JP2000194265A - Hologram laminate and hologram label - Google Patents

Abstract

(57) [Summary] [Problem] To provide a forgery prevention label using a volume hologram,
There is no problem in the manufacturing process itself, there is certainty in the process where the anti-counterfeiting effect occurs, and it is difficult to see the traces that have been processed for anti-counterfeiting,
And a hologram label. The adhesive strength when a protective film (8) is adhered on a hologram (7) with a second adhesive (9) is partially changed, and when the protective film (8) is peeled off, a part of the second adhesive (9) remains on the hologram (7). You can see that it was peeled off. The same adhesive strength can be partially changed for the first adhesive 6. Further, the adhesive force of the first pressure-sensitive adhesive 6 was set to be larger than the 1% tensile strength of the hologram 7, and when the hologram 7 was to be peeled off, the hologram 7 was stretched and discolored.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a means for checking, such as an object having a monetary value, such as a cash voucher or a security, an identification card, or a credit card. And a hologram laminate in which a hologram label is attached to expensive goods such as a luxury watch or a cosmetic box for those goods in order to prove that the goods are genuine. The present invention relates to a hologram sticking label suitable for the above applications. When the hologram laminate and the hologram label of the present invention are peeled off after being pasted, the protective film on the surface is peeled off, and the adhesive is partially left on the hologram, or another layer is peeled off, and in the peeled portion. When the adhesive is partially left, or when the exposed hologram is further peeled off, the hologram expands, and in any case, the hologram has a special structure in which the peeling is obvious.

[0002]

2. Description of the Related Art A hologram itself is a product of a photographic technique that has been known for a long time. An interference fringe generated by the interference between two laser beams, a reference beam and an object beam containing information on an object, is generated.
It was exposed on a photographic plate and developed to obtain a silver halide photograph. In recent years, by exposing and developing interference fringes on a photosensitive resin, relief holograms recorded by replacing the interference fringes with irregularities on the surface can be mass-replicated by a duplication technique using resin, and used in various applications. It is becoming popular. In particular, since holograms are difficult to manufacture, they are attached to various articles as one of countermeasures against forgery.

On the other hand, among the holograms, there is a so-called volume hologram in which interference fringes are recorded three-dimensionally in the thickness direction of the photosensitive material. Due to the development and the like, mass production has become possible. However, even though this volume hologram is duplicated with a photosensitive resin, its mechanical strength is smaller than that of a relief hologram in which the resin is completely cured. However, it is difficult to process directly, and it is a restrictive condition when countermeasures are taken.

[0004] Similarly to a relief hologram, it is difficult to manufacture a volume hologram, even if it is difficult to obtain a genuine hologram. Since the hologram itself is genuine, it is extremely difficult to determine whether or not there has been an incorrect intention.

Therefore, various techniques have been proposed in order to prevent the latter, in particular, from replacing a genuine hologram.
For example, Japanese Patent Application Laid-Open No. 10-86565 discloses a hologram having a transparent protective sheet formed on its surface, which is adhered to a substrate, and an adhesive layer for bonding the transparent protective sheet and the hologram, or a hologram and a base. A technique is described in which a distribution of an adhesive force is provided in one of the adhesive layers of an adhesive layer that adheres to a material, and the hologram is destroyed if the hologram is to be peeled off. However, in order to generate the adhesive force distribution, two kinds of adhesives themselves are used, which not only complicates the processing, but also when using different types of adhesives, due to a difference in the refractive index, such an adhesive is used. There was a risk that the appearance of processing would be apparent from the appearance.

Japanese Patent Application Laid-Open No. 10-133552 has a similar layer structure, except that the adhesiveness of the pressure-sensitive adhesive layer between the protective film and the volume hologram layer is determined by comparing the adhesiveness between the substrate and the volume hologram layer. A technique is described in which, when the adhesive is set to be weaker than the adhesiveness of an adhesive layer between the layers, a peeling line is generated in a direction perpendicular to the direction of the peeling when the peeling is attempted. However, the peeling line is not formed at a predetermined position in advance, but is generated during the peeling process. The state of the peeling line differs depending on the pulling direction and the magnitude of the force at the time of peeling. Was questioned.

[0007]

According to the present invention, there is no problem in the manufacturing process itself, and there is a certainty in the process in which the forgery prevention effect is produced, and it can be seen that there is evidence that the forgery prevention process has been performed. Difficult, hologram laminate,
And a hologram label.

[0008]

According to the present invention, when attaching a hologram to an article, the protective film is peeled off by partially changing the adhesive strength between the protective film and the adhesive in contact with the protective film. In this case, a part of the adhesive is left on the hologram, so that it can be seen that the adhesive has peeled off. In the present invention, preferably, the adhesive strength between the hologram and the base material is 1% of the hologram. By making it larger than the tensile strength, the film was stretched when peeling was attempted, so that it could be seen that the film was peeled.

