JP6419613B2 - Anti-reuse adhesive sheet - Google Patents

Description

  The present invention relates to a reuse prevention pressure-sensitive adhesive sheet.

  A dedicated label may be attached to a package of expensive electronic equipment, music software, computer software, or the like in order to ensure that it is a genuine product. However, since there is a counterfeit means such as peeling off the label from the regular product and replacing it with a counterfeit product, a label or sheet for preventing reuse is used for the purpose of preventing it.

Examples of such reuse prevention labels or sheets include those disclosed in Patent Documents 1 to 3.
Patent Document 1 discloses a tamper-proof label or sheet obtained by applying information to a surface and coating the information with a transparent protective layer, at least a transparent base material that cuts off ultraviolet rays, and a color former that develops color by ultraviolet rays. An anti-tamper label or sheet having a configuration including an adhesive layer in which is dispersed is disclosed.
Patent Document 2 includes at least an oxygen barrier film layer having transparency, a printing ink layer whose color tone changes depending on the presence or absence of oxygen, an oxygen absorption layer, an oxygen barrier layer, and an end face of a laminate in which an adhesive layer is sequentially laminated. An anti-tamper label characterized by being sealed is disclosed.
Patent Document 3 includes a polystyrene film having a thickness of 10 μm or more and 40 μm or less, and a heat-resistant pressure-sensitive adhesive layer having an adhesive strength defined by JIS Z 0237 of 15 N / 25 mm or more at 80 ° C. laminated on one surface thereof. A tamper-proof label or sheet is disclosed.

JP-A-9-277423 JP 2008-52013 A JP 2010-281948 A

However, the tamper-proof label or sheet described in Patent Document 1 does not have the effect of preventing reuse when it is opened in a place where ultraviolet rays do not exist.
Further, the tamper-proof label described in Patent Document 2 identifies whether or not the printing ink layer has been opened due to a change in color tone caused by a chemical reaction due to the presence or absence of oxygen. Since it is used, there is a disadvantage that the cost becomes high.
And although the tamper-proof label or sheet described in Patent Document 3 can prevent the label from being misused as a display of counterfeit goods, the base material used is limited to polystyrene.

  The present invention has been made in view of such circumstances, and it does not require ultraviolet light or special printing ink, and even if it is peeled off, the fact that it has been peeled off can be easily found. An object of the present invention is to provide an anti-reuse pressure-sensitive adhesive sheet that can prevent the disappearance of the material.

As a result of intensive studies, the present inventors have found that the above-described problems can be solved when the easily breakable layer constituting the reuse-reducing pressure-sensitive adhesive sheet contains a resin component having a specific glass transition point.
That is, the present invention provides the following [1] to [7].
[1] An easily breakable layer (B1) and a printed layer (C1) are laminated in this order on one surface of the substrate (A1), and further on the other surface of the substrate (A1) or the printed layer. A laminate (I) provided with a pressure-sensitive adhesive layer (D1) on the surface of (C1), and a protective sheet (II) having a transparent substrate (A2) and a pressure-sensitive adhesive layer (D2),
The pressure-sensitive adhesive layer (D2) of the protective sheet (II) is a re-use prevention pressure-sensitive adhesive sheet having a configuration laminated on the surface opposite to the pressure-sensitive adhesive layer (D1) of the laminate (I),
The reuse preventive pressure-sensitive adhesive sheet, wherein the easily breakable layer (B1) contains the resin component (b), and the glass transition point of the resin component (b) is 200 ° C or higher.
[2] The pressure-sensitive adhesive layer (D1) is provided on the surface of the substrate (A1) of the laminate (I), and the adhesive of the protective sheet (II) is provided on the surface of the printed layer (C1) of the laminate (I). The reuse prevention pressure-sensitive adhesive sheet according to [1] above, wherein the agent layer (D2) has a laminated structure.
[3] The adhesive layer (D1) is provided on the printed layer (C1) of the laminate (I), and the adhesive layer of the protective sheet (II) is provided on the surface of the substrate (A1) of the laminate (I). The reuse prevention pressure-sensitive adhesive sheet according to [1] above, wherein (D2) has a laminated structure.
[4] Reuse according to any one of [1] to [3], wherein the printing coat layer (E1) is laminated between the easily breakable layer (B1) and the printing layer (C1). Prevention adhesive sheet.
[5] The reuse prevention pressure-sensitive adhesive sheet according to any one of [1] to [4], wherein the resin component (b) is a polyamideimide resin.
[6] The reuse prevention pressure-sensitive adhesive sheet according to [5], wherein the polyamideimide resin has a number average molecular weight (Mn) of 4,000 to 12,000.
[7] The reuse prevention pressure-sensitive adhesive sheet according to any one of [1] to [6], wherein the easily breakable layer (B1) has a thickness of 100 to 2,500 nm.

  According to the present invention, UV or special printing ink is not required, and even if it is peeled off, the fact that it has been peeled off can be easily found, so that the reuse of the peeled label or sheet can be prevented. It is possible to provide a sheet.

