO 1/02883 by Bacon can be peeled off by incorporating an organofunctional coupling agent into the adhesive layer in contact with the specular reflection layer in the retroreflective sheeting It is stated that a new and novel retroreflective sheet will be provided.
- the specular reflection layer remains on the side of the fine glass spheres and the retroreflective performance of the sheet is maintained, so a new adhesive layer must be laminated. It is not preferable from the viewpoint of falsification prevention and replay because it can be used again.
- Adhesion-promoting layer Z-reflective layer At least partly bonded adhesive of embossed layer / protective layer composite
- the bonding between the reflective layer and the adhesion promoting layer, and the bonding between the adhesion promoting layer and the adhesive are stronger than the bonding between the reflective layer and the embossing layer, respectively, and furthermore, the bonding with the adhesive
- the bonding with the accelerating layer is A security laminate that is stronger than bonding is disclosed.
- the security layer is broken by partially installing the reflection layer, the adhesive layer, and the adhesion promoting layer provided in the hologram, and the effect of preventing tampering is exhibited.
- the security layer is broken by partially installing the reflection layer, the adhesive layer, and the adhesion promoting layer provided in the hologram, and the effect of preventing tampering is exhibited.
- the various types of authentication stickers that use the above-mentioned retroreflective sheets have excellent visibility at night, and their use as reflective stickers to be attached to vehicles is increasing.
- a sticker called a third plate has the same number as the vehicle number on the number plate, and is installed outside the vehicle by attaching this third plate to a window in the company. It helps to prevent theft of a number plate.
- retroreflective sheets are also increasing in so-called validation stickers, which are used as certificate plates and are attached to vehicle tax delivery certificate stickers that are attached to the windows inside the vehicle.
- the retroreflective sheeting has a very complicated configuration. They are often used for authentication stickers, etc., because they are difficult to obtain or counterfeit.
- the present invention while utilizing the excellent characteristics of the above-mentioned retroreflective sheeting, it is clearly recognizable that when the authentication sticker that has been adhered is peeled off, it is clearly peeled off. It is an object of the present invention to provide a retroreflective sheet having such a falsification preventing effect or a re-peeling preventing effect.
- the tampering prevention layer is installed.
- the problem that the action of the tamper-proof layer is reduced over a long period of use is likely to occur.
- An object of the present invention is to provide a tampering prevention sticker that can withstand such long-term use at high temperatures and maintain a stable tampering prevention effect.
- a surface layer, a binder layer, a fine glass sphere, a focusing layer, a specular reflection layer, and an adhesive are provided in order from the surface layer of the sheet.
- An example is a retroreflective sheet made of an agent layer.
- the adhesive layer can also be placed on the surface layer in applications where it is internally bonded to the surface of glass or the like.
- Examples of the structure of the capsule lens type retroreflective sheet that can be used in the present invention include a surface layer, an air layer, a fine glass sphere, a specular reflection layer, and a binder layer in order from the surface layer of the sheet.
- An example is a retroreflective sheet comprising a support layer and an adhesive layer.
- the surface layer and the binder layer are partially joined so that an air layer is formed to form a hermetically sealed structure.
- the adhesive layer can be placed on the surface layer for applications where the adhesive is to be adhered to the inside of glass or other surfaces.
- an embodiment without an adhesive layer is preferable.
- an adhesive layer can be provided according to the use.
- resins that can be used in the surface layer, support layer, and binder layer of the above-mentioned retroreflective sheet that can be used in the present invention include acryl resin, methacryl resin, and the like. Examples include, but are not limited to, alkyd resins, polyester resins, polyurethane resins, epoxy resins, polystyrene resins, vinyl chloride resins and butyl ether resins. Absent. Of these, acrylic resin is particularly preferred.
- resins that can be used in the adhesive layer of the above-mentioned retroreflective sheet that can be used in the present invention include acryl resin, metal acrylate resin, resin, alkyd resin, and poly resin.
- examples include, but are not limited to, ester resins, polyurethane resins, epoxy resins, silicone resins, natural rubber, synthetic rubber, and butyl ether resins. Of these, acrylic resin is particularly preferred.
- specular reflection layer examples include aluminum, silver, nickel, and copper, but are not limited thereto. It is not something to be done. Of these, aluminum is particularly suitable for its bright appearance. I like it.