According to a first aspect of the present invention, a hologram layer is laminated on a substrate via a first adhesive layer, and a transparent film is laminated on the hologram layer via a second adhesive layer. The adhesive force between the substrate and the hologram layer is greater than the adhesive strength between the hologram layer and the transparent film, and the second pressure-sensitive adhesive layer, when peeling the transparent film, the transparent A first portion in which the adhesive strength with the film is stronger than the adhesive strength with the hologram layer and which remains on the transparent film side, and the adhesive strength with the transparent film is weaker than the adhesive strength with the hologram layer, and And a second portion remaining in the hologram laminate. The second invention relates to the hologram laminate according to the first invention, wherein the hologram laminate has a layer partially weakening the adhesive strength between the transparent film and the second pressure-sensitive adhesive layer between the two layers. The third invention relates to the hologram laminate according to the first invention, wherein a hologram laminate partially includes a layer for increasing the adhesive strength between the transparent film and the second pressure-sensitive adhesive layer between the two layers.
A fourth invention relates to the hologram laminate according to any one of the first to third inventions, wherein an adhesive strength between the hologram layer and the substrate is larger than a 1% tensile strength of the hologram. is there. In a fifth invention, a first pressure-sensitive adhesive layer, a hologram layer, a second pressure-sensitive adhesive layer, and a transparent film are laminated in this order from the bottom, and the second pressure-sensitive adhesive layer is formed by peeling the transparent film. In this case, the adhesive strength with the transparent film is stronger than the adhesive strength with the hologram layer, the first portion remaining on the transparent film side, and the adhesive strength with the transparent film is greater than the adhesive strength with the hologram layer. A hologram label having a second portion which is weakly left on the hologram layer. In a sixth aspect based on the fifth aspect, the second aspect is the second aspect.
The present invention relates to a hologram label having, between both layers of an adhesive layer and a transparent film, a layer partially weakening the adhesive strength between the two layers. The seventh invention relates to the hologram label according to the fifth invention, wherein the hologram label partially includes a layer for increasing the adhesive strength between the second pressure-sensitive adhesive layer and the transparent film. The eighth invention relates to the hologram label according to any one of the fifth to seventh inventions, wherein an adhesive strength between the hologram layer and the base material is larger than a 1% tensile strength of the hologram layer. . The ninth invention relates to the hologram label according to any one of the fifth to eighth inventions, wherein a peelable sheet is further laminated below the first pressure-sensitive adhesive layer. Tenth
The invention is characterized in that a hologram layer is laminated on a base material via a first pressure-sensitive adhesive layer, and the hologram layer has a first transparent film laminated on a lower surface via a second pressure-sensitive adhesive layer, On the hologram layer, a second transparent film is laminated via a third pressure-sensitive adhesive layer, and the adhesive force between the base material and the first transparent film is different from that of the hologram layer. The adhesive strength with the second transparent film is larger than the adhesive strength with the hologram layer, and the third adhesive layer has an adhesive strength with the second transparent film when the second transparent film is peeled off. A first portion remaining on the second transparent film side stronger than the adhesive strength of the second transparent film, and a second portion remaining on the holographic layer weaker than the adhesive strength with the second transparent film than the adhesive strength with the hologram layer. Characterized by having a portion of The present invention relates to gram laminate.
An eleventh invention is directed to the hologram laminate according to the tenth invention, wherein the hologram laminate partially includes a layer for weakening the adhesive strength between the second transparent film and the third pressure-sensitive adhesive layer between the two layers. Things. A twelfth invention is directed to the hologram laminate according to the tenth invention, wherein the hologram laminate partially includes a layer for increasing the adhesive strength between the second transparent film and the third pressure-sensitive adhesive layer, between the two layers. Things. Thirteenth
The invention according to any one of the tenth to twelfth inventions, wherein the adhesive strength between the first transparent film and the substrate is larger than the 1% tensile strength of the hologram. It is. According to a fourteenth aspect, a first pressure-sensitive adhesive layer, a first transparent film, a second pressure-sensitive adhesive layer, a hologram layer, a third pressure-sensitive adhesive layer, and a second transparent film are laminated in this order from the bottom. And the adhesive force between the substrate and the first transparent film is greater than the adhesive strength between the hologram layer and the second transparent film, and the third adhesive layer is A first portion remaining on the side of the second transparent film, the adhesive strength of the second transparent film being stronger than the adhesive strength of the second transparent film when peeling the second transparent film;
And a second portion remaining on the hologram layer, the adhesive strength of the hologram layer being lower than that of the hologram layer. A fifteenth invention is directed to the hologram label according to the fourteenth invention, wherein the hologram label partially includes a layer for weakening the adhesive strength between the third pressure-sensitive adhesive layer and the second transparent film. is there. A sixteenth invention is directed to the hologram label according to the fourteenth invention, wherein the hologram label partially includes a layer for increasing the adhesive strength between the third pressure-sensitive adhesive layer and the second transparent film. is there. A seventeenth invention relates to the hologram label according to any one of the fourteenth to sixteenth inventions, wherein the adhesive strength between the first transparent film and the substrate is larger than the 1% tensile strength of the hologram layer. Things. First
The invention of an eighth aspect is the invention according to any one of the fourteenth to seventeenth aspects,
The present invention relates to a hologram label in which a releasable sheet is further laminated below a first pressure-sensitive adhesive layer. In a nineteenth aspect, a hologram layer is laminated on a base material via a first pressure-sensitive adhesive layer, and a transparent film is formed on the hologram layer by a second adhesive layer.
Laminated via an adhesive layer, the adhesive force between the substrate and the hologram layer is smaller than the adhesive strength between the hologram layer and the transparent film, and the first adhesive layer, When the hologram layer and the base material are peeled off, the adhesive strength between the hologram layer and the first portion which is stronger than the adhesive strength with the base material and which remains on the hologram layer side, A hologram laminate having a second portion weaker than the adhesive strength with the substrate and remaining on the substrate. In a twentieth aspect, a hologram layer is laminated on a substrate via a first pressure-sensitive adhesive layer, and a transparent film is laminated on the hologram layer via a second pressure-sensitive adhesive layer. And the adhesive force between the hologram layer and the adhesive strength between the hologram layer and the transparent film is smaller or larger,
In addition, the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer both have a portion that remains on the upper layer side and a portion that remains on the lower layer side when peeled off, and a hologram laminate according to the present invention. Things. According to a twenty-first aspect, a first pressure-sensitive adhesive layer, a hologram layer, a second pressure-sensitive adhesive layer, and a transparent film are laminated in this order from the bottom, and the first pressure-sensitive adhesive layer is used for peeling of the hologram layer. In this case, the hologram label has a first portion having a high adhesive strength with the hologram layer and remaining on the hologram layer side, and a second portion having a low adhesive strength with the hologram layer. It is about. In a twenty-second aspect, a hologram layer is laminated on a base material via a first pressure-sensitive adhesive layer, and the hologram layer is formed by laminating a first transparent film on a lower surface via a second pressure-sensitive adhesive layer. A second transparent film is laminated on the hologram layer via a third pressure-sensitive adhesive layer, and an adhesive force between the base material and the first transparent film is reduced by the hologram. The first pressure-sensitive adhesive layer has a lower adhesive strength between the first transparent film and the first transparent film when the first transparent film is peeled off. A first portion that is stronger than the adhesive strength with the material and remains on the first transparent film side, and the adhesive strength with the first transparent film is weaker than the adhesive strength with the base material and remains on the base material; A hologram laminate having a second portion. Is shall. The twenty-third invention includes a first pressure-sensitive adhesive layer, a first transparent film,
A second pressure-sensitive adhesive layer, a hologram layer, a third pressure-sensitive adhesive layer, and a second transparent film are laminated in this order; and
The adhesive force between the substrate and the first transparent film,
The adhesive strength between the hologram layer and the second transparent film is smaller than the adhesive strength between the first transparent film and the first adhesive layer when the first transparent film is peeled off. The first strongly remaining on the first transparent film side
And a second portion having a weak adhesive strength with the second transparent film. According to a twenty-fourth aspect of the present invention, a hologram layer is laminated on a base material with a first pressure-sensitive adhesive layer interposed therebetween, and the hologram layer has a first surface on a lower surface with a second pressure-sensitive adhesive layer interposed therebetween.
Are laminated on the hologram layer, a second transparent film is laminated via a third adhesive layer, and the first to third adhesive layers are an upper layer and a lower layer thereof. A hologram laminate characterized in that it has a difference in adhesive strength with the hologram, and both have a portion that remains on the upper layer side and a portion that remains on the lower layer side when the adhesive layer is peeled off. It is about the body. According to the invention of claim 25, a first adhesive layer, a first transparent film, a second adhesive layer, a hologram layer, a third adhesive layer, and a second transparent film are laminated in this order from the lower side. And the first to third pressure-sensitive adhesive layers have a difference in adhesive strength, and, when peeled off in any of the pressure-sensitive adhesive layers, a portion remaining on the upper layer side and a portion not remaining on the upper layer side A hologram label characterized by having:

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a plan view showing an example in which the laminate of the present invention is applied to an identification card. Photo 3 is laminated on a base material 2 and sealed on photo 3. 1 shows an identification card 1 on which a hologram seal 4 is laminated. In addition,
“Label” and “seal” are almost synonymous, but “seal” refers to the case where the “label” is used for sealing purposes.
Characters 5 such as the name of the holder, the place of issue, the expiration date, and the serial number are printed or printed on the base material 2. Although not shown, in addition to these, a part of the base material includes a magnetic stripe, an IC or an LSI,
It may have an imprint, a writable layer and the like. In addition,
Photograph 3 may be any of a silver salt type, a dye sublimation transfer, and an electrophotographic toner formed. In this example, a hologram seal 4 is placed on the photo 3 in order to prevent the photo from being replaced.
However, the position where the hologram seal 4 is laminated is not limited as long as it is not on the imprint having irregularities. When a hologram described later is colorless and transparent or colored and transparent, the hologram seal 4 may be laminated even if characters or the like are printed below.

FIG. 2 is a cross-sectional view taken along the line AA of FIG. , The hologram seal 4 is laminated.

In the description referring to FIG. 1 and FIG.
Is a card for an identification card, but the base material 2 of the hologram laminate of the present invention can be various. Similar articles for identification cards include passports and credit cards, and these substrates can be used as the substrate 2 of the present invention. The present invention can also be applied to objects having a monetary value such as cash vouchers or securities. Gold vouchers, such as gift certificates and gift cards used in department stores, have a limited range of value as a substitute for money, beer tickets used for gifts, ice cream tickets, or cash vouchers. There is a card that can be exchanged for a specific product, such as a U.S. ticket, or a prepaid card used in transportation or a playground.
Alternatively, there is a check, a promissory note, or the like, for which a monetary value is generated by filling in the information, and the character is different from these, but the present invention is also applicable to a passbook or the like used by a financial institution such as a bank. The securities include stock certificates, bonds, insurance policies, and the like, which cannot be immediately exchanged for money, but have a monetary value. Portable and expensive, for example,
Luxury watches, cigarette lighters, and the like are also products that are likely to be counterfeited, and can be base materials for the laminate of the present invention. The dial or back side of a watch, or a decorative case or the like used when selling a watch can be the base material. In addition, documents and certificates that evaluate and appraise art and antiques such as precious metals, paintings, etc. also support the value of the article, so they are easily subject to forgery, and the base material of the laminate of the present invention Can be
Furthermore, recorded videotapes, compact discs for music or video, and CD-Rs containing computer software
Laminates of the present invention, such as OM and popular game software, which are likely to cause damage to copyright holders or distributors when pirated copies are sold can be used. In addition, it is mainly clothing for outdoor use, and outerwear with excellent breathability and moisture permeability function,
Famous brands such as rain gear, leather brands such as handbags and famous brands which are often found in bags are expensive, and inexpensive counterfeit products may be available. Each of these products, or those obtained by packaging them, can be used as a substrate in the laminate of the present invention.