It is sectional drawing which shows the state which attached the one aspect | mode of the reuse prevention adhesive sheet of this invention to the peeling sheet. It is sectional drawing which shows the state which attached the one aspect | mode of the reuse prevention adhesive sheet of this invention to the peeling sheet. When the protective sheet (II) of the reusable prevention adhesive sheet of the present invention shown in FIG. 1 attached to the adherend is removed, the layer from the easily breakable layer (B1) to the printed layer (C1) is broken by zipping. It is a schematic diagram showing the cross section of the state made. When the protective sheet (II) of the adhesive sheet of the present invention shown in FIG. 2 attached to the adherend is peeled off, the layer from the easily breakable layer (B1) to the printed layer (C1) is broken by zipping. It is a schematic diagram showing the cross section of the state made.

[Reuse prevention adhesive sheet]
The reuse prevention pressure-sensitive adhesive sheet of the present invention comprises an easily breakable layer (B1) and a printed layer (C1) laminated in this order on one surface of the substrate (A1), and further the substrate (A1). Laminate (I) provided with an adhesive layer (D1) on the other surface or the surface of the printing layer (C1), and a protective sheet (II) having a transparent substrate (A2) and an adhesive layer (D2) )
The pressure-sensitive adhesive layer (D2) of the protective sheet (II) is a re-use prevention pressure-sensitive adhesive sheet having a configuration laminated on the surface opposite to the pressure-sensitive adhesive layer (D1) of the laminate (I),
The easily destructible layer (B1) contains a resin component (b), and the glass transition point of the resin component (b) is 200 ° C. or higher.

An example of a preferred embodiment of the reuse prevention pressure-sensitive adhesive sheet according to an embodiment of the present invention will be described with reference to FIG. 1 and FIG. 2, but the reuse prevention pressure-sensitive adhesive sheet of the present invention has the following effects. It is not limited to the following examples.
The reuse prevention pressure-sensitive adhesive sheet 10 shown in FIG. 1 includes a base material (A1), an easily breakable layer (B1), and a printing layer (C1) laminated in this order, and further on the surface of the base material (A1). The laminate (I) provided with the pressure-sensitive adhesive layer (D1), and the protective sheet (II) having the transparent substrate (A2) and the pressure-sensitive adhesive layer (D2) are provided. And it is the reuse prevention adhesive sheet 10 which has the structure which the adhesive layer (D2) of protective sheet (II) laminated | stacked on the surface of the printing layer (C1) of laminated body (I). FIG. 1 shows a state in which the reuse prevention pressure-sensitive adhesive sheet 10 is affixed to a release sheet 11.
The reuse prevention pressure-sensitive adhesive sheet 10 shown in FIG. 2 includes a base material (A1), an easily breakable layer (B1), and a printing layer (C1) laminated in this order, and further on the surface of the printing layer (C1). The laminate (I) provided with the pressure-sensitive adhesive layer (D1), and the protective sheet (II) having the transparent substrate (A2) and the pressure-sensitive adhesive layer (D2) are provided. And it is the reuse prevention adhesive sheet 10 which has the structure which the adhesive layer (D2) of protective sheet (II) laminated | stacked on the surface of the base material (A1) of laminated body (I). FIG. 2 shows a state in which the reuse prevention adhesive sheet 10 is affixed to the release sheet 11.

  Hereinafter, each member of the reuse prevention pressure-sensitive adhesive sheet will be described.

<Laminated body (I)>
The layered product (I) possessed by the reuse prevention pressure-sensitive adhesive sheet of the present invention comprises a substrate (A1), an easily breakable layer (B1) and a printed layer (C1) laminated in this order, and further a substrate (A1). Or it is a laminated body (I) which provided the adhesive layer (D1) on either surface of the printing layer (C1).

(Base material (A1))
As a base material (A1) used for the reuse prevention adhesive sheet of this invention, if it is a range which does not impair the effect of this invention, it will not restrict | limit, It is commonly used for the conventional reuse prevention adhesive sheet or a label. Things. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyurethane resins such as polyurethane acrylate, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins Film containing resin such as ethylene-vinyl acetate copolymer, polystyrene resin, polycarbonate resin, acrylic resin, norbornene resin, cycloolefin resin; woven or non-woven fabric using fibers such as rayon, acrylic, polyester, etc. Papers such as fine paper, glassine paper, impregnated paper, coated paper; metal foils such as aluminum and copper; foams such as urethane foam and polyethylene foam; and laminates of two or more of these.
When a film containing a resin is used as the base material (A1), an uneven surface treatment by sandblasting, solvent treatment, or the like is performed for the purpose of improving the adhesiveness with a layer provided on one or both surfaces of the film. Alternatively, oxidation treatment such as corona discharge treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment can be performed.
The thickness of the substrate (A1) is not particularly limited and may be appropriately selected depending on the situation, but is preferably 10 to 300 μm, more preferably 30 to 150 μm.