- the retroreflective sheet provided with the rupture layer is a retroreflective sheet comprising at least a surface layer, a retroreflective element layer and an adhesive layer, and a layer constituting the retroreflective sheet. At least one layer of the blasting layer is installed between them, and the resin constituting the layer of blasting is
- the position where the rupture layer is provided is not particularly limited.
- the rupture layer and the rupture layer are in close contact with each other. It must be installed so that it can be peeled off at the interface with the layer or by the breaking of the breaking layer.
- the structure in which the destruction layer is axed between the microscopic glass sphere and the specular reflection layer has improved retroreflective performance after peeling. It is particularly preferred in the sense of falsification prevention and reputation because it can be eliminated.
- the layers constituting the sheet and the destruction layer may be the same. ⁇ If the retroreflective sheet is adhered to the substrate and then separated from the substrate, the destruction layer and the destruction layer It is only required that the layer be formed so as to be peeled off at the interface between the layer and the layer that is in close contact with the layer or by the destruction of the breakage layer.
- the printing layer may be provided with the performance of the crush layer in the present patent, and may be partially or entirely provided on the upper surface or the lower surface of the protective layer as necessary.
- a part of the print layer of several colors is used as a destruction layer. May be used.
- Such a structure in which the printed layer is used as a destructive layer is preferable because the presence or absence of peeling can be easily visually determined.
- the thickness of the rupture layer to be installed can be determined as appropriate depending on the installation position, but for example, 0.1 to 100 ⁇ is preferred. In the case of a reflection sheet in which the form of rupture is peeling at the interface between the rupture layer and the layer that adheres to the rupture layer, it is not necessary to particularly increase the thickness, and the thickness is 0.1 to 10 ⁇ m. Is more preferable, and particularly preferably 0.1 to 5 ⁇ . In the case of a reflection sheet such as peeling due to the destruction of the rupture layer, 1 to ⁇ 0 ⁇ is more preferable, and 5 to 5 ⁇ is particularly preferable.
- the thickness is less than 0.1 ⁇ m, it will not function sufficiently as a ruptured layer, resulting in incomplete peeling. If the thickness exceeds ⁇ ⁇ ⁇ , This is inconvenient because breakage occurs in the fracture layer before bonding, and deformation tends to occur in the broken layer during transportation or storage.
- a coating method, a printing method, a laminating method, a spraying method, or the like can be appropriately searched.
- the resin that can be used for the fracture layer is an alicyclic polyolefin resin or an alicyclic acryl resin, and it is necessary to appropriately select a resin according to the form of fracture.
- the resins constituting the destruction layer include cyclopentane-based resin (the following formula 1a), bicyclopentane-based resin (the following formula 1b), and cyclopentanorbornene-based resin (the following formula). 1c), and as the bicyclopentane-based resin, Pentane-based resin (formula 2a below), biennik-type pentanorpolpolene-based resin (formula 2b below), or cyclohexadiene resin (formula 3a) or cyclohexane-based resin (formula 3a) Equation 3b) below,
- the alicyclic acrylic resin that constitutes the fracture layer is a methacrylate resin (formula 4 below).
- cyclopentane-based resin (the above formula la) is used to convert cycloolefins such as norbornene, dicyclopentagen, and tetracyclododecene into transition metal compounds such as tungsten and molybdenum, and alkyl aluminum. It is obtained by saturating a double bond by hydrogenation of an intermediate polymer obtained by ring-opening polymerization using a metathesis catalyst consisting of As a commercially available product, ZEONEX manufactured by Nippon Zeon Co., Ltd. can be used.
- the substituent R1 of the above-mentioned neck-open pentane resin (the above formula la) is a hydrogen atom or a mouth-hexyl group.
- the crystallinity tends to increase and the transparency tends to decrease.
- the substituent R1 is a hydrogen or cyclohexyl group, it is particularly preferable to use it in the fracture layer of the present invention because it becomes an amorphous polymer and the transparency is improved.
- the bicyclopentane-based resin (formula 2a) and the bicyclopentanorbornene-based resin (formula 2b) are used to form a metal acrylate group obtained by norpolene and methyl methacrylate. Is obtained by ring-opening polymerization of a norbornane derivative having a side chain with a catalyst combining a tungsten-aluminum compound and saturating the butyl group by hydrogenation of an intermediate compound. . Since such a compound has an ester group structure, it tends to have relatively high adhesion to other resin layers and a specular reflection layer constituting a retroreflective sheet. Arton (ARTON) manufactured by JSR Corporation can be used as a commercially available product.