The base materials 2 to be used are roughly divided into
One of them is that which has a high economic value, such as one having a financial value or a high selling price, and thus is easily subject to forgery. The other, which has little direct economic value, is fraudulently gaining a certain status or qualification. An ID card such as an identification card, a passport, or a credit card is applicable.

As a material of the above-mentioned base material 2, if it is an ID card, vinyl chloride resin is conventionally mainstream.
Polyolefin resins such as polyethylene resins and polypropylene resins, acrylic resins, polycarbonate resins, polyethylene terephthalate resins, and triacetyl cellulose resins can also be used. Other materials for the base material 2 include paper, synthetic paper, rubber, cloth, wood base materials such as wood and bamboo,
Metals, ceramics, or the like can be used, and products obtained by processing those materials may be used. The shape of the substrate 2 is
Depending on the article, there are various shapes such as a sheet, a flat plate, a secondary curved surface, and a three-dimensional curved surface.

FIG. 3A is a detailed drawing of a laminated body 1 in which a hologram label 4 is laminated on a base material 2, and FIG. 3B is a detailed drawing of a label 10 used therefor. It is. As shown in FIG. 3A, in the laminate 1 of the present invention, the hologram layer 7
The transparent film 8 is laminated on the hologram layer 7 via the second pressure-sensitive adhesive layer 9. FIG. 3B shows a label 1 for that purpose.
0, the upper four layers are the same as those in the laminate 1, except that the peelable sheet 11 is laminated on the lowermost layer.

The hologram of the hologram layer 7 may be a relief hologram, but is preferably a volume hologram. The volume hologram is obtained by recording interference light between object light and reference light on a photosensitive material sufficiently thicker than the interval between interference fringes. The three-dimensional structure of the interference fringes is recorded as it is. In order to form this volume hologram, the interference light between the object light and the reference light is recorded directly on the laminated material of the volume hologram forming material on the support film, or the original volume hologram is adhered. It is obtained by copying by exposure, and industrially by the latter method.

Hereinafter, the materials for forming the volume hologram and the forming method will be described in detail. The support film to be coated with the volume hologram forming material has a thickness of 1 μm.
A polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polyvinyl chloride film, an acrylic film, a triacetylcellulose film, a cellulose acetate butyrate film having a thickness of m to 1 mm, preferably 10 μm to 100 μm is used. It is desirable to use a film having high transparency and high smoothness as the support film.

Generally, hologram-forming materials include:
Known volume hologram recording materials such as a silver salt material, a dichromated gelatin emulsion, a photopolymerizable resin, and a photocrosslinkable resin may be mentioned.In the volume hologram of the present invention, a matrix polymer, It is preferable to use, as a material for forming a volume hologram, a photosensitive material for dry volume phase hologram recording, which comprises a photopolymerizable compound, a photopolymerization initiator, and a sensitizing dye.

Examples of the matrix polymer as a binder resin include polymethacrylic acid ester or its partial hydrolyzate, polyvinyl acetate or its hydrolyzate, polyvinyl alcohol or its partial acetalized product, triacetyl cellulose, polyisoprene, polybutadiene, Polychloroprene, silicone rubber, polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinyl carbazole or a derivative thereof,
Poly-N-vinylpyrrolidone or a derivative thereof, a copolymer of styrene and maleic anhydride or a half ester thereof, acrylic acid, acrylate ester, methacrylic acid, methacrylic ester, acrylamide, acrylonitrile,
A copolymer containing at least one of a group of copolymerizable monomers such as ethylene, propylene, vinyl chloride, and vinyl acetate as a polymerization component or the like, or a mixture thereof is used. Preferably polyisoprene, polybutadiene, polychloroprene, polyvinyl alcohol, or polyvinyl acetal which is a partially acetalized product of polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, or the like, or a mixture thereof. .

As a step of stabilizing the recorded hologram, there is a step of monomer transfer by heating. For this purpose, these matrix polymers preferably have a relatively low glass transition temperature and facilitate monomer transfer. It is necessary to be.

Examples of the photopolymerizable compound include photopolymerizable and photocrosslinkable monomers and oligomers having at least one ethylenically unsaturated bond in one molecule as described below.
Prepolymers, and mixtures thereof, for example, unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids and aliphatic polyhydric amine compounds and Amide bond.

Specific examples of unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and their halogen-substituted unsaturated carboxylic acids such as chlorinated unsaturated carboxylic acids. And brominated unsaturated carboxylic acids and fluorinated unsaturated carboxylic acids. Examples of the salts of unsaturated carboxylic acids include the above-mentioned sodium salts and potassium salts.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butanediol diacrylate. Acrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate Acrylate,
Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol Tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, phenol ethoxylate monoacrylate, 2- (p-
(Chlorophenoxy) ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenylethyl acrylate, (2-acryloxyethyl) ether of bisphenol A, ethoxylated bisphenol A diacrylate, 2- (1-naphthyloxy) ethyl Acrylate and o-biphenyl acrylate.

Of the specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid, methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethyl glycol dimethacrylate. Methylol propane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexa Methacrylate,
Sorbitol trimethacrylate, sorbitol tetramethacrylate, bis- [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (acryloxyethoxyphenyl)
Examples include dimethylmethane, 2,2-bis (4-methacryloyloxyphenyl) propane, and 2-naphthyl methacrylate.

Among specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid, itaconic esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-
Butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaethasritol diitaconate, sorbitol tetritaconate, and the like.

Among the specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid, crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, Sorbitol tetracrotonate and the like.

Among the specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid, the isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Etc.

Among the specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid, maleic esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, Sorbitol tetramaleate and the like.

The halogenated unsaturated carboxylic acids include
2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H, 1H, 2H, 2H-heptadeca Fluorodecyl methacrylate, methacrylic acid
2,4,6-tribromophenyl, dibromoneopentyl dimethacrylate, (trade name; NK ester DBN,
Shin-Nakamura Chemical Co., Ltd.), dibromopropyl acrylate (trade name: NK Ester A-DBP, Shin-Nakamura Chemical Co., Ltd.), dibromopropyl methacrylate (trade name: NK Ester DBP, Shin-Nakamura Chemical Co., Ltd.) )),
Methacrylic acid chloride, methacrylic acid-2,4,6-
Trichlorophenyl, p-chlorostyrene, methyl-2
-Chloroacrylate, ethyl-2-chloroacrylate, n-butyl-2-chloroacrylate, tribromophenol acrylate, tetrabromophenol acrylate and the like.

Specific examples of the amide monomer of an unsaturated carboxylic acid and an aliphatic polyamine compound include methylenebisacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebisacrylamide,
6-Hexamethylenebismethacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, N-phenylmethacrylamide, diacetoneacrylamide and the like.

As another example, see JP-B-48-417.
08, a polyisocyanate compound having two or more isocyanate groups in one molecule, a compound represented by the general formula CH
₂ ＣC (R) COOCH ₂ (R ′) OH (wherein R and R ′
Represents hydrogen or a methyl group. A) a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer having a hydroxyl group is added.

Urethane acrylates described in JP-A-51-37193, JP-A-48-6418
No. 3, JP-B-49-43191, JP-B-52
Polyester acrylates and polyfunctional acrylate methacrylates such as an epoxy group and (meth) acrylic acid as described in JP-A-30490 can be exemplified.

Further, the Journal of the Adhesion Society of Japan, Vol. 20, N
o. 7, those introduced as photocurable monomers and oligomers on pages 300 to 308 can also be used.

Other monomers containing phosphorus include mono (acryloyloxyethyl) acid phosphate (trade name: Light Ester PA, manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and mono (2-methacryloyloxyethyl) acid Phosphate (trade name; light ester PM,
Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), and an epoxy acrylate-based product name; Lipoxy VR-60
(Trade name (Lipoxy VR-90, manufactured by Showa Polymer Co., Ltd.)
(Manufactured by Showa Polymer Co., Ltd.).

Further, NK ester M-230G (trade name)
(Manufactured by Shin-Nakamura Chemical Co., Ltd.), trade name: NK ester 2
3G (manufactured by Shin-Nakamura Chemical Co., Ltd.) is also included.

Further, triacrylates having the following structure

[0037]

Embedded image

(Trade name: Aronix M-315, manufactured by Toagosei Chemical Industry Co., Ltd.), triacrylates having the following structure

[0039]

Embedded image

(Trade name: Aronix M-325, manufactured by Toa Gosei Chemical Industry Co., Ltd.) and 2,2'-bis (4-
Acryloxy diethoxyphenylpropane (trade name;
NK ester A-BPE-4), tetramethylolmethanetetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-TMMT) and the like.