(Easily destructible layer (B1))
The easily breakable layer (B1) used for the reuse prevention pressure-sensitive adhesive sheet of the present invention is a layer provided between the base material (A1) and the print layer (C1), and is a layer containing a resin component (b). is there.
When the protective sheet (II) is peeled off from the adherend and the laminate (I), the reuse-preventing pressure-sensitive adhesive sheet of the present invention has the easy-to-break layer (B1). The layer composed of (C1) is not peeled off continuously and smoothly, but is peeled off while causing so-called zipping such as intermittent destruction of the layer and formation of peeling stripes at the time of peeling. It has preventive properties.
As an example of the destruction state due to the zipping, a description will be given with reference to FIGS. 3 and 4 show cross sections after the protective sheet (II) of the reuse prevention pressure-sensitive adhesive sheet 10 shown in FIGS. 1 and 2 attached to the adherend 12 is peeled from the laminate (I), respectively. It is a schematic diagram. The state after the protective sheet (II) is peeled from the left side to the right side in FIGS. 3 and 4 or from the right side to the left side is shown. Here, in FIG.3 and FIG.4, when peeling protective sheet | seat (II) from laminated body (I), zipping generate | occur | produced and the printing layer (C1) from the easily breakable layer (B1) of laminated body (I). In the meantime, destruction has occurred. Thus, the destruction by zipping occurs in the part including the easily breakable layer (B1), so that the reuse prevention pressure-sensitive adhesive sheet of the present invention can exhibit sufficient reuse prevention performance.

[Resin component (b)]
The resin component (b) contained in the easily breakable layer (B1) has a glass transition point (hereinafter also simply referred to as “Tg”) of 200 ° C. or higher.
The resin component (b) refers to a polymer having a number average molecular weight (Mn) of 1,000 or more and having a certain repeating unit derived from a monomer used for polymerization.
When the glass transition point of the resin component (b) is less than 200 ° C., the brittleness of the easily breakable layer is insufficient, so that it is sufficient when the protective sheet (II) is peeled off from the adherend and the laminate (I). Zippering does not occur, and the reusability is poor. From the viewpoint of improving the reusability prevention, the glass transition point is preferably 220 ° C. or higher, more preferably 230 ° C. or higher, still more preferably 250 ° C. or higher, and still more preferably 255 ° C. or higher. The upper limit of the glass transition point is not particularly limited, but is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, from the viewpoint of being easily dissolved in a solvent and easy to apply uniformly during production.
The resin component (b) may be a component obtained by mixing one or more resins.
Here, when the resin component (b) is a mixture of two or more resins, the glass transition point is calculated from the glass transition point of each resin and the mixing ratio (mass ratio) of each resin. It is shown as a value expressed as a weighted average. The glass transition point is specifically a value measured by the method described in the examples described later.
The number average molecular weight (Mn) of the resin component (b) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, and still more preferably 3,000 to 100,000. 000, more preferably 4,000 to 50,000.

  The resin used as the raw material of the resin component (b) is not particularly limited as long as the resin component (b) has a glass transition point in the above range. Specifically, for example, polyamideimide resin, polyimide resin, epoxy resin, and the like can be used. Among these, a polyamide-imide resin is preferable because it is easily breakable.

{Polyamideimide resin}
The polyamide-imide resin is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include a polyamide-imide resin using trimellitic acid.
Examples of commercially available products of polyamideimide resin include, for example, Bilomax HR-11N, Bilomax HR-12N2, Bilomax HR-13NX, Bilomax HR-14ET, Bilomax HR-15ET, Bilomax HR-16NN, etc. “Vilomax” (registered trademark, manufactured by Toyobo Co., Ltd.), HPC-1000EDP, HPC-1000, HPC-5000, HPC-5010S, HPC-5020, HPC-5030, HPC-6000, HPC-6100, HPC-7200, Examples thereof include polyamideimide resins (product name, manufactured by Hitachi Chemical Co., Ltd.) such as HPC-9000 and HPC-9100.
The number average molecular weight (Mn) of the polyamideimide resin is preferably 2,000 to 50,000, more preferably 3,000 to 25,000, still more preferably 4,000 to 12,000, and still more preferably. Is 5,000 to 11,000.

The content of the resin component (b) in the easily breakable layer (B1) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably. It is 90-100 mass%.
In addition to the resin component (b), the easily breakable layer (B1) may contain other components such as an antioxidant, a stabilizer, a filler, a pigment, and a dye.

  The method for coating the base material (A1) with the material for forming the easily breakable layer (B1) is not particularly limited, and a conventionally known method such as a gravure method, a bar coating method, a knife coating method, or a roll coating method. A blade coating method, a die coating method, or the like can be used. Moreover, a solvent can be used as needed. The thickness of the easily breakable layer (B1) thus formed is preferably 100 to 2,500 nm, more preferably 250 to 1,500 nm. When the thickness of the easily breakable layer (B1) is 100 nm or more, sufficient breakability can be obtained. On the other hand, when it is 2,500 nm or less, the solvent can be sufficiently removed during coating and drying.

(Print layer (C1))
The printing layer (C1) used for the reuse-preventing pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as the effects of the present invention are not impaired. For example, acrylic resin, polyurethane resin, butyral resin, nitro resin, Inks containing binders such as cellulose resins, acetylcellulose resins, polyester resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, colorants such as pigments and dyes, extender pigments, solvents, etc. Can be formed by a general printing method such as gravure printing, screen printing, offset printing, flexographic printing, and the like.
The thickness of the printed layer (C1) thus formed is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.01 to 50 μm, more preferably 0.1 to 30 μm, More preferably, it is 1-5 micrometers. Sufficient visibility is acquired as the thickness of a printing layer (C1) is 0.01 micrometer or more. On the other hand, when it is 50 μm or less, it can be sufficiently peeled when peeled together with the easily breakable layer.