- Substituents R2, R3 of the Bierushiku Ropenta emissions based resin (above formula 2a) ⁇ Pi Byurushi click Ropenta norbornene ⁇ (above formula 2b) are hydrogen (- H), main Chinore group (one CH 3), Shiano group ( - CN), main Chinorekaruboki sheet rate group (- COOCH 3), Echinore force Norebokishire preparative group (- COOC 2 H 5), Kishinore force Norebokishire preparative group to consequent b (-COO (cC 6 H 5) ), n - Bed chill carboxymethyl rate group (- COO (n- C 4 H 9)) which the optical properties it is transparency and refractive index using, particularly preferred arbitrariness in terms of heat resistance.
- the hexakis-hexa resin (formulas 3a and 3b above) is a poly-1,3-cyclohexadiene resin, and a polykis-hexane resin.
- These cyclohexadiene-based polymers can be obtained by subjecting 1,3-cyclohexadiene to living-ayon polymerization using a catalyst composed of alkyllithium and an amide compound.
- poly 1,3-cyclohexadiene resin is particularly preferred in terms of heat resistance.
- the alicyclic acrylate resin is preferably a methacrylate ester polymer (formula 4 above), particularly a copolymer of tricyclodecyl methacrylate and methyl methacrylate.
- a methacrylate ester polymer for this product, Hitachi Chemical Co., Ltd. Optlet OZ-1000 can be used.
- benzyl methacrylate having high heat resistance and a copolymer of tricyclode-ermeta acrylate and methyl methacrylate can also be used.
- the appropriate molecular weight is in the range of 1,000 to 100,000, preferably 5,000 to 50,000 in terms of styrene, and is appropriately adjusted depending on the molecular structure and polymerization method. There must be.
- the cohesive force can be reduced by adding another resin to the resin constituting the above-mentioned fracture layer.
- additive resins that can be used include various cellulose compounds, for example, cellulose acetate butyrate, and various waxes, for example, aliphatic hydrocarbons, fatty acid esters, saturated aliphatic acids, and saturated fatty acids.
- examples include alcohols and metal stones, and examples of aliphatic hydrocarbons include polyethylene waxes, polypropylene waxes, and microcrocs.
- Stalin Wax, No examples include raffin wax and fishtrope wax.
- fatty acid ester-based compounds include sasol wax, monate ester, carnauba wax, and rice.
- Wax, honey and cande examples of saturated aliphatic acids include stearic acid and montanic acid.
- saturated alcohols include stearic alcohol and base alcohol.
- the metal stone include calcium stearate and zinc stearate, and the amount of these waxes added:! To 100 parts by weight. Can be added within the range.
- a light-transmissive organic or inorganic filler can be preferably added to the above-mentioned resins.
- Glass powder, silicon dioxide, titanium oxide, aluminum hydroxide, magnesium hydroxide can be used as an inorganic filler, and acrylic resin can be used as an organic filler. Examples include powder.
- the preferred size of the filler particles is 0.1 to 5 ⁇ , and the added amount is preferably 1 to 100 parts by weight.
- a silicon resin, a fluorine resin or the like is used.
- a silicon resin, a fluorine resin or the like is used.
- Each of them can be used alone or in combination with a resin that can be used in the above-mentioned rupture layer.
- an ultraviolet absorber an antioxidant, and a light stabilizer to the fracture layer in order to impart durability and weather resistance.
- UV absorbers examples include benzophenone UV absorbers, salicylate UV absorbers, and benzotriazole UV absorbers.
- antioxidants examples include phosphorus antioxidants, zeolite antioxidants, and phenolic antioxidants.
- light stabilizers examples include hindered amine light stabilizers.
- the retroreflective sheet provided with the rupture layer in the present invention is a retroreflective sheet comprising a surface layer and a retroreflective element layer, and at least one layer is provided between the layers constituting the retroreflective sheet.
- a rupture layer is provided, and the resin constituting the rupture layer is an alicyclic polyolefin resin or an alicyclic acryl resin, and the rupture layer is further bonded to the retroreflective sheet.