Next, as a photopolymerization initiator in the initiator system, 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-
(Butyldioxycarbonyl) benzophenone, N-phenylglycine, 2,4,6-tris (trichloromethyl) s-triazine, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, imidazole dimer, etc. Is exemplified. The photopolymerization initiator is preferably decomposed after recording the hologram from the viewpoint of stabilizing the recorded hologram. For example, organic peroxides are preferred because they are easily decomposed by ultraviolet irradiation.

The sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, and oxonol dyes having absorption light at 350 to 600 nm. Dyes, cyanine dyes, rhodamine dyes, thiopyrylium salt dyes, pyrylium ion dyes, and diphenyliodonium ion dyes are exemplified. A sensitizing dye having absorption light in a wavelength region of 350 nm or less or 600 nm or more may be present.

Comprising the above-mentioned matrix polymer, photopolymerizable compound, photopolymerization initiator and sensitizing dye,
The compounding ratio of the volume hologram forming material is as follows. The photopolymerizable compound is 10 parts by weight to 1000 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the binder resin.
It is used in a proportion of 100 parts by weight to 100 parts by weight. The photopolymerization initiator is 1 part by weight to 1 part by weight based on 100 parts by weight of the binder resin.
0 parts by weight, preferably 5 parts by weight to 10 parts by weight. The sensitizing dye is used in an amount of 0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the binder resin.

Other components of the material for forming a volume hologram include, for example, a plasticizer, glycerin, diethylene glycol, triethylene glycol and various nonionic surfactants, cationic surfactants, anionic surfactants Is mentioned.

The material for forming the volume hologram is acetone,
Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4-dioxane, 1,2-dichloroethane, dichloromethane, Using chloroform, methanol, ethanol, isopropanol, etc., or a mixed solvent thereof, and having a solid content of 15% to
The coating liquid is about 25%. In addition, as such a coating liquid, for example, Omnidex 35 manufactured by DuPont
You may use what is marketed as 2,706. If the support film is applied in the form of a single sheet (each sheet) using these coating solutions, the support film is rolled into a long length by bar coating, spin coating, dipping or the like. If it is applied in the state of, apply by gravure coat, roll coat, die coat, comma coat, etc., and after applying all, solidify using the drying or curing means according to the application liquid Let it. The thickness of the material for forming a volume hologram thus obtained is 0.1 μm to 50 μm,
Preferably it is 5 μm to 20 μm.

A protective film may be stuck on the material for forming a volume hologram obtained by coating on the support film until the hologram information is exposed. The protective film has a thickness of 1 μm to 1 mm, preferably 1 μm to 1 mm.
A highly transparent, highly smooth resin film such as a polyethylene terephthalate film of 0 μm to 100 μm, a polyethylene film, a polypropylene film, a polyvinyl chloride film, an acrylic film, a triacetyl cellulose film, a cellulose acetate butyrate film, and the like, using a rubber roller or the like. It is good to stick. Alternatively, instead of attaching a transparent resin film, a protective film may be formed by applying a coating material in which a film-forming material such as triacetyl cellulose, polyvinyl alcohol, or polymethyl methacrylate is dissolved by spin coating or the like.

The material for forming a volume hologram on the support film, when a protective film is adhered, as it is, or after peeling off the protective film, directly from the support film side, a two-beam laser beam, for example, Recording interference fringes using an argon laser (wavelength 514.5 nm), a krypton laser (wavelength 647 nm), or the like;
After recording the interference light between the object light and the reference light, or after peeling off the protective film, the volume hologram forming material is directly adhered to the volume hologram forming material, and from the support film side of the volume hologram forming material. An argon laser (wavelength: 514.5 nm) is incident, and interference fringes between the reflected light from the original and the incident light are recorded to give volume hologram information.

[0048] Then, ultra-high pressure mercury lamp, high pressure mercury lamp, carbon arc, xenon arc, from a light source such as a metal halide lamp, 0.1~10,000mJ / cm ^2, preferably, ultraviolet radiation 10~1,000mJ / cm ² , And a heat treatment, for example, a step of diffusing and moving a photopolymerizable compound by heating at 120 ° C. for 120 minutes to obtain a stable volume hologram.

In the hologram laminate of the present invention, a material for forming a volume hologram and a hologram layer 7 obtained by the above-described method are laminated on the base material 2 via the first pressure-sensitive adhesive layer 6. And a transparent film 8
Are laminated via the second pressure-sensitive adhesive layer 9.

Next, the transparent film 8 will be described.
The transparent film 8 covers the uppermost layer of the hologram laminate or hologram label or the lower surface of the hologram layer 7. The transparent film 8 is a polyethylene film, a polypropylene film, a polyethylene fluoride film, a polyvinylidene fluoride film, a polyvinyl chloride film, a polyvinylidene chloride film, an ethylene-vinyl alcohol film, a polyvinyl alcohol film, a polymethyl methacrylate film, a polyether sulfone Film, polyetheretherketone film, polyamide film, tetrafluoroethylene-perfluoroalkylvinylether copolymer film, polyester film such as polyethylene terephthalate film, polyimide film, etc. are exemplified, and the thickness of the transparent film 8 is 2 μm to 200 μm.
m, preferably 10 μm to 50 μm.

The transparent film 8 may be subjected to a hard coat treatment, if necessary, in order to enhance the protective function of the surface, especially when applied to the uppermost layer of the hologram laminate or hologram label. . The hard coat treatment is, for example, coating a silicone-based, fluorine-containing silicone-based, melamine alkyd-based, urethane-acrylate-based (ultraviolet curable) or the like to a film thickness of 1 μm to 50 μm by a dipping method, a spray method, a roll coating method, or the like. Good to do. A release treatment may be performed on the transparent film 8 or on the hard coat treated surface as described above. In the release treatment, a fluorine-based release agent, a silicone-based release agent, a stearic acid-based release agent, a wax-based release agent, or the like may be applied by a dipping method, a spray method, a roll coating method, or the like. The transparent film 8 may be colored, especially when it is on the lower surface of the hologram layer 7.

In the example shown in FIG. 3, the first pressure-sensitive adhesive layer 6 is for laminating the hologram layer 7 on the base material 2 and the second pressure-sensitive adhesive layer 9 is for laminating the transparent film 8 on the hologram layer 7. .
Here, the base material 2 and the hologram layer 7 by the first pressure-sensitive adhesive layer 6
Is set to be larger than the adhesive strength S2 between the hologram layer 7 and the transparent film 8 by the second pressure-sensitive adhesive layer 9, preferably 100 gf / 2.5 cm or more. When the hologram label 4 is to be peeled from the hologram laminate 1, the transparent film 8 is firstly peeled.

When the second pressure-sensitive adhesive layer 9 and the transparent film 8 are bonded to each other, a portion where the bonding strength is not sufficient is set. A part of the agent remains on the hologram layer 7 and the other is removed together with the transparent film 8.

Examples of the adhesive constituting the first adhesive layer 6, the second adhesive layer 9, and the third adhesive layer 9 'to be described later include, for example, acrylic resin, acrylate resin,
Or copolymers thereof, styrene-butadiene copolymer, natural rubber, casein, gelatin, rosin ester,
Terpene resins, phenolic resins, styrene resins, coumarone indene resins, polyvinyl ethers, silicone resins, and the like are exemplified.Also, α-cyanoacrylate,
Silicone type, maleimide type, styrene type, polyolefin type, resorcinol type, polyvinyl ether type,
An adhesive such as a silicone adhesive may be used.

As the pressure-sensitive adhesive constituting the first pressure-sensitive adhesive layer 6, in addition to the above, heat sealants such as ethylene-vinyl acetate copolymer resin, polyamide resin, polyester resin, polyethylene resin, ethylene-isobutyl Examples include acrylate copolymer resin, butyral resin, polyvinyl acetate and its copolymer resin, cellulose derivative, polymethyl methacrylate resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin, polypropylene resin, epoxy resin, and phenol resin. Alternatively, SBS (styrene-butadiene-
Styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), SEBS
A thermoplastic elastomer such as (styrene-ethylene-butylene-styrene block copolymer) or a reactive hot-melt resin may be used. The first pressure-sensitive adhesive layer 6, the second pressure-sensitive adhesive layer 9, and the third pressure-sensitive adhesive layer 9 'are preferably formed using the above-mentioned materials so as to have a thickness of 4 μm to 20 μm.