(Adhesive layer (D1))
The pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer (D1) used in the reuse-resistant pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it does not impair the effects of the present invention. For example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or a silicone-based pressure-sensitive adhesive can be used.

  Examples of the acrylic pressure-sensitive adhesive include, as a main component, an acrylate homopolymer, a copolymer containing two or more acrylate ester units, and a copolymer of an acrylate ester and another functional monomer. Those containing at least one selected from the above (hereinafter also simply referred to as “acrylic polymer”) are used. Examples of the acrylic acid ester include (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, ( Examples include (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, and the like. Examples of the functional monomer include hydroxyl group-containing monomers such as (meth) acrylic acid hydroxyethyl ester and (meth) acrylic acid hydroxypropyl ester; (meth) acrylamide, dimethyl (meth) acrylamide and the like. Amide group-containing monomer; and the like. The acrylic pressure-sensitive adhesive is generally roughly classified into a solvent type and an emulsion type, and the solvent type is usually the acrylic polymer, solvent, cross-linking agent, and tackifier, plasticizer, and antistatic agent that are used as desired. And a UV absorber, etc., and methylol group condensation, ionic crosslinking, urethane crosslinking, epoxy crosslinking and the like are used as the crosslinking system. On the other hand, the emulsion type is usually composed of the acrylic polymer, an emulsifier, an aqueous solvent, a tackifier used as desired, and the like.

Examples of the rubber-based adhesive include, as a main component, natural rubber, polyisoprene rubber, polyisobutylene, polybutadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and the like. Those containing at least one selected (hereinafter also simply referred to as “rubber main component”) are used. The rubber-based pressure-sensitive adhesive can contain a tackifier, a plasticizer, an anti-aging agent, a filler and the like as desired. As the form, a solvent type or an emulsion type using the rubber-based latex is preferably used. Further, as the silicone-based pressure-sensitive adhesive, for example, a solvent-type one containing polydimethylsiloxane or polydiphenylsiloxane as a main component and further containing a tackifier, a plasticizer, a filler or the like as desired is preferable. Used.
Although the thickness of an adhesive layer (D1) will not be restrict | limited especially if it is a range which does not impair the effect of this invention, Preferably it is 5-80 micrometers, More preferably, it is 10-50 micrometers.

(Coat layer for printing (E1))
The laminate (I) of the reuse-preventing pressure-sensitive adhesive sheet according to the present invention has a printing coat layer for imparting printability on the easily breakable layer (B1) surface opposite to the substrate (A1) side ( E1) may be included. The coating layer for printing (E1) prevents the printing portion from coming off due to protrusions (fish eyes) due to undissolved portions of the resin mixed during the formation of the easily breakable layer (B1), and the printing layer ( C1) has the effect of improving the adhesion.
As a material constituting the coating layer for printing (E1) used for the reuse-preventing pressure-sensitive adhesive sheet of the present invention, it has good adhesion to the easily breakable layer (B1) and is formed on the surface of the easily breakable layer (B1). In addition, there is no particular limitation as long as it can conceal protrusions due to undissolved resin and can form a coating layer (E1) for printing with good adhesion to the printing layer (C1), and various types are used. Can do.
Examples of such materials include acrylic resins, styrene resins, cross-linked polyester urethane resins, polyester resins, polyurethane resins, polyol resins, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives, acetate derivatives, polychlorinated resins. An organic binder such as vinyl resin, polyimide resin, latex resin, starch, gelatin, vegetable protein, casein, gum arabic, and albumin; inorganic binder such as silica sol, alumina sol, zirconia sol, and titania sol; Roughening agent as desired, specifically, silica, zirconia, clay, talc, kaolin, diatomaceous earth, alumina, titania, zeolite, calcium carbonate, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium phosphate Inorganic powder such as glass; organic powder such as acrylic resin, urethane resin, vinyl chloride resin, benzoguanamine resin, benzoguanamine / melamine / formaldehyde condensate, ion exchange resin, urea resin, polystyrene resin, etc. Can be mentioned. The material for forming these coating layers for printing (E1) can be appropriately selected according to the type of resin constituting the easily breakable layer (B1), but the easily breakable layer (B1) and the printed layer (C1). From the viewpoint of excellent adhesion to both, a polyurethane-based resin is preferable.
In addition, when the reuse prevention adhesive sheet is requested | required of transparency, it is desirable that the coating layer for printing (E1) also has transparency. In that case, as an index of these transparency, the reuse prevention pressure-sensitive adhesive sheet or printing coat layer (E1) is transparent, from one surface side of the reuse prevention pressure-sensitive adhesive sheet or printing coat layer (E1), If an arbitrary object existing on the other surface side is visible, it can be regarded as having transparency.