- the peel strength between the destruction layer provided using the above-mentioned resin and another layer in contact with the destruction layer is lower than the peel strength between the other layers constituting the sheet. It must be designed to be
- an adhesive that bonds to the substrate is designed so that the peel strength is low, and the peel strength is, for example, 5 to 20 N / 25 mm for an aluminum base material.
- the alicyclic side chain or main chain structure constituting the resin is different from that of the other layers. It is possible to reduce the peel strength between the resin constituting the metal and the metal layer used for the specular reflection layer.
- the peel strength of the destructive layer in the present invention is preferably designed to be 0.1 to 15 N / 25 mm.
- the breakage layer will tend to break before bonding to the substrate, or will tend to deform during transport or storage. I don't like it.
- peel strength is more than 15 N / 25 mm, peeling in the destructive layer is less likely to occur, and the effect of preventing tampering is reduced.
- the glass transition point (T g) of the rupture layer provided on the retroreflective sheet may be 90 to 190 ° C. in consideration of the ultimate temperature of the environment where the sheet is used. Especially preferred. If the glass transition point is lower than 90 ° C, the resin used for the destruction i in the use environment undergoes glass transition, increasing the adhesion strength to other layers in contact with the transition layer, or causing the fracture layer itself to fail. It is not preferable because it causes problems such as thermal deformation. In addition, in the case of a resin whose glass transition point exceeds 190 ° C, the resin structure becomes complicated, and the solubility of the solvent when the destruction layer is installed is lowered, which is not preferable. In addition, the total light transmittance of the rupture layer provided on the retroreflective sheet in the present invention is preferably 75 to 99%. If the total light transmittance is less than 75%, the retroreflection efficiency decreases, which is not preferable.
- the resin constituting the destructive layer installed on the retroreflective sheet in the present invention is an alicyclic polyolefin resin or an alicyclic acrylic resin
- the resin has an alicyclic structure, and therefore, has an all-ray structure. It is easy to obtain a highly transparent resin with a transmittance exceeding 75%.
- the alicyclic polyolefin resin or alicyclic acryl resin which is a resin constituting the destructive layer in the present invention, is generally used for optical applications, and is not tampered with in the present invention. Especially preferred for retroreflective sheets used for prevention authentication stickers.
- the retroreflective sheet provided with the destructive layer in the present invention constitutes the retroreflective sheet in at least a retroreflective sheet comprising a surface layer, a retroreflective element layer and an adhesive layer. At least one destruction layer is provided between the layers, and the resin constituting the destruction layer is an alicyclic polyolefin resin or an alicyclic acryl resin.
- the reflection sheet is peeled off after being adhered to the substrate, the reflection sheet is peeled off at an interface between the destruction layer and a layer in contact with the destruction layer, or is peeled off due to rupture of the destruction layer. are doing.
- the peel strength of the fracture layer in the present invention is designed to be 0.1 to 15 N 25 mm, it is designed that the above-mentioned peeling action occurs in a most preferable form. I have.
- FIG. 1 is a cross-sectional view showing an example of the structure of a conventionally known sealed lens type retroreflective sheet.
- FIG. 2 is a cross-sectional view showing another example of the structure of a conventionally known sealed lens type retroreflective sheet.
- FIG. 3 is a cross-sectional view of a preferred embodiment of a sealed lens type retroreflective sheet without an adhesive layer provided with a breaking layer according to the present invention.
- FIG. 4 is a cross-sectional view of a preferred embodiment of an encapsulated lens type retroreflective sheet provided with a breaking layer according to the present invention.
- FIG. 5 is a cross-sectional view of another preferred embodiment of an encapsulated lens type retroreflective sheet provided with a breaking layer according to the present invention.
- FIG. 6 is a cross-sectional view of another preferred embodiment of an encapsulated lens type retroreflective sheet provided with a breaking layer according to the present invention.
- FIG. 7 is a cross-sectional view of another preferred embodiment of an encapsulated lens type retroreflective sheet provided with a breaking layer according to the present invention.
- FIG. 8 is a cross-sectional view of a preferred embodiment of a capsule lens type retroreflective sheet provided with a destruction layer according to the present invention.
- FIG. 1 shows an example of the structure of a conventionally known encapsulated lens type retroreflective sheet used for comparison with the present invention.
- a surface layer (1) a printing layer (2) placed below the surface layer, and a holding layer (3) that holds a large number of small glass spheres ( 4 ).