There are several methods for bonding by applying a pressure-sensitive adhesive, one of which is applied to one or both sides of the bonding surface, dried if necessary, and then There is a method of crimping. At the time of press bonding, heating may be performed if necessary. Alternatively, a pressure-sensitive adhesive is applied to the releasable surface of the releasable sheet, called a separator, and then pressure-bonded to one of the adhesive surfaces, and the separator is peeled off after the pressure-bonding,
There is a method of pressing another adhesive surface to the pressure-sensitive adhesive surface exposed by peeling. When applying the adhesive immediately after applying the pressure-sensitive adhesive to the separator, one separator may be used, but one in which the pressure-sensitive adhesive layer is sandwiched between two separators
There is a method of using a "double-sided tape" in which one separator is peeled off and bonded, and then the other separator is peeled off and bonded.

In the example shown in FIG. 3, the first pressure-sensitive adhesive layer 6
The adhesive strength S1 between the substrate 2 and the hologram layer 7
To set the adhesive strength between the hologram layer 7 and the transparent film 8 by the pressure-sensitive adhesive layer 9 to be larger than S2,
Use different pressure-sensitive adhesives and use different pressure-sensitive adhesives, or use different pressure-sensitive adhesives, and use two types of mixed adhesives with different mixing ratios. , So that an appropriate adhesive strength difference occurs, or
A common pressure-sensitive adhesive may be used, and any method may be used such as changing the amount of a cross-linking agent such as an isocyanate-based cross-linking agent or a tackifier resin to increase or decrease the adhesive strength. Changing the adhesive strength of the first to third pressure-sensitive adhesive layers is similarly performed.

As for the adhesion between the second pressure-sensitive adhesive layer 9 and the transparent film 8, a portion having sufficient adhesive strength and a portion having insufficient adhesive strength are set. Explaining with reference to FIGS. 5 and 6, the surface of the transparent film 8 on the side in contact with the second pressure-sensitive adhesive layer 9 has an adhesive property with respect to a paint that gives releasability, for example, the transparent film 8. In a paint containing a binder resin as a main component, a material obtained by adding a substance that gives releasability such as wax or silicone is applied or printed in a pattern to form a releasable pattern 12, and on the releasable pattern 12, (2) The method is performed so that the adhesive layer 9 does not sufficiently adhere. Conversely, by applying or printing in a pattern using a paint containing a substance that plays a role of a primer that enhances the adhesive strength between the two, the second adhesive layer 9 is sufficiently adhered to the applied portion by a method. Alternatively, a method of applying or printing a component for crosslinking the adhesive on the transparent film 8 side in a pattern may be used. In any case, the pattern can be provided in the form of dots, stripes, lattices, symbols, other patterns, or characters.
It is preferable to provide a word such as "opened" or the English character "VOID" (= invalid meaning) so that the user can see that it has been peeled off. The pressure-sensitive adhesive layer may be arbitrarily colored with a coloring agent such as a pigment or a dye.

Alternatively, a method of irradiating ionizing radiation such as an ultraviolet ray or an electron beam in a pattern to partially perform crosslinking may be employed. When partially increasing the adhesive strength, it is checked whether or not the adhesive strength of the entire transparent film 8 is lower than the adhesive strength of the lower first adhesive layer 6. Care should be taken not to peel off the hologram layer 7 when the transparent film 8 is peeled off. The control of the adhesive strength as described above is performed by the second pressure-sensitive adhesive layer 9.
And the hologram layer 7. In addition, the strength of the adhesive between the second adhesive layer 9 and the hologram layer 7 and between the transparent film 8 and the second adhesive layer 9 can be controlled in terms of the adhesive strength. However, since the hologram layer 7 composed of a volume hologram is not so tough and is somewhat soft and easily stretched when pulled, the control of the adhesive strength is performed by the transparent protective film 8 and the second pressure-sensitive adhesive layer 9. It is better to do it in between.

When the second pressure-sensitive adhesive layer 9 and the transparent film 8 are bonded to each other, a portion having a sufficient adhesive strength and a portion having an insufficient adhesive strength are set. If the pattern 12 is separated and visually recognizable, a person who intends to peel it off for an unauthorized purpose is more cautious, so that attention is paid so that visibility is not caused by a difference in refractive index or the like.

By setting a portion where the adhesive strength is sufficient and a portion where the adhesive strength is not sufficient between the hologram layer 7 and the transparent film 8, when the transparent film 8 is peeled off, a case where partial peelability is given is used. Assuming that, as shown in FIG. 6, on the pattern 12, since the adhesive strength of the adhesive constituting the second adhesive layer 9 is relatively weak, peeling occurs on or near the surface of the pattern 12, As a result, on the pattern 12, a very small amount of adhesive adheres and peels off.
At the corresponding position on the hologram layer 7, most of the adhesive remains without being removed. In addition, since the portions other than the pattern 12 are bonded with a normal adhesive force, the pattern 12
Since a larger amount of the pressure-sensitive adhesive is removed together with the transparent film 8 as compared with the above, there is a difference in the degree to which the pressure-sensitive adhesive is removed depending on the presence or absence of the pattern 12.

In FIG. 6, all the adhesive is removed together with the transparent film in the portion without the pattern 12, but this is caused by the difference between the second adhesive layer 9 and the transparent film. Is sufficiently higher than the adhesive strength between the second pressure-sensitive adhesive layer 9 and the hologram layer 7. When the hologram layer 7 is cross-linked and cured, the adhesive strength between the second pressure-sensitive adhesive layer 9 and the hologram layer 7 does not easily increase, so that a peeling state similar to that shown in FIG. 6 is obtained.

As shown in FIG. 6, when the transparent film 8 is peeled off, the second pressure-sensitive adhesive layer 9 is peeled off between the layers closer to the transparent film 8 corresponding to the peelable pattern 12, and Side, the surface of the hologram layer 7 and the peeled surface of the transparent film have a whitish visible pattern. It can be seen that the transparent film 8 has been peeled off. Since the generated rough surface is not solved even if it is carefully reattached, it is possible to prevent the hologram label from being peeled off and transferred to another.

The whitish portion corresponding to the pattern 12 is prominent when the transparent film 8 is to be peeled off.
Although there is no intention of peeling between the transparent protective film 8 and the hologram layer 7, white turbidity occurs. In this case as well, it is possible to prevent the hologram label from being peeled off and transferred to another. Probably, if the sheet in such a sheet state is pulled to be peeled, the sheet will be bent to 90 ° or more. At the bent portion, the second pressure-sensitive adhesive layer 9 is compressed, and a search for an escape site is performed. It is considered that since the film swells in the direction in which the film is peeled off, the transparent film 8 is peeled off at a position where the adhesive strength is weak, while the entirety of the transparent film 8 remains adhered.

In the hologram laminate 1 of the present invention, countermeasures are taken between the transparent film 8 and the second pressure-sensitive adhesive layer 9, but after the transparent film 8 is peeled off, the hologram layer 7 remains. Even if there is a person who wants to paste the hologram layer 7 on another article by wiping off the pressure-sensitive adhesive, the hologram layer 7 and the first pressure-sensitive adhesive layer 6 have the following fixed relationship, It can prevent unauthorized intentions.

As described above, the hologram layer 7 composed of the volume hologram is not so tough, is easily stretched when stretched, and is somewhat soft. Specifically, the adhesive strength between the hologram layer 7 and the base material 2 is set to be equal to or greater than the 1% tensile strength of the hologram layer 7 (the tensile force required to extend the hologram layer 7 by 1%), and When the hologram layer 7 is to be peeled, the hologram layer 7 is stretched. Assuming that the size of the hologram label is 2 cm in length and width, it is 0.2 mm even if it extends 1%.
Although it is difficult to recognize a change in size with the naked eye, volume holograms have several interference fringes in the direction of thickness, so when stretched, the spacing between the interference fringes becomes narrower and the color of the entire hologram shifts to the blue side Then, the extension is visually recognized as a color change, and it can be seen that the film has been peeled off.

The color change of the hologram layer 7 is also caused by the solvent. After the transparent film 8 has been peeled off, if the remaining adhesive is to be wiped off with a solvent, the solvent penetrates into the hologram layer 7 and swells the hologram layer 7. As a result, the interval between interference fringes is increased, and as a result, the entire hologram is removed. Is shifted to the red side, and the elongation is visually recognized as a change in color. As described above, the volume hologram 7 has a built-in property that can be a countermeasure against counterfeiting. However, similar discoloration due to expansion and contraction can also be realized in a relief hologram by controlling the crosslink density to an extent that the hologram is easy to expand without making it a hard sphere generally distributed. In this case, the hue of the hologram layer shifts to the red side because the interval between the interference fringes is widened regardless of whether it is pulled or swollen.