  The method for coating the material for forming the printing coat layer (E1) on the easily breakable layer (B1) is not particularly limited, and conventionally known methods such as gravure method, bar coating method, knife coating method, roll A coating method, a blade coating method, a die coating method, or the like can be used. Moreover, a solvent can be used as needed. The thickness of the coating layer for printing (E1) thus formed is preferably 0.2 to 30 μm, more preferably 0.5 to 30 μm. When the thickness of the coating layer for printing (E1) is 0.2 μm or more, sufficient adhesion of the printing layer (C1) is obtained, and the effect of concealing protrusions due to undissolved resin on the surface of the easily breakable layer (B1) Can be fully demonstrated. Moreover, the effect of an easily breakable layer (B1) can fully be exhibited as it is 30 micrometers or less.

(Manufacturing method of laminated body (I))
Although it does not restrict | limit especially as a manufacturing method of laminated body (I), For example, if it is laminated body (I) shown in FIG. 1, an adhesive will be apply | coated and dried on one surface of a base material (A1). Then, the pressure-sensitive adhesive layer (D1) is formed, and the easily breakable layer (B1) is formed on the surface of the base material (A1) opposite to the pressure-sensitive adhesive layer (D1) side. Subsequently, after forming the coating layer (E1) for printing on the easily breakable layer (B1) as needed, the printing layer (C1) is further formed on the easily breakable layer (B1) or the coating layer for printing (E1). It can be provided.
Further, for example, in the case of the laminate (I) shown in FIG. 2, an easily breakable layer (B1) is formed on one surface of the substrate (A1), and then opposite to the substrate (A1) side. After forming the printing coat layer (E1) on the easily breakable layer (B1) side as required, the printing layer (C1) is further formed on the breakable layer (B1) or the printing coat layer (E1). Is provided. Thereafter, the pressure-sensitive adhesive layer (D1) can be formed by applying and drying a pressure-sensitive adhesive on the surface of the printed layer (C1) opposite to the substrate (A1) side. From the method for forming the pressure-sensitive adhesive layer (D1), the pressure-sensitive adhesive is also applied to a part or all of the surface of the easily breakable layer (B1) or the printing coat layer (E1) where the printed layer (C1) is not formed. A person skilled in the art can naturally understand that the layer (D1) is in contact.

When applying the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer (D1), it is preferable to dilute the pressure-sensitive adhesive with an organic solvent to form a pressure-sensitive adhesive solution in order to facilitate the formation of a thin pressure-sensitive adhesive layer.
Examples of the organic solvent to be used include toluene, ethyl acetate, methyl ethyl ketone, and the like. By blending these organic solvents into a pressure-sensitive adhesive solution having an appropriate solid content concentration, a thin pressure-sensitive adhesive layer can be easily formed.
As solid content concentration of an adhesive solution, Preferably it is 5-60 mass%, More preferably, it is 10-40 mass%. If the amount is 5% by mass or more, the amount of the solvent used is sufficient, and if it is 60% by mass or less, the viscosity becomes appropriate and the workability is improved when the adhesive solution is applied.
In preparing the resin contained in the pressure-sensitive adhesive, when the resin is prepared in a state of being contained in an organic solvent, the same solid content as the organic solvent used in the resin preparation is used. You may dilute so that.
The method for forming the pressure-sensitive adhesive layer (D1) on the substrate (A1) or the printed layer (C1) is not particularly limited. For example, a known coating method using a pressure-sensitive adhesive (solution) containing the above organic solvent. The method of forming by is mentioned.
Examples of the coating method include known methods such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
Separately, a release sheet is prepared, and an adhesive is applied to the surface of the release sheet and dried to produce a release sheet with an adhesive layer (D1), and then the adhesive layer on the release sheet. (D2) may be bonded to the substrate (A1) or the printing layer (C1).
Also, in order to prevent residual solvents and low-boiling components, and when a crosslinking agent is blended, the adhesive solution is used as a base material (A1) or printing in order to promote crosslinking (reaction) and develop adhesiveness. After applying to the layer (C1), a drying process is performed.
As temperature conditions of a drying process, Preferably it is 70-150 degreeC, More preferably, it is 80-120 degreeC. The treatment time for the drying treatment is preferably 30 seconds to 5 minutes, more preferably 40 to 180 seconds.

<Protective sheet (II)>
The protective sheet (II) which the reuse prevention adhesive sheet of this invention has is a protective sheet (II) which has a transparent base material (A2) and an adhesive layer (D2).
(Transparent substrate (A2))
As a base material (A2) used for the reuse prevention pressure-sensitive adhesive sheet of the present invention, it is transparent to the extent that the printed content of the printed layer (C1) can be sufficiently visually recognized and does not impair the effects of the present invention. It does not restrict | limit in particular, What is conventionally used for the conventional reuse prevention adhesive sheet or a label etc. is mentioned.
The transparent base material (A2) is transparent as long as the transparent base material (A2) is transparent, and any object existing on the other surface side is visible from one surface side of the transparent base material (A2). For example, a transparent plastic film is preferably used. Examples of the material for the plastic film include acrylic resins such as polymethacrylate; polyamides such as wholly aromatic polyamide, nylon 6, nylon 66, and nylon copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate. Polyester resins such as polyurethane acrylate, polyurethane resins such as polyurethane acrylate, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymers, polystyrene resins Polycarbonate resin; norbornene resin; cycloolefin resin and the like. From the viewpoint of transparency, cost, and versatility, polyamide and polyester resin are preferable.
Although the thickness of a transparent base material (A2) will not be restrict | limited especially if it is a range which does not impair the effect of this invention, Preferably it is 10-300 micrometers, More preferably, it is 30-150 micrometers.