- a recursive system consisting of a focus adjustment layer (5) and a specular reflection layer (6) for specularly reflecting light
- the reflective element layers (3 to 6) are adhered by an adhesive layer (7) provided on the back surface of the specular reflection layer (6).
- FIG. 2 shows another example of the structure of a conventionally known encapsulated lens type retroreflective sheet used for comparison with the present invention.
- the retroreflective sheet is attached to a light-transmitting substrate by a light-transmitting adhesive layer (9) provided on the surface.
- FIG. 3 shows a preferred embodiment of an encapsulated lens type retroreflective sheeting without an adhesive layer provided with a breaking layer according to the present invention.
- the light-transmitting rupture layer (11) is located between the focusing layer (.5) and the specular reflection layer (6), as shown in Fig. 4.
- the retroreflective sheet is further provided with an adhesive layer, which is adhered to the base material (8) via the adhesive layer (7) provided on the back surface. As a result, the microscopic glass sphere and the specular reflection layer are separated, and the retroreflective performance is lost.
- FIG. 4 shows an embodiment in which the adhesive layer is provided in the embodiment of FIG. 3, so that the light-transmitting destruction layer (11) is provided between the focus adjustment layer (5) and the specular reflection layer (6).
- the sheet is adhered to the base material (8) via an adhesive layer (7) provided on the back surface. When the sheet is detached, detachment occurs in the destructive layer, and the glass microspheres and mirror reflection are caused. The layers are separated and lose retroreflective performance.
- FIG. 5 shows another preferred embodiment of an encapsulated lens type retroreflective sheeting provided with a breaking layer according to the present invention.
- the light-transmitting rupture layer (11) is provided between the focusing layer (5) and the specular reflection layer (6), and the adhesive layer (9) provided on the surface is provided.
- peeling occurs in the destruction layer (11), and the microscopic glass spheres and the specular reflection layer are separated, and the retroreflection performance is improved. lose.
- FIG. 6 shows another preferred embodiment of an encapsulated lens type retroreflective sheet provided with a breaking layer according to the present invention.
- the light-transmitting destructive layer (11) is provided between the adhesive layer (7) and the specular reflection layer (6), and the base material is provided via the adhesive layer (7) provided on the back surface. It is attached to (8), and when this sheet is peeled, peeling occurs in the destruction layer (11). At that time, the specular reflection layer (6) is partially torn off by the destruction layer (11), so that the retroreflection performance is remarkably reduced and the mirror reflection layer (6) is not practical.
- FIG. 7 shows another preferred embodiment of an encapsulated lens type retroreflective sheet provided with a breaking layer according to the present invention.
- the retroreflective sheet according to the present invention includes a surface layer (1), a destruction layer (11) provided on the surface layer, and a holding layer (3) holding a large number of microscopic glass spheres ( 4 ).
- the retroreflective element layers (3 to 6), which consist of a focus adjustment layer (5) and a specular reflection layer (6) for reflecting light specularly, are provided with an adhesive to efficiently and retroreflect incident light. It is adhered to the back surface protective layer (10) which protects the specular reflection layer by the layer (7).
- the surface layer (1) is adhered to the transparent substrate (8) by an adhesive layer (9).
- the destruction layer (11) is provided by printing.
- the peel strength is designed to be smaller than the peel strength of the adhesive layer (9), so that when the sheet is peeled off, the rupture layer (11) will break Or, it is designed to be separated at the interface, and is designed so that a trace of the separation is clearly left.
- FIG. 8 shows another preferred embodiment of a capsule lens type retroreflective sheeting provided with a breaking layer according to the present invention.
- the base material (27) to be attached is shown.
- the binder layer (24) is designed so that the peel strength is lower than that of the adhesive layer (26), and the retroreflective sheet attached to the base material is peeled off. When it is made to act, it acts as a destructive layer and peels off in the binder layer, losing its function as a retroreflective sheet.
- the retroreflective sheet of the present invention was evaluated by the following test methods. 1) Peel strength
- the peeled part and the peeled state of the test piece were visually observed, and the appearance was evaluated according to the following criteria.
- test pieces before and after the peel test were applied to a 100 mm x 100 mm test piece using Advanced Retro 'Technology Co., Ltd.
- the retroreflective performance was measured from the material side surface. The measurement was performed at an observation angle of 0 in accordance with JIS-9-111.