The peelable sheet 11 may be omitted or laminated in the field of an adhesive label. If the upper surface of the transparent protective film 8 is peelable, the sheet of FIG. By overlapping or winding up a hologram label having the same structure as the hologram seal shown by 10, there is no problem.
Can be stored. However, the hologram label of the present invention is generally small, though it depends on the article to be pasted and the application, and the peelable sheet 11 is laminated to form the form shown in FIG. Each sheet other than the releasable sheet 11 is punched so as to have a predetermined outer shape, so-called “half-blanking”. Easy to use because the label can be removed. When mechanically attaching a hologram label, leave the peelable sheet attached,
It is easier to use the hologram label only by "half punching" and winding it up using a continuous peelable sheet to form a roll.

The release sheet may be a synthetic resin laminated paper, a synthetic paper, a synthetic resin film that has been subjected to a release treatment,
For example, it is preferable to use a PET film whose surface has been release-treated with a fluorine-based release agent, a silicone-based release agent, a stearic acid-based release agent, a wax-based release agent, or the like.

The peelable sheet 11 of the hologram label 10
The other layers are the same as the contents of the hologram laminate and will not be described because they are the same as those of the hologram laminate, and a method of manufacturing the hologram label 10 of the example shown in FIG. 3 will be described below. In order to manufacture the hologram label 10, the base material 2 is prepared beforehand, and a hologram-forming material and a protective film are laminated on a support film, and the hologram layer 7 is formed on the base material 2. Prepared in the form of a double-sided tape having a separator attached to both sides thereof, and applying a pressure-sensitive adhesive after forming, for example, a releasable pattern on the transparent protective film 8;
Laminate the separator to create an adhesive sheet.

First, after the protective film of the hologram-forming material is peeled off, exposure is performed from the support film side, the hologram is recorded, and then ultraviolet irradiation and heat treatment are performed to form a hologram. After the hologram is formed, the pressure-sensitive adhesive prepared in the form of a double-sided tape is applied to the trace where the protective film has been stuck, and an adhesive label for sticking the hologram layer 7 is formed. Leave the other separator on the double-sided tape intact. Next, the support film is peeled off to expose the hologram layer 7, and a transparent film is adhered to the exposed surface by peeling the separator. Thus, a label on which the transparent film 8, the second pressure-sensitive adhesive layer 9, the hologram layer 7, the first pressure-sensitive adhesive layer 6, and the separator are laminated is obtained from above. Finally, the separator below the first pressure-sensitive adhesive layer is peeled off and attached to the substrate. By the above process, the hologram label of the present invention and the hologram laminate of the present invention can be obtained.

In the description so far, the description will be made mainly with reference to FIGS. 3 (a) and 3 (b). The second adhesive layer 9 between the hologram layer 7 under the second adhesive layer 9 and the second adhesive layer 9 has a sufficient adhesive strength and a low adhesive strength. May be applied. For example, even in the case shown in FIGS. 3A and 3B, the first adhesive layer 6 may be provided with a portion having sufficient adhesive strength and a portion having insufficient adhesive strength.
In this case, the strength of the first pressure-sensitive adhesive layer bonding the upper and lower layers is smaller than the strength of the second pressure-sensitive adhesive layer bonding the upper and lower layers. When peeling is to be performed, it may be configured to peel at the position of the first pressure-sensitive adhesive layer 6.

4 (a) and 4 (b) are more complicated than those shown in FIGS. 3 (a) and 3 (b), but just below the adhesive layer 9 on the lower surface of the hologram layer 7. '
And a three-layer structure in which a transparent film 8 'is laminated through the hologram layer 7, which corresponds to the hologram layer 7 in FIGS. 3 (a) and 3 (b). In this case, since there are three pressure-sensitive adhesive layers, the setting of a portion having a sufficient adhesive strength and a portion having an insufficient adhesive strength in the pressure-sensitive adhesive layer 6 is performed for any one of the pressure-sensitive adhesive layers, It may be performed on two pressure-sensitive adhesive layers or on all three pressure-sensitive adhesive layers. In the hologram laminate or hologram label as shown in FIGS. 4A and 4B, the lowermost one of the three pressure-sensitive adhesive layers is a pressure-sensitive adhesive layer 6 such as a pigment or a dye. It may be composed of an adhesive colored with. The strength of each adhesive layer bonding the upper and lower layers, if all are the same, the site of peeling is not determined, so set the adhesive strength of the place you want to peel the lowest, and thereafter, peel first It is preferable that the adhesive strength of the part to be removed is set to the next lowest value, and the part to be peeled off last is set to the highest adhesive strength.

[0074]

EXAMPLES (Example 1) As a base material, an identification card with a credit card-sized photo of a face was prepared, and a hologram seal was attached on the photo to seal the photo of the face. As a material for forming a hologram, a photosensitive resin composition (Omidex 706) is applied to a thickness of 50 μm on a polyethylene terephthalate film with a thickness of 20 μm.
Further, a polyvinyl chloride film having a thickness of 50 μm was adhered to prepare a laminate A for forming a hologram. Next, the first adhesive having the following composition was used.

[0075]

[Table 1]

On a silicone separator (manufactured by Tokyo Cellophane Co., Ltd., SP-PET05, thickness 50 μm),
The first pressure-sensitive adhesive having the composition shown in "Table 1" was applied using a comma coater so that the thickness of the coating film after drying became 12 μm. Separately, a polyethylene terephthalate film (Lumilar T-60, manufactured by Toray Industries, Inc., having a thickness of 50 μm) is prepared.
A predetermined character was printed by gravure printing using a material obtained by adding 8% of silicone to 100 parts by weight of an acrylic resin-based binder, and the first adhesive was applied before printing. The laminated body B was obtained by bonding together such that the side faced the inner surface.

Next, the second adhesive having the following composition was used.

[0078]

[Table 2]

The same silicone separator as used in the laminate B (SP-PET0 manufactured by Tokyo Cellophane Co., Ltd.)
5, 50 μm in thickness), and applying a second pressure-sensitive adhesive having the composition shown in Table 2 using a comma coater so that the coating thickness when dried becomes 25 μm, and then another silicone separator (Tokyo) SP-PET0 manufactured by Cellophane Co., Ltd.
2. A thickness of 50 μm, this silicone separator requires a greater force when peeling than the silicone separator of the product number SP-PET05. ) Were laminated to obtain a laminate C. The laminate C is used when attaching the hologram layer to the substrate 2.

First, after the polyvinyl chloride film of the laminate A was peeled off, the surface of the photosensitive resin composition was exposed, and a volume hologram master (having a Lippmann hologram) was brought into close contact therewith, and from the polyethylene terephthalate film side. Exposure using an argon laser having a wavelength of 488 nm to form a Lippmann hologram, and after exposure,
An ultraviolet ray of 600 mJ / cm ² was irradiated.

On the side of the hologram layer on which the polyethylene terephthalate film is not attached, a silicone separator of the laminate C (SP-PE, manufactured by Tokyo Cellophane Co., Ltd.)
T05, with a thickness of 50 μm), and the two were laminated. As a result, a polyethylene terephthalate film / hologram layer / second pressure-sensitive adhesive / silicone separator (symbol "/" indicates that both layers were laminated) was obtained. Subsequently, the polyethylene terephthalate film on the hologram layer is peeled off, and a laminate obtained by peeling the silicone separator from the laminate B is pasted on the mark, so that the printed polyethylene terephthalate film / first adhesive / hologram layer / second adhesive A hologram seal consisting of the agent / silicone separator was obtained, and further subjected to a heat treatment at 140 ° C. for 15 minutes.

The silicone separator was peeled off from the obtained hologram seal, stuck on the photograph of the identification card, and left overnight at room temperature. The hologram sticker attached to the identification card did not change its appearance even after being left overnight, and the characters printed on the transparent film were not visible from the surface. When I tried to peel off the attached hologram seal from the photo, the polyethylene terephthalate film as a transparent protective film was peeled off, the hologram layer remained on the photo, and the adhesive remained on the hologram layer in a character shape, Similarly, the pressure-sensitive adhesive remained on the transparent film side in the form of letters. At this stage, an attempt was made to return the transparent film to its original state, but the characters formed did not disappear and traces of peeling remained. Furthermore, when I tried to peel off the hologram layer left on the photo, the hologram stretched and turned green,
Reuse is no longer possible.