(Adhesive layer (D2))
The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer (D2) used in the reuse-preventing pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it does not impair the effects of the present invention. For example, various pressure-sensitive adhesives exemplified in the pressure-sensitive adhesive layer (D1) can be used.
If the thickness of an adhesive layer (D2) is a range which does not impair the effect of this invention, it will not restrict | limit, Preferably it is 5-80 micrometers, More preferably, it is 10-50 micrometers.

(Method for producing protective sheet (II))
Although it does not restrict | limit especially as a manufacturing method of protective sheet (II), For example, if it is protective sheet (II) shown in FIG.1 and FIG.2, an adhesive will be provided on one surface of a transparent base material (A2). It can be produced by applying and drying to form an adhesive layer (D2).
Separately, a release sheet is prepared, and a pressure-sensitive adhesive is applied on the surface of the release sheet and dried to produce a release sheet with a pressure-sensitive adhesive layer (D2), and then the pressure-sensitive adhesive layer on the release sheet. (D2) and a transparent base material (A2) can also be bonded together and produced. The release sheet is not particularly limited, and for example, those exemplified in the release sheet described later can be used.
When applying the adhesive to the transparent substrate (A2) or the release sheet, it is preferable to dilute the adhesive with an organic solvent to make an adhesive solution in order to facilitate the formation of a thin adhesive layer. .
Examples of the organic solvent to be used include toluene, ethyl acetate, methyl ethyl ketone, and the like. By blending these organic solvents into a pressure-sensitive adhesive solution having an appropriate solid content concentration, a thin pressure-sensitive adhesive layer can be easily formed.
As solid content concentration of an adhesive solution, Preferably it is 5-60 mass%, More preferably, it is 10-40 mass%. If the amount is 5% by mass or more, the amount of the solvent used is sufficient, and if it is 60% by mass or less, the viscosity becomes appropriate and the workability is improved when the adhesive solution is applied.
In preparing the resin contained in the pressure-sensitive adhesive, when the resin is prepared in a state of being contained in an organic solvent, the same solid content as the organic solvent used in the resin preparation is used. You may dilute so that.

The method for forming the pressure-sensitive adhesive layer (D2) on the transparent substrate (A2) or the release sheet is not particularly limited. For example, a pressure-sensitive adhesive (solution) containing the above organic solvent is applied by a known coating method. The method of forming is mentioned.
Examples of the coating method include known methods such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
Moreover, in order to prevent the residue of a solvent and a low boiling-point component, and when a crosslinking agent is mix | blended, in order to advance bridge | crosslinking (reaction) and to express adhesiveness, an adhesive solution is used for a transparent base material (A2) or After apply | coating to this peeling sheet, a drying process is performed.
As temperature conditions of a drying process, Preferably it is 70-150 degreeC, More preferably, it is 80-120 degreeC. The treatment time for the drying treatment is preferably 30 seconds to 5 minutes, more preferably 40 to 180 seconds.

<Peeling sheet>
In the reuse prevention pressure-sensitive adhesive sheet of the present invention, if desired, a release sheet can be provided on the surface of the reuse prevention pressure-sensitive adhesive sheet opposite to the transparent base material (A2). Examples of the release sheet include paper such as glassine paper, coated paper, and laminated paper, and various resin films coated with a release agent such as a silicone resin.
When using the reuse prevention pressure-sensitive adhesive sheet of the present invention, the release sheet is peeled off, and the pressure-sensitive adhesive layer (D1) is brought into contact with the surface of the adherend and attached.

[Manufacturing method of reusable PSA sheet]
It does not restrict | limit especially as a manufacturing method of the reuse prevention adhesive sheet of this invention. For example, if it is the reuse prevention adhesive sheet shown in FIG. 1, after preparing a laminated body (I) and a protection sheet (II) by the method mentioned above beforehand, the adhesive layer (D2) surface of a protection sheet (II) Can be manufactured by bonding them onto the printed layer (C1) surface of the laminate (I).
Moreover, if it is the reuse prevention adhesive sheet shown in FIG. 2, after preparing laminated body (I) and protective sheet (II) by the method mentioned above, the adhesive layer (D2) surface of protective sheet (II) Can be manufactured by adhering to the base material (A1) surface of the laminate (I).
The method for laminating the laminate (I) and the protective sheet (II) is not particularly limited, and examples thereof include conventionally known methods. For example, a method such as laminating can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not restrict | limited by these examples.