- the measurement was performed five times under the conditions of 2 ° and an incident angle of 5 °, and the average value was used as the retroreflective performance.
- test piece adhered to the aluminum plate used for the peel test was subjected to heat treatment in a hot air drier controlled at 80 ° C for 20 days.
- Et al is, 1 0 wt manufactured by JSR Corporation on the focusing layer alicyclic poly olefin emission resin (trade name ARTON D4532) 0 /.
- the toluene solution was mixed and stirred, and the mixture was dried by drying, and a destruction layer having an average thickness of 0.5 ⁇ was provided.
- This destruction layer is coated with aluminum with a purity of 99.9% or more.
- An intermediate product 1 was prepared by installing a specular reflection layer with a thickness of 0.1 ⁇ by the empty deposition method.
- a release paper made by Lintec Co., Ltd. (trade name ⁇ 2 ⁇ — L — ⁇ ⁇ ( ⁇ )) was added to an acrylic adhesive (trade name ⁇ ⁇ — 18 18) made by Nippon Carbide Industry Co., Ltd. ) 80 parts by weight of Acryl-based adhesive (KP — 1656) manufactured by Nippon Carbide Co., Ltd. and 20 parts by weight of chelate-based cross-linking agent manufactured by Japan Carbide Co., Ltd. 0 1) A mixture obtained by stirring and mixing 0.76 parts by weight was applied and dried, and an adhesive layer having a thickness of 40 ⁇ was provided to prepare an adhesive sheet 1.
- the adhesive sheet 1 and the aluminum-deposited surface of the intermediate product 1 were bonded together to obtain a retroreflective sheet 1 of the present invention.
- the prepared retroreflective sheet 1 was adhered to a 2 mm-thick aluminum plate for performance measurement to obtain a test piece 1 for a peeling test.
- the adhesive sheet 1 created in Example 1 was bonded to the surface of the surface layer of the intermediate product 1 created in Example 1.
- a 38 ⁇ thick polytetrafluoroethylene sheet was used on the specular reflection layer, and a 40 ⁇ thick acrylic adhesive was used to create adhesive sheet 1.
- the retroreflective sheet 2 of the present invention was prepared.
- the prepared retroreflective sheet 2 was adhered to a performance measurement acryl plate with a thickness of 2 mm, and a test specimen 2 for a peeling test adhered so as to transmit through the acrylic plate and reflect retroreflectively.
- Example 2 the resin used for the fracture layer was A retroreflective sheet 3 was obtained by the same method except that a norbornene-based resin (trade name: ZE0NEX480) was used.
- the prepared retroreflective sheet 3 was attached to a 2 mm-thick aluminum plate for performance measurement to obtain a test piece 3 for a peeling test.
- Example 2 a retroreflective sheet 4 was obtained by the same method except that the resin used for the destruction layer was an alicyclic acrylic resin (trade name Optlet OZ1000) manufactured by Hitachi Chemical Co., Ltd.
- the prepared retroreflective sheet 4 was attached to a 2 mm-thick aluminum plate for performance measurement to obtain a test piece 4 for a peeling test.
- a retroreflective sheet 5 of the present invention was obtained in the same manner as in Example 1, except that the destruction layer was provided on the back surface of the surface layer instead of being provided between the focus adjustment layer and the specular reflection layer.
- the prepared retroreflective sheet 5 was adhered to a 2 mm-thick aluminum plate for performance measurement to obtain a test piece 5 for a peeling test.
- a retroreflective sheet 6 of the present invention was obtained in the same manner as in Example 2, except that the destruction layer was provided on the back surface of the surface layer instead of being provided between the focusing layer and the specular reflection layer.
- the prepared retroreflective sheet 6 is adhered to a performance measurement acrylic plate with a thickness of 2 mm, and a test for a peeling test is applied so that it passes through the acrylic plate and is retroreflected. Piece 6 was selected.
- Capsule Lens type retroreflective sheet (trade name: Nitsuka Light ULSF 812) A mixture of 15% by weight of toluene solution of alicyclic polyolefin resin (trade name: ARTON D4532) manufactured by the company was mixed and stirred, and a dot with a diameter of 5 mm and a spacing of 2 cm was screened with a screen. Was printed in a grid pattern and dried, and a breaking layer having an average thickness of 2 ⁇ was provided.