Example 2 A laminate A was prepared in the same manner as in Example 1, and the adhesive 2 in Table 2 of Example 1 was used as the first adhesive. A laminate B was obtained in the same manner as in Example 1. This laminate B is used when the hologram layer is attached to the base material. Next, a laminate D was obtained by the same operation as in the production of the laminate C in Example 1 except that the one in "Table 2" in Example 1 was used as the second pressure-sensitive adhesive.

After performing hologram exposure and ultraviolet irradiation using the prepared laminate A, a laminate obtained by removing the silicone separator from the laminate C on the side of the hologram layer having no polyethylene terephthalate was printed. A hologram seal composed of a polyethylene terephthalate film / second pressure-sensitive adhesive layer / hologram layer / third pressure-sensitive adhesive layer / silicone separator was obtained.

Further, the hologram seal of the third
Peeling off the silicone separator on the pressure-sensitive adhesive layer, laminating the laminate B on the peeled mark, and printing the printed polyethylene terephthalate film / second pressure-sensitive adhesive layer / hologram layer /
Third adhesive layer / polyethylene terephthalate film /
A hologram seal comprising the first pressure-sensitive adhesive layer / silicone separator was obtained.

The silicone separator was peeled off from the obtained hologram seal, stuck on the photograph of the identification card, and left overnight at room temperature. The hologram sticker attached to the identification card did not change its appearance even after being left overnight, and the characters printed on the transparent film were not visible from the surface. If you try to peel off the attached hologram sticker from the photograph, the characters will appear between the first adhesive layer and the polyethylene terephthalate film. It was clear that the letters that had turned off did not disappear and were removed.

[0087]

According to the invention of claim 1, when the hologram label stuck on the article is to be peeled off, the transparent protective film on the surface is separated and peeled off, and the transparent protective film is stuck. Since the adhesive remains separately on the transparent protective film and the lower hologram layer, it is clear that the adhesive has been peeled off.Moreover, since it does not return even if it is tried to return to its original state, the hologram label is peeled off with improper intention. It is possible to prevent the genuine state from being re-attached. According to the invention of claim 2, in addition to the effect of the invention of claim 1, when peeling the transparent protective film, the effect that the adhesive does not partially adhere to the transparent protective film side is promoted. Claim 3
According to the invention of (1), in addition to the effect of the invention of claim 1, when peeling the transparent protective film, the effect that the adhesive partially adheres to the transparent protective film side is promoted. According to the fourth aspect of the present invention, in addition to the effects of any one of the first to third aspects, when the hologram layer is to be peeled, the hologram layer is elongated and the interval between interference fringes is reduced. It is clear that the layer has discolored and peeled, and the color will be different from the authentic one, so even if the change of the transparent protective film can be cleared, the hologram layer is reused with an unintended intention Can be prevented. According to the invention of claim 5, when the adhesive is applied to an article and then is to be peeled off, the transparent protective film on the surface is separated and peeled off. The hologram layer is separated into the lower hologram layer and the lower hologram layer, which makes it clear that the hologram layer has been peeled off. Can easily be manufactured for various articles. According to the invention of claim 6, in addition to the effect of the invention of claim 5, when the transparent protective film is peeled off, the laminate in which the effect that the adhesive does not partially adhere to the transparent protective film side is promoted, Can be manufactured. According to the invention of claim 7, in addition to the effect of the invention of claim 5, when the transparent protective film is peeled off, the laminate in which the effect that the adhesive partially adheres to the transparent protective film side is facilitated can be easily formed. Can be manufactured. According to the invention of claim 8, in addition to the effect of any one of the inventions of claims 5 to 7, when the hologram layer is to be peeled off, the hologram layer is elongated and the interval between interference fringes is reduced. It is clear that the layer has discolored and peeled, and the color will be different from the authentic one, so even if the change of the transparent protective film can be cleared, the hologram layer is reused with an unintended intention It is possible to easily manufacture a laminate that can prevent the occurrence of the above. According to the ninth aspect of the present invention, in addition to the effect of any one of the fifth to eighth aspects, a peelable sheet is added, which is convenient for handling a hologram label. According to the tenth aspect of the present invention, the hologram is peeled off from the adherend, and at that time, the pressure-sensitive adhesive that has been applied remains separately in the transparent protective film and the lower hologram layer.
Since it is clear that the hologram label has been peeled off and the hologram label is not returned even if it is returned, it is possible to prevent the hologram label from being peeled off with an unintended intention and replaced with another to impersonate a genuine state. According to the eleventh aspect, in addition to the effect of the tenth aspect, an effect that the adhesive does not partially adhere to the hologram side when the hologram is peeled off is promoted. According to the twelfth aspect of the invention, in addition to the effect of the tenth aspect, the effect of the adhesive partially adhering to the hologram side when the hologram is peeled off is promoted. According to the thirteenth aspect, in addition to the effect of any one of the tenth to twelfth aspects, when the hologram layer is to be peeled, the hologram layer is elongated, and the interval between the interference fringes is reduced. It is clear that the layer has been discolored and peeled, and the color is different from the authentic one, so that it is possible to prevent the hologram layer from being reused with improper intention. According to the invention of claim 14, in addition to the effect of any of the inventions of claims 10 to 12, when the hologram layer is to be peeled off, the hologram layer is elongated and the interval between interference fringes is reduced. It is clear that the layer has been discolored and peeled, and the color is different from the authentic one, so that it is possible to prevent the hologram layer from being reused with improper intention. According to the invention of claim 15, in addition to the effect of the invention of claim 14, the effect that the adhesive does not partially adhere to the hologram side when peeling the hologram is promoted. According to the invention of claim 16,
In addition to the effect of the fourteenth aspect, the effect that the adhesive partially adheres to the hologram side when peeling the hologram is promoted. According to the seventeenth aspect, claims 14 to
16 In addition to the effects of any one of the inventions, when the hologram layer is to be peeled, the hologram layer is elongated, and the interval between the interference fringes is narrowed. Since the color of the hologram layer is different from that of the hologram layer, it is possible to prevent the hologram layer from being reused with improper intention. According to the eighteenth aspect of the present invention,
17 In addition to the effects of any one of the inventions, when the hologram layer is to be peeled, the hologram layer is elongated, and the interval between the interference fringes is narrowed. Since the color of the hologram layer is different from that of the hologram layer, it is possible to prevent the hologram layer from being reused with improper intention. According to the invention of claim 19, in addition to the effect of the invention, when the hologram layer is to be peeled, the hologram layer is elongated, and the interval between the interference fringes is narrowed. The hologram layer is clear and has a different color from the authentic one, so that it is possible to prevent the hologram layer from being reused with an unintended intention. According to the twentieth aspect of the present invention, since it can be configured to separate and adhere to the upper layer and the lower layer when peeling off to any of the pressure-sensitive adhesive layers, it is possible to prevent unauthorized peeling according to the application. According to the invention of the twenty-first aspect, it is possible to provide a hologram label which is peeled off together with the hologram, and in which traces of the peeling remain. According to the invention of claim 22, the lower surface of the hologram is protected by the transparent film, and the entire hologram is peeled off.
Moreover, it is possible to provide a hologram laminate in which traces of peeling remain. According to the invention of claim 23, it is possible to provide a hologram label in which the lower surface of the hologram is protected by the transparent film, and the hologram is peeled off together with a trace of the peeling. According to the invention of claim 24, it is possible to provide a hologram laminate in which the three pressure-sensitive adhesive layers can be peeled off in an arbitrarily set order, and even if any one of the three pressure-sensitive adhesive layers is peeled off, a trace of peeling remains. According to the invention of claim 25, the three pressure-sensitive adhesive layers can be peeled off in an arbitrary set order, and
Whichever is peeled off, it is possible to provide a hologram label that leaves a trace of peeling.

[Brief description of the drawings]

FIG. 1 is a plan view of a hologram laminate of the present invention applied to an identification card.

FIG. 2 is a sectional view taken along line AA of the identification card of FIG.

FIG. 3 is a sectional view of a hologram laminate and a label.

FIG. 4 is a cross-sectional view of another hologram laminate and a label.

FIG. 5 is a view showing a structure for partial peeling of a transparent protective film.