The measurement method and evaluation method in the present invention are as follows.
[Measuring method]
<Number average molecular weight of raw material (Mn)>
Using a gel permeation chromatograph, measurement was performed under the following conditions, and values measured in terms of standard polystyrene were used.
(Measurement condition)
Measuring device: Product name “HLC-8220GPC” (manufactured by Tosoh Corporation)
Column: Product name “TSKgelGMHXL”, “TSKgelGMHXL”, and “TSKgel12000HXL” (both manufactured by Tosoh Corporation) are sequentially connected. Developing solvent: Dimethylformamide (containing 0.01 mol / L lithium bromide)
Injection volume: 80 μl
Column temperature: 40 ° C
Flow rate: 1.0 mL / min
Detector: Differential refractometer

<Thickness of each layer>
The easily destructible layer (B1) was measured using a spectroscopic ellipsometer (product name: “M-2000”, manufactured by JA Woollam Japan Co., Ltd.).
The printing layer (C1), the pressure-sensitive adhesive layer (D1), and the pressure-sensitive adhesive layer (D2) were measured using a constant pressure thickness measuring instrument (product name: “PG-02”, manufactured by Teclock Co., Ltd.).

<Glass transition point (Tg) of resin component (b)>
Resin of resin component (b) shown in the following Table 1 is subjected to a thermomechanical measuring device (TMA) (product name: “TMA-4000S”, under a temperature rising rate of 5 ° C./min in accordance with JIS K7197. The glass transition temperature was calculated according to JIS K7095.
Here, when the resin component (b) is a mixture of two or more resins, the glass transition point is calculated from the glass transition point of each resin and the mixing ratio (mass ratio) of each resin. A weighted average was used.

<Peeling form of reusable PSA sheet>
After the laminates obtained in Examples and Comparative Examples were cut into a shape of 25 mm × 250 mm, one of the short sides of the protective sheet (II) of the reuse prevention pressure-sensitive adhesive sheet was peeled off and bent, and 23 ° C., 50% RH ( (Relative humidity) environment, using a tensile tester (product name “RTG-1225”, manufactured by A & D Co., Ltd.) under the conditions of a tensile speed of 1,000 mm / min and a peeling direction of 180 °. The sheet (II) was peeled from the laminate (I), and the fracture mode was evaluated according to the following criteria.
In addition, the said peeling was performed 24 hours after bonding protective sheet (II).
A: All layers from the easily breakable layer (B1) to the printed layer (C1) of the laminate (I) were broken by zipping.
B: Peeled between the printed layer (C1) of the laminate (I) and the adhesive layer (D2) of the protective sheet (II).
C: It peeled between the base material (A1) of a laminated body (I), and the easily breakable layer (B1).

[Example 1]
Polyamideimide resin having a glass transition point of 260 ° C. (product name “Vilomax HR-15ET”) on a polyethylene terephthalate film (product name “Lumirror”, manufactured by Toray Industries, Inc.) having a thickness of 50 μm as a base material (A1) An average molecular weight of 6,000, a solid content concentration of 25% by mass, manufactured by Toyobo Co., Ltd. was applied using a Mayer bar and dried to obtain an easily breakable layer (B1) having a thickness of 500 nm. On this easily breakable layer (B1), a polyurethane-based resin (product name “Ramic F220 Shiro”, manufactured by Dainichi Seika Kogyo Co., Ltd.) is applied and dried using a Mayer bar, and a printed layer (C1) having a thickness of 3 μm. )
Next, an acrylic pressure-sensitive adhesive (product name “PA-T1”, manufactured by Lintec Corporation) is applied to the surface of the base material layer (A1) opposite to the surface on which the easily breakable layer (B1) is provided, and dried ( 90 ° C., 1 minute), and a pressure-sensitive adhesive layer (D1) having a thickness of 20 μm was provided. A release sheet 11 obtained by treating glassine paper with a silicone release agent was bonded to the pressure-sensitive adhesive layer (D1) surface to obtain a laminate (I).
The protection which provided the acrylic adhesive as an adhesive layer (D2) on the 50-micrometer-thick polyethylene terephthalate film as a transparent base material (A2) on the printing layer (C1) of the obtained laminated body (I) Sheet (II) (product name “PET50 PL Thin”, manufactured by Lintec Co., Ltd.) was bonded using a 2 kg rubber roll to obtain a reuse prevention pressure-sensitive adhesive sheet having the same configuration as 10 in FIG.

[Example 2]
A reuse prevention pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the (B1) thickness of the easily breakable layer was changed to 700 nm.

[Example 3]
A reuse preventive pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the thickness of the easily breakable layer (B1) was changed to 1,400 nm.

[Example 4]
A reuse prevention pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the thickness of the easily breakable layer (B1) was changed to 300 nm.

[Example 5]
A reuse prevention pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the thickness of the easily breakable layer (B1) was 100 nm.

[Example 6]
Polyamideimide resin having a glass transition point of 260 ° C. (product name “Vilomax HR-15ET”, number average molecular weight 10,000, solid content concentration 25% by mass, manufactured by Toyobo Co., Ltd.) and polyamideimide resin having a glass transition point of 250 ° C. ( An easily destructible layer (B1) having a thickness of 500 nm using a resin in which the product name “Vilomax HR-14ET”, solid content concentration 25% by mass, manufactured by Toyobo Co., Ltd.) is mixed at a mass ratio of 80:20. Except for having obtained, the reuse prevention adhesive sheet was obtained like Example 1.