- a red ink of Tokushiki Co., Ltd. (trade name: 5-315) was printed on the crushed layer by a screen with letters A BC of 10 cm in height.
- a release paper made by Lintec Co., Ltd. (trade name: E 2 P — L — PE (P)) is applied to an acrylic adhesive (trade name: KP — 18 18) 8 0 parts by weight of an acrylic adhesive (KP-16656) manufactured by Nippon Carpaidoe Co., Ltd. 20 parts by weight and a chelating cross-linking agent (product name: CK-4 0 1)
- a mixture obtained by stirring and mixing 0.76 parts by weight was applied and dried, and an adhesive layer having a thickness of 40 ⁇ was provided to prepare an adhesive sheet 1.
- Adhesive sheet 1 was adhered on the red print layer to obtain retroreflective sheet 7 of the present invention.
- the prepared retroreflective sheet 7 is adhered to a 2 mm thick acrylic plate for performance measurement, and a test specimen 7 for a peeling test is adhered so that it passes through the acrylic plate and retroreflects.
- a retroreflective sheet C1 of the present invention was produced in the same manner as in Example 1 except that no destruction layer was provided.
- the prepared retroreflective sheet C1 was adhered to a performance measuring aluminum plate having a thickness of 2 mm to obtain a test piece C1 for a peeling test.
- Reflection sheet C2 was prepared.
- the prepared retroreflective sheet C2 is attached to a performance measuring acrylic plate with a thickness of 2mm, and a peeling test is applied so that it passes through the acrylic plate and is retroreflected.
- Piece C 2 was used. Comparative Example 3
- a 38 ⁇ thick transparent polyethylene terephthalate film (trade name SEW-38) manufactured by Teijin Limited is coated on the surface layer of Dainippon Inki Chemical Industry Co., Ltd. VC Medium S) 100 parts by weight of a coloring agent made by mixing the above-mentioned VC Medium S with carbon black (manufactured by Dainippon Ink Chemical Industry Co., Ltd. (product name: VC Black) 6.5 parts by weight)
- a printing ink with mixed parts a trademark ink with a diameter of 7 mm was printed by Daravia and then dried to form a printing layer with a thickness of about 1 ⁇ .
- an acrylic resin solution (trade name: RS-50000) manufactured by Nippon Carpa-Dye Industry Co., Ltd.
- a resin solution obtained by mixing and mixing 5.5 parts by weight of a crosslinking agent (trade name: MS-11) was applied and dried, and a focusing layer having an average thickness of 14 ⁇ was provided.
- 100 parts by weight of an acrylic resin solution (trade name: RS-100) manufactured by Nippon Carbide Dyeing Co., Ltd. is added to a CAB solution (trade name by Eastman Chemical Company).
- a mixture of 108 parts by weight of a butyl acetate solution having a solid content of CAB of 20% by weight) was mixed and stirred, and the mixture was dried by coating to form a fracture layer having an average thickness of 0.5 ⁇ .
- An intermediate product C 3 was prepared by installing a mirror reflection layer having a thickness of 0.1 ⁇ on the surface of this destruction layer with aluminum having a purity of 99.9% or more by vacuum evaporation.
- the adhesive sheet 1 prepared in Example 1 was bonded to the aluminum-deposited surface of the intermediate product C 3 to obtain a retroreflective sheet C 3.
- the created retroreflective sheet C3 was adhered to a 2 mm-thick aluminum plate for performance measurement to obtain a test piece C3 for a peeling test.
- the prepared retroreflective sheet C3 was adhered to a 2 mm-thick aluminum plate for performance measurement to obtain a test piece C3 for a peeling test.
- Table 1 shows the results of performance tests of the test pieces prepared in the above Examples and Comparative Examples.
- the present invention relates to a retroreflective sheet provided with a useful debris layer in a reflector plate of infrared light reflective sensors.