FIG. 6 is a view showing a state of peeling of a transparent protective film.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Identification card 2 Base material 3 Photograph 4 Hologram seal 5 Character 6 First adhesive layer 7 Hologram layer 8 Transparent protective film 9 Second adhesive layer 10 Hologram label 11 Peelable sheet 12 Pattern

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G09F 19/12 G09F 19/12 L

Claims (25)

[Claims] 1. A hologram layer is laminated on a base material via a first pressure-sensitive adhesive layer, and a transparent film is laminated on the hologram layer via a second pressure-sensitive adhesive layer. The adhesive force between the hologram layer and the hologram layer is greater than the adhesive strength between the transparent film and the second pressure-sensitive adhesive layer, when peeling the transparent film, the adhesive between the hologram layer and the transparent film A first portion whose strength is higher than the adhesive strength with the hologram layer and which remains on the transparent film side, and a second portion whose adhesive strength with the transparent film is weaker than the adhesive strength with the hologram layer and which remains on the hologram layer.
And a hologram laminate comprising: 2. The hologram laminate according to claim 1, further comprising a layer between both the transparent film and the second pressure-sensitive adhesive layer, the layer weakening the adhesive strength between the two layers. 3. The hologram laminate according to claim 1, wherein a layer for increasing the adhesive strength between the transparent film and the second pressure-sensitive adhesive layer is partially provided between the two layers. 4. The hologram laminate according to claim 1, wherein an adhesive strength between the hologram layer and the substrate is larger than a 1% tensile strength of the hologram. 5. A first pressure-sensitive adhesive layer, a hologram layer, a second pressure-sensitive adhesive layer, and a transparent film are laminated in this order from the lower side, and the second pressure-sensitive adhesive layer is used when the transparent film is peeled off. In addition, the adhesive strength with the transparent film is stronger than the adhesive strength with the hologram layer, and the first portion remaining on the transparent film side, and the adhesive strength with the transparent film is weaker than the adhesive strength with the hologram layer. A hologram label having a second portion remaining on the hologram layer. 6. The hologram label according to claim 5, wherein a layer for weakening the adhesive strength between the second pressure-sensitive adhesive layer and the transparent film is partially provided between the two layers. 7. The hologram label according to claim 5, wherein a layer for increasing the adhesive strength between the second pressure-sensitive adhesive layer and the transparent film is partially provided between the two layers. 8. The hologram label according to claim 5, wherein an adhesive strength between the hologram layer and the substrate is larger than a 1% tensile strength of the hologram layer. 9. The hologram label according to claim 5, wherein a releasable sheet is further laminated below the first pressure-sensitive adhesive layer. 10. A hologram layer is laminated on a base material via a first pressure-sensitive adhesive layer, and the hologram layer has a second surface on a lower surface thereof.
A first transparent film is laminated via the pressure-sensitive adhesive layer, a second transparent film is laminated on the hologram layer via a third pressure-sensitive adhesive layer, and The adhesive strength between the first transparent film is larger than the adhesive strength between the hologram layer and the second transparent film, and the third pressure-sensitive adhesive layer is used for peeling of the second transparent film. At this time, the adhesive strength between the first portion remaining on the second transparent film side and the adhesive strength between the second transparent film and the second transparent film is stronger than the adhesive strength with the hologram layer. A hologram laminate comprising: a second portion that is weaker than the adhesive strength with the hologram layer and remains on the hologram layer. 11. The hologram laminate according to claim 10, further comprising a layer between the two layers of the second transparent film and the third pressure-sensitive adhesive layer, the layer weakening the adhesive strength between the two layers. 12. The hologram laminate according to claim 10, wherein a layer for increasing the adhesive strength between the second transparent film and the third pressure-sensitive adhesive layer is partially provided between the two layers. 13. The hologram laminate according to claim 10, wherein the adhesive strength between the first transparent film and the substrate is larger than the 1% tensile strength of the hologram. 14. A first pressure-sensitive adhesive layer, a first transparent film, a second pressure-sensitive adhesive layer, a hologram layer, a third pressure-sensitive adhesive layer, and a second transparent film are laminated in this order from the lower side. And, the adhesive force between the substrate and the first transparent film is larger than the adhesive strength between the hologram layer and the second transparent film, and the third adhesive layer,
A first portion remaining on the side of the second transparent film, wherein the adhesive strength with the second transparent film is stronger than the adhesive strength with the hologram layer when the second transparent film is peeled off; 2. A hologram label, comprising: a second portion having a lower adhesive strength with the transparent film than the adhesive strength with the hologram layer and remaining on the hologram layer. 15. The hologram label according to claim 14, further comprising a layer for weakening the adhesive strength between the third pressure-sensitive adhesive layer and the second transparent film, between the two layers. 16. The hologram label according to claim 14, wherein a layer for increasing the adhesive strength between the third pressure-sensitive adhesive layer and the second transparent film is partially provided between the two layers. 17. The hologram label according to claim 14, wherein the adhesive strength between the first transparent film and the substrate is larger than the 1% tensile strength of the hologram layer. 18. The hologram label according to claim 14, wherein a releasable sheet is further laminated below the first pressure-sensitive adhesive layer. 19. A hologram layer is laminated on a base material via a first pressure-sensitive adhesive layer, and a transparent film is laminated on the hologram layer via a second pressure-sensitive adhesive layer. The adhesive strength between the hologram layer is smaller than the adhesive strength between the hologram layer and the transparent film, and
The first pressure-sensitive adhesive layer, when peeling the hologram layer and the substrate, the first portion that remains on the hologram layer side, the adhesive strength with the hologram layer is stronger than the adhesive strength with the base material, A hologram laminate comprising: a second portion having a lower adhesive strength with the hologram layer than the adhesive strength with the substrate and remaining on the substrate. 20. A hologram layer is laminated on a base material via a first pressure-sensitive adhesive layer, and a transparent film is laminated on the hologram layer via a second pressure-sensitive adhesive layer. The adhesive strength between the hologram layer and the adhesive strength between the hologram layer and the transparent film is larger or smaller, and the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are both peeled off. A hologram laminate having a portion remaining on the upper layer side and a portion remaining on the lower layer side. 21. A first pressure-sensitive adhesive layer, a hologram layer, a second pressure-sensitive adhesive layer, and a transparent film are laminated in this order from below, and the first pressure-sensitive adhesive layer is used when the hologram layer is peeled off. A hologram label comprising: a first portion having a high adhesive strength with the hologram layer and remaining on the hologram layer side; and a second portion having a low adhesive strength with the hologram layer. 22. A hologram layer is laminated on a base material via a first pressure-sensitive adhesive layer, and the hologram layer has a second surface on a lower surface thereof.
A first transparent film is laminated via the pressure-sensitive adhesive layer, a second transparent film is laminated on the hologram layer via a third pressure-sensitive adhesive layer, and The adhesive force between the first transparent film is smaller than the adhesive strength between the hologram layer and the second transparent film, and the first pressure-sensitive adhesive layer is used for peeling of the first transparent film. At this time, the adhesive strength between the first transparent film and the first portion remaining on the first transparent film side, where the adhesive strength with the first transparent film is stronger than the adhesive strength with the base material, A hologram laminate comprising: a second portion that is weaker in adhesive strength to the substrate and remains on the substrate. 23. A first pressure-sensitive adhesive layer, a first transparent film, a second pressure-sensitive adhesive layer, a hologram layer, a third pressure-sensitive adhesive layer, and a second transparent film are laminated in this order from the lower side. And, the adhesive force between the substrate and the first transparent film is smaller than the adhesive strength between the hologram layer and the second transparent film, and the first pressure-sensitive adhesive layer,
When the first transparent film is peeled off, the adhesive strength between the first transparent film and the first portion remaining on the first transparent film side and the adhesive strength between the first transparent film and the second transparent film are increased. A hologram label having a weak second portion. 24. A hologram layer is laminated on a substrate with a first pressure-sensitive adhesive layer interposed therebetween, and the hologram layer has a second
A first transparent film is laminated via the pressure-sensitive adhesive layer, and a second transparent film is laminated on the hologram layer via a third pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer has a difference in the adhesive strength between the upper layer and the lower layer, and both, when peeled in the pressure-sensitive adhesive layer,
A hologram laminate having a portion remaining on the upper layer side and a portion remaining on the lower layer side. 25. A first pressure-sensitive adhesive layer, a first transparent film, a second pressure-sensitive adhesive layer, a hologram layer, a third pressure-sensitive adhesive layer, and a second transparent film are laminated in this order from the lower side. , The first to third pressure-sensitive adhesive layers have a difference in adhesive strength,
In addition, a hologram label characterized by having a portion that remains on the upper layer side and a portion that does not remain on the upper layer side when the adhesive layer is peeled off.