[Comparative Example 1]
Reuse prevention adhesive in the same manner as in Example 1 except that the resin component (b) used for the easily breakable layer (B1) was replaced with chlorinated polyethylene (product name “HPE1305”, manufactured by FENGHUA YURON CHEMICAL INDUSTRY MATERIAL). A sheet was produced. The evaluation results of the obtained reuse prevention pressure-sensitive adhesive sheet are shown in Table 1.

[Comparative Example 2]
Reuse prevention adhesive in the same manner as in Example 1 except that the resin component (b) used for the easily breakable layer (B1) was replaced with chlorinated polyethylene (product name “HPEP1505”, manufactured by FENGHUA YURON CHEMICAL INDUSTRY MATERIAL). A sheet was produced. The evaluation results of the obtained reuse prevention pressure-sensitive adhesive sheet are shown in Table 1.

[Comparative Example 3]
Reuse prevention adhesive in the same manner as in Example 1 except that the resin component (b) used for the easily breakable layer (B1) was replaced with chlorinated polyethylene (product name “HPE2200”, manufactured by FENGHUA YURON CHEMICAL INDUSTRY MATERIAL). A sheet was produced. The evaluation results of the obtained reuse prevention pressure-sensitive adhesive sheet are shown in Table 1.

From Table 1, the reuse prevention pressure-sensitive adhesive sheets produced in Examples 1 to 6 caused zipping when peeling the protective sheet (II) from the laminate (I), and the laminate (I) was easily destroyed. Breakage occurred from the layer (B1) to the printed layer (C1), and the layer could not be reused. Therefore, it turned out that the reuse prevention adhesive sheet produced in the said Examples 1-6 can exhibit sufficient reuse prevention performance.
On the other hand, when the protective sheet (II) is peeled from the laminate (I), the anti-reuse pressure-sensitive adhesive sheets prepared in Comparative Examples 1 to 3 are printed with the printed layer (C1) and the protective sheet (II) of the laminate (I). ) Between the pressure-sensitive adhesive layer (D2) or between the base material (A1) and the easily breakable layer (B1) of the laminate (I), and the printed layer (C1) is broken. In addition, it could be reused. Therefore, the reuse prevention adhesive sheet produced in the comparative examples 1 to 3 resulted in inferior reuse prevention performance.

  The reusable pressure-sensitive adhesive sheet of the present invention does not require ultraviolet rays or special printing ink, and even if it is peeled off, the fact that it has been peeled off can be easily found, so that abuse of the peeled label or sheet is prevented. Can do. Therefore, for example, it is suitable for fields such as a pressure-sensitive adhesive sheet that is affixed to packages that require high security such as pharmaceuticals and foods, and a pressure-sensitive adhesive sheet that is affixed to expensive electronic devices.

I Laminate (I)
A1 base material (A1)
B1 Easily destructible layer (B1)
C1 printing layer (C1)
D1 Adhesive layer (D1)
II Protection sheet (II)
A2 Transparent substrate (A2)
D2 Adhesive layer (D2)
10 Reuse Prevention Adhesive Sheet 11 Release Sheet 12 Substrate

Claims (7)

An easily breakable layer (B1) and a printing layer (C1) are laminated in this order on one surface of the substrate (A1), and further on the other surface of the substrate (A1) or the printing layer (C1). A laminate (I) provided with an adhesive layer (D1) on the surface thereof, and a protective sheet (II) having a transparent substrate (A2) and an adhesive layer (D2),
The pressure-sensitive adhesive layer (D2) of the protective sheet (II) is a re-use prevention pressure-sensitive adhesive sheet having a configuration laminated on the surface opposite to the pressure-sensitive adhesive layer (D1) of the laminate (I),
The reuse preventive pressure-sensitive adhesive sheet, wherein the easily breakable layer (B1) contains the resin component (b), and the glass transition point of the resin component (b) is 200 ° C or higher.   The pressure-sensitive adhesive layer (D1) is provided on the surface of the substrate (A1) of the laminate (I), and the pressure-sensitive adhesive layer (II) of the protective sheet (II) is provided on the surface of the printed layer (C1) of the laminate (I). The reuse prevention pressure-sensitive adhesive sheet according to claim 1, wherein D2) has a laminated structure.   It has an adhesive layer (D1) on the printed layer (C1) of the laminate (I), and the adhesive layer (D2) of the protective sheet (II) on the surface of the substrate (A1) of the laminate (I) The reuse prevention pressure-sensitive adhesive sheet according to claim 1, having a configuration in which the layers are laminated.   The reuse prevention adhesive sheet of any one of Claims 1-3 which has the structure which the coating layer (E1) for printing laminated | stacked between the easily breakable layer (B1) and the printing layer (C1).   The reuse prevention pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the resin component (b) is a polyamideimide resin.   The reuse prevention pressure-sensitive adhesive sheet according to claim 5, wherein the polyamideimide resin has a number average molecular weight of 4,000 to 12,000.   The reuse prevention pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the easily breakable layer (B1) has a thickness of 100 to 2,500 nm.