- the retroreflective sheet used for various authentication stickers, etc. once the retroreflective sheet pasted once was peeled off and tried to be used for another purpose, it was destroyed in part of the retroreflective sheet. Since the layer is provided, the retroreflective sheet can be broken and cannot be diverted, and it can withstand long-term use at high temperatures and have a stable tamper-proof effect. A retroreflective sheeting with a broken layer can be used for a tamper-proof sticker that can be maintained.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Elements Other Than Lenses (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Road Signs Or Road Markings (AREA)
- Adhesive Tapes (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE602004005351T DE602004005351T2 (de) | 2003-08-29 | 2004-08-30 | Retroreflexions-blatt mit einer zerbrechbaren schicht |
US10/569,869 US20080198461A1 (en) | 2003-08-29 | 2004-08-30 | Retroreflective Sheeting Provided With Destructive Layer |
EP04772821A EP1666925B1 (en) | 2003-08-29 | 2004-08-30 | Retroreflection sheet provided with breakable layer |
JP2005513559A JP4846365B2 (ja) | 2003-08-29 | 2004-08-30 | 破壊層の設置された再帰反射シート |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003-209580 | 2003-08-29 | ||
JP2003209580 | 2003-08-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005022211A1 true WO2005022211A1 (ja) | 2005-03-10 |
WO2005022211A8 WO2005022211A8 (ja) | 2005-06-16 |
Family
ID=34263968
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/012872 WO2005022211A1 (ja) | 2003-08-29 | 2004-08-30 | 破壊層の設置された再帰反射シート |
Country Status (7)
Country | Link |
---|---|
US (1) | US20080198461A1 (ja) |
EP (1) | EP1666925B1 (ja) |
JP (1) | JP4846365B2 (ja) |
CN (1) | CN100458473C (ja) |
AT (1) | ATE357004T1 (ja) |
DE (1) | DE602004005351T2 (ja) |
WO (1) | WO2005022211A1 (ja) |
Cited By (4)
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JP2006349842A (ja) * | 2005-06-14 | 2006-12-28 | Nippon Carbide Ind Co Inc | 再帰反射シート |
JP2008033002A (ja) * | 2006-07-28 | 2008-02-14 | Nippon Carbide Ind Co Inc | 再帰反射シート |
WO2010014929A2 (en) * | 2008-08-01 | 2010-02-04 | Bates Aaron P | Process for forming a reflective surface |
JP2012098568A (ja) * | 2010-11-04 | 2012-05-24 | Kyodo Printing Co Ltd | 偽造防止シール |
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WO2005083661A1 (ja) * | 2004-02-27 | 2005-09-09 | Nippon Carbide Kogyo Kabushiki Kaisha | 盗難防止構造を具備した表示装置 |
JPWO2006085690A1 (ja) * | 2005-02-10 | 2008-06-26 | 日本カーバイド工業株式会社 | 再帰反射シート |
US8758644B2 (en) | 2007-04-10 | 2014-06-24 | Valspar Sourcing, Inc. | Oxygen-scavenging materials and articles formed therefrom |
US8308976B2 (en) | 2008-10-10 | 2012-11-13 | Valspar Sourcing, Inc. | Oxygen-scavenging materials and articles formed therefrom |
WO2010042122A1 (en) | 2008-10-10 | 2010-04-15 | Valspar Sourcing, Inc. | Oxygen-scavenging composition and article formed therefrom |
US20120043749A1 (en) * | 2010-08-23 | 2012-02-23 | Watson Gullett | Business form with label |
US20140160540A1 (en) * | 2011-04-01 | 2014-06-12 | Nhk Spring Co., Ltd. | Identification medium |
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US10232593B2 (en) | 2013-03-13 | 2019-03-19 | The Sherwin-Williams Company | Oxygen-scavenging composition and articles thereof |
CN112534184A (zh) | 2018-07-24 | 2021-03-19 | 3M创新有限公司 | 图案化波长选择性图像 |
EP3827290A4 (en) | 2018-07-24 | 2022-04-27 | 3M Innovative Properties Company | PATTERNED WAVELENGTH SELECTIVE FOIL |
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Also Published As
Publication number | Publication date |
---|---|
CN1842729A (zh) | 2006-10-04 |
EP1666925A4 (en) | 2006-09-27 |
DE602004005351T2 (de) | 2007-11-29 |
ATE357004T1 (de) | 2007-04-15 |
CN100458473C (zh) | 2009-02-04 |
US20080198461A1 (en) | 2008-08-21 |
WO2005022211A8 (ja) | 2005-06-16 |
JP4846365B2 (ja) | 2011-12-28 |
DE602004005351D1 (de) | 2007-04-26 |
JPWO2005022211A1 (ja) | 2006-10-26 |
EP1666925B1 (en) | 2007-03-14 |
EP1666925A1 (en) | 2006-06-07 |